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TWI859372B - Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device and resin - Google Patents

Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device and resin Download PDF

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TWI859372B
TWI859372B TW109142390A TW109142390A TWI859372B TW I859372 B TWI859372 B TW I859372B TW 109142390 A TW109142390 A TW 109142390A TW 109142390 A TW109142390 A TW 109142390A TW I859372 B TWI859372 B TW I859372B
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TW202128841A (en
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野崎敦靖
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日商富士軟片股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/145—Polyamides; Polyesteramides; Polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G03F7/008—Azides
    • G03F7/012—Macromolecular azides; Macromolecular additives, e.g. binders
    • G03F7/0125—Macromolecular azides; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the macromolecular azides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/094—Multilayer resist systems, e.g. planarising 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

本發明提供一種硬化性樹脂組成物、將上述硬化性樹脂組成物硬化而成之硬化膜、包含上述硬化膜之積層體、上述硬化膜的製造方法及包含上述硬化膜或上述積層體之半導體器件以及提供一種包含特定結構之新型的樹脂，其中，該硬化性樹脂組成物包括包含下述式（1-1）所表示之重複單元且包含選自包括下述式（2-1）所表示之重複單元、下述式（2-2）所表示之重複單元、下述式（2-3）所表示之重複單元及下述式（2-4）所表示之重複單元之群組中的至少一種重複單元之樹脂及溶劑。The present invention provides a curable resin composition, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate, and a novel resin including a specific structure, wherein the curable resin composition includes a resin including a repeating unit represented by the following formula (1-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (2-1), a repeating unit represented by the following formula (2-2), a repeating unit represented by the following formula (2-3), and a repeating unit represented by the following formula (2-4), and a solvent.

Description

硬化性樹脂組成物、硬化膜、積層體、硬化膜的製造方法、半導體器件及樹脂Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device and resin

本發明係有關一種硬化性樹脂組成物、硬化膜、積層體、硬化膜的製造方法、半導體器件及樹脂。The present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, a semiconductor device and a resin.

由於聚醯亞胺的耐熱性及絕緣性優異，因此適用於各種用途。作為上述用途並無特別限定，若舉出實際安裝用半導體器件為例，則可以舉出作為絕緣膜或密封材料的材料或保護膜的利用。又，亦可以用作撓性基板的基底膜或覆蓋膜等。Since polyimide has excellent heat resistance and insulation, it is suitable for various uses. The above uses are not particularly limited. If a semiconductor device for actual mounting is cited as an example, it can be used as an insulating film or a sealing material or a protective film. In addition, it can also be used as a base film or a cover film of a flexible substrate.

例如，在上述用途中，聚醯亞胺有時以包含聚醯亞胺之硬化性樹脂組成物的形態使用，亦有時以包含聚醯亞胺前驅物等之硬化性樹脂組成物的形態使用。上述前驅物例如藉由加熱等進行環化而形成為聚醯亞胺等樹脂。 該等硬化性樹脂組成物能夠藉由公知的塗佈方法等而適用於基材等，因此可以說製造上的適應性優異，例如所適用之硬化性樹脂組成物的形狀、大小、適用位置等設計的自由度高等。 從除了聚醯亞胺等樹脂具有之高性能以外該種製造上的適應性亦優異之觀點考慮，越來越期待針對包含聚醯亞胺或聚醯亞胺前驅物之硬化性樹脂組成物在產業上的應用拓展。For example, in the above-mentioned uses, polyimide is sometimes used in the form of a curable resin composition containing polyimide, and sometimes in the form of a curable resin composition containing a polyimide precursor. The above-mentioned precursor is cyclized by heating, etc. to form a resin such as polyimide. Such curable resin compositions can be applied to substrates, etc. by known coating methods, etc., so it can be said that the adaptability in manufacturing is excellent, for example, the degree of freedom in designing the shape, size, and application position of the curable resin composition to be applied is high. In addition to the high performance of resins such as polyimide, the manufacturing adaptability is also excellent. Therefore, the application of curable resin compositions containing polyimide or polyimide precursors in the industry is increasingly expected to expand.

例如，在專利文獻1中記載了一種感光性樹脂組成物，其係包含：具有特定結構之聚醯胺酸；光聚合性化合物；及光聚合起始劑。For example, Patent Document 1 describes a photosensitive resin composition comprising: a polyamine having a specific structure; a photopolymerizable compound; and a photopolymerization initiator.

[專利文獻1]日本特表2004-285129號公報[Patent Document 1] Japanese Patent Publication No. 2004-285129

在包含聚醯亞胺之硬化性樹脂組成物中，期望提供一種所獲得之硬化膜的耐藥品性優異之硬化性樹脂組成物。It is desirable to provide a curable resin composition containing polyimide, in which the obtained cured film has excellent chemical resistance.

本發明的一實施態樣的目的為，提供一種所獲得之硬化膜的耐藥品性優異之硬化性樹脂組成物、將上述硬化性樹脂組成物硬化而成之硬化膜、包含上述硬化膜之積層體、上述硬化膜的製造方法及包含上述硬化膜或上述積層體之半導體器件。 又，本發明的另一實施態樣的目的為，提供一種新型的樹脂。The purpose of one embodiment of the present invention is to provide a curable resin composition having excellent chemical resistance of the obtained cured film, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for manufacturing the cured film, and a semiconductor device including the cured film or the laminate. In addition, the purpose of another embodiment of the present invention is to provide a new type of resin.

以下，記載本發明的代表性實施態樣的例子。 ＜1＞一種硬化性樹脂組成物，其係包括包含下述式（1-1）所表示之重複單元且包含選自包括下述式（2-1）所表示之重複單元、下述式（2-2）所表示之重複單元、下述式（2-3）所表示之重複單元及下述式（2-4）所表示之重複單元之群組中的至少一種重複單元之樹脂及溶劑； [化學式1] 式（1-1）中，Y1 表示2價連接基，Ar1 表示取代基或可以具有縮合環結構之芳香族烴基，Y2 表示單鍵或2價連接基； 式（2-1）中，X1 表示4價連接基，A1 及A2 分別獨立地表示氧原子或-NRN -，R1 及R2 分別獨立地表示1價有機基，RN 表示氫原子或烴基； 式（2-2）中，X2 表示4價連接基； 式（2-3）中，X3 表示3價連接基； 式（2-4）中，X4 表示3價連接基，A4 表示氧原子或-NRN -，R4 表示1價有機基，RN 表示氫原子或烴基。 ＜2＞如＜1＞所述之硬化性樹脂組成物，其中，上述樹脂係包含選自包括下述式（3-1）所表示之重複單元、下述式（3-2）所表示之重複單元、下述式（3-3）所表示之重複單元及下述式（3-4）所表示之重複單元之群組中的至少一種重複單元， [化學式2] 式（3-1）中，X5 表示4價連接基，R3 及R4 分別獨立地表示1價有機基，Z1 表示2價連接基，R3 、R4 及Z1 中的至少一個包含聚合性基； 式（3-2）中，X6 表示4價連接基，Z2 表示具有聚合性基之2價連接基； 式（3-3）中，X7 及X8 分別獨立地表示3價連接基，Z3 及Z4 分別獨立地表示2價連接基，Z3 及Z4 中的至少一者表示具有聚合性基之2價連接基； 式（3-4）中，X7 及X8 分別獨立地表示3價連接基，Z3 及Z4 分別獨立地表示2價連接基，R5 及R6 分別獨立地表示1價有機基，Z3 及Z4 中的至少一者表示具有聚合性基之2價連接基，R5 、R6 、Z3 及Z4 中的至少一個包含聚合性基。 ＜3＞如＜2＞所述之硬化性樹脂組成物，其中，上述式（3-1）所表示之重複單元中所包含之聚合性基或上述式（3-2）所表示之重複單元中所包含之聚合性基為包括包含乙烯性不飽和鍵之基團、環狀醚基、羥甲基或烷氧基甲基之基團。 ＜4＞如＜1＞至＜3＞之任一項所述之硬化性樹脂組成物，其中，上述式（1-1）所表示之重複單元的含量相對於樹脂的總質量為0.1質量%～60質量%。 ＜5＞如＜1＞至＜4＞之任一項所述之硬化性樹脂組成物，其係包含聚合性化合物。 ＜6＞如＜1＞至＜5＞之任一項所述之硬化性樹脂組成物，其係用於形成再配線層用層間絕緣膜。 ＜7＞一種硬化膜，其係將＜1＞至＜6＞之任一項所述之硬化性樹脂組成物硬化而成。 ＜8＞一種積層體，其係具有兩層以上的＜7＞所述之硬化膜，並且在任意上述硬化膜彼此之間具有金屬層。 ＜9＞一種硬化膜的製造方法，其係包括將＜1＞至＜6＞之任一項所述之硬化性樹脂組成物適用於基板上以形成膜之膜形成步驟。 ＜10＞如＜9＞所述之硬化膜的製造方法，其係包括在50～450℃下對上述膜進行加熱之步驟。 ＜11＞一種半導體器件，其係具有＜7＞所述之硬化膜或＜8＞所述之積層體。 ＜12＞一種樹脂，其係包含下述式（1-1）所表示之重複單元且包含選自包括下述式（3-1）所表示之重複單元、下述式（3-2）所表示之重複單元、下述式（3-3）所表示之重複單元及下述式（3-4）所表示之重複單元之群組中的至少一種重複單元； [化學式3] 式（1-1）中，Y1 表示2價連接基，Ar1 表示取代基或可以具有縮合環結構之芳香族烴基，Y2 表示單鍵或2價連接基； 式（3-1）中，X5 表示4價連接基，R3 及R4 分別獨立地表示1價有機基，Z1 表示2價連接基，R3 、R4 及Z1 中的至少一個包含聚合性基； 式（3-2）中，X6 表示4價基團，Z2 表示具有聚合性基之2價連接基； 式（3-3）中，X7 及X8 分別獨立地表示3價連接基，Z3 及Z4 分別獨立地表示2價連接基，Z3 及Z4 中的至少一者表示具有聚合性基之2價連接基； 式（3-4）中，X7 及X8 分別獨立地表示3價連接基，Z3 及Z4 分別獨立地表示2價連接基，R5 及R6 分別獨立地表示1價有機基，Z3 及Z4 中的至少一者表示具有聚合性基之2價連接基，R5 、R6 、Z3 及Z4 中的至少一個包含聚合性基。 [發明效果]Representative embodiments of the present invention are described below. <1> A curable resin composition comprising a resin including a repeating unit represented by the following formula (1-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (2-1), a repeating unit represented by the following formula (2-2), a repeating unit represented by the following formula (2-3), and a repeating unit represented by the following formula (2-4), and a solvent; [Chemical Formula 1] In formula (1-1), Y1 represents a divalent linking group, Ar1 represents a substituent or an aromatic alkyl group which may have a condensed ring structure, and Y2 represents a single bond or a divalent linking group; In formula (2-1), X1 represents a tetravalent linking group, A1 and A2 each independently represent an oxygen atom or -NR N -, R1 and R2 each independently represent a monovalent organic group, and RN represents a hydrogen atom or a alkyl group; In formula (2-2), X2 represents a tetravalent linking group; In formula (2-3), X3 represents a trivalent linking group; In formula (2-4), X4 represents a trivalent linking group, A4 represents an oxygen atom or -NR N -, R4 represents a monovalent organic group, and RN represents a hydrogen atom or a alkyl group. <2> The curable resin composition as described in <1>, wherein the resin comprises at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), a repeating unit represented by the following formula (3-3), and a repeating unit represented by the following formula (3-4), [Chemical Formula 2] In formula (3-1), X5 represents a 4-valent connecting group, R3 and R4 each independently represent a monovalent organic group, Z1 represents a divalent connecting group, and at least one of R3 , R4 and Z1 contains a polymerizable group; In formula (3-2), X6 represents a 4-valent connecting group, and Z2 represents a divalent connecting group having a polymerizable group; In formula (3-3), X7 and X8 each independently represent a trivalent connecting group, Z3 and Z4 each independently represent a divalent connecting group, and at least one of Z3 and Z4 represents a divalent connecting group having a polymerizable group; In formula (3-4), X7 and X8 each independently represent a trivalent connecting group, Z3 and Z4 each independently represent a divalent connecting group, R5 and R6 each independently represent a monovalent organic group, and Z3 and Z4 each independently represent a divalent connecting group. At least one of R 5 , R 6 , Z 3 and Z 4 represents a divalent linking group having a polymerizable group, and at least one of R 5 , R 6 , Z 3 and Z 4 contains a polymerizable group. <3> The curable resin composition as described in <2>, wherein the polymerizable group contained in the repeating unit represented by the above formula (3-1) or the polymerizable group contained in the repeating unit represented by the above formula (3-2) is a group containing an ethylenically unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group. <4> The curable resin composition as described in any one of <1> to <3>, wherein the content of the repeating unit represented by the above formula (1-1) is 0.1 mass% to 60 mass% relative to the total mass of the resin. <5> The curable resin composition as described in any one of <1> to <4>, which contains a polymerizable compound. <6> A curable resin composition as described in any one of <1> to <5>, which is used to form an interlayer insulating film for a redistribution layer. <7> A cured film, which is formed by curing the curable resin composition as described in any one of <1> to <6>. <8> A laminate having two or more layers of the cured films as described in <7>, and having a metal layer between any of the cured films. <9> A method for producing a cured film, which includes a film forming step of applying the curable resin composition as described in any one of <1> to <6> on a substrate to form a film. <10> The method for producing a cured film as described in <9>, which includes a step of heating the above-mentioned film at 50 to 450°C. <11> A semiconductor device having the cured film described in <7> or the laminate described in <8>. <12> A resin comprising a repeating unit represented by the following formula (1-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), a repeating unit represented by the following formula (3-3), and a repeating unit represented by the following formula (3-4); [Chemical Formula 3] In formula (1-1), Y1 represents a divalent linking group, Ar1 represents a substituent or an aromatic hydrocarbon group which may have a condensed ring structure, and Y2 represents a single bond or a divalent linking group; In formula (3-1), X5 represents a tetravalent linking group, R3 and R4 each independently represent a monovalent organic group, Z1 represents a divalent linking group, and at least one of R3 , R4 and Z1 contains a polymerizable group; In formula (3-2), X6 represents a tetravalent group, and Z2 represents a divalent linking group having a polymerizable group; In formula (3-3), X7 and X8 each independently represent a trivalent linking group, Z3 and Z4 each independently represent a divalent linking group, and at least one of Z3 and Z4 represents a divalent linking group having a polymerizable group; In formula (3-4), X7 and X8 each independently represent a trivalent linking group, Z3 and Z4 each independently represent a divalent linking group, and at least one of Z3 and Z4 represents a divalent linking group having a polymerizable group; R5 and R6 each independently represent a trivalent linking group, Z3 and Z4 each independently represent a divalent linking group, R5 and R6 each independently represent a monovalent organic group, at least one of Z3 and Z4 represents a divalent linking group having a polymerizable group, and at least one of R5 , R6 , Z3 and Z4 contains a polymerizable group. [Effects of the Invention]

依據本發明的一實施態樣，提供一種所獲得之硬化膜的耐藥品性優異之硬化性樹脂組成物、將上述硬化性樹脂組成物硬化而成之硬化膜、包含上述硬化膜之積層體、上述硬化膜的製造方法及包含上述硬化膜或上述積層體之半導體器件。 又，依據本發明的另一實施態樣，提供一種新型的樹脂。According to one embodiment of the present invention, a curable resin composition having excellent chemical resistance of the obtained cured film, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for manufacturing the cured film, and a semiconductor device including the cured film or the laminate are provided. In addition, according to another embodiment of the present invention, a new type of resin is provided.

以下，對本發明的主要實施形態進行說明。然而，本發明並不限於所明示之實施形態。 在本說明書中，用“～”記號表示之數值範圍表示將記載於“～”的前後之數值分別作為下限值及上限值包括之範圍。 在本說明書中，“步驟”這一用語不僅表示獨立之步驟，只要能夠實現該步驟所預期之作用，則亦表示包括無法與其他步驟明確區分之步驟。 關於本說明書中之基團（原子團）的標記，未標註經取代及未經取代的標記同時包括不具有取代基的基團（原子團）和具有取代基之基團（原子團）。例如，“烷基”不僅包括不具有取代基的烷基（未經取代的烷基），而且還包括具有取代基之烷基（取代烷基）。 在本說明書中，在簡單記載為“脂肪族基”、“脂肪族烴基”、“飽和脂肪族烴基”、“烷基”、“伸烷基”等之情況下，除非另有說明，則該等基團可以具有支鏈結構及環狀結構中的至少一者。例如，除非另有說明，則“烷基”中包括直鏈烷基、支鏈烷基、環狀烷基及由該等組合表示之烷基。 在本說明書中，除非另有說明，則“曝光”不僅包括利用光之曝光，而且還包括利用電子束、離子束等粒子束之曝光。又，作為用於曝光之光，可以舉出水銀燈的明線光譜、以準分子雷射為代表之遠紫外線、極紫外線（EUV光）、X射線、電子束等光化射線或放射線。 在本說明書中，“（甲基）丙烯酸酯”表示“丙烯酸酯”及“甲基丙烯酸酯”這兩者或其中任一者，“（甲基）丙烯酸”表示“丙烯酸”及“甲基丙烯酸”這兩者或其中任一者，“（甲基）丙烯醯基”表示“丙烯醯基”及“甲基丙烯醯基”這兩者或其中任一者。 在本說明書中，結構式中的Me表示甲基，Et表示乙基，Bu表示丁基，Ph表示苯基。 在本說明書中，總固體成分是指組成物的所有成分中除了溶劑以外之成分的總質量。又，在本說明書中，固體成分濃度為除了溶劑以外之其他成分相對於組成物的總質量之質量百分率。 在本說明書中，除非另有說明，則重量平均分子量（Mw）及數量平均分子量（Mn）按照凝膠滲透層析法（GPC測定）被定義為聚苯乙烯換算值。在本說明書中，關於重量平均分子量（Mw）及數量平均分子量（Mn），例如能夠藉由使用HLC-8220GPC（TOSOH CORPORATION製），並使用保護管柱HZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、TSKgel Super HZ2000（TOSOH CORPORATION製）作為管住來求出。除非另有說明，則該等分子量為使用THF（四氫呋喃）作為洗滌液進行測定者。又，除非另有說明，則GPC測定中之檢測為使用UV線（紫外線）的波長254nm檢測器者。 在本說明書中，關於構成積層體之各層的位置關係，記載為“上”或“下”時，只要在所關注之複數層中成為基準之層的上側或下側存在其他層即可。亦即，亦可以在成為基準之層與上述其他層之間進一步夾有第3層或第3要素，並且成為基準之層與上述其他層無需接觸。又，除非另有說明，則將在基材上堆疊層之方向稱為“上”，或在存在硬化性樹脂組成物層之情況下，將從基材朝向硬化性樹脂組成物層之方向稱為“上”，將其相反方向稱為“下”。另外，該種上下方向的設定係為了便於說明本說明書，在實際態樣中，本說明書中之“上”方向亦可以與鉛垂朝上不同。 在本說明書中，除非另有說明，則作為組成物中所包含之各成分，組成物亦可以包含與該成分對應之兩種以上的化合物。又，除非另有說明，則組成物中之各成分的含量表示與該成分對應之所有化合物的合計含量。 在本說明書中，除非另有說明，則溫度為23℃，氣壓為101,325Pa（1氣壓），相對濕度為50%RH。 在本說明書中，較佳態樣的組合為更佳態樣。The main embodiments of the present invention are described below. However, the present invention is not limited to the embodiments indicated. In this specification, the numerical range indicated by the "～" sign indicates a range including the numerical values recorded before and after the "～" as the lower limit and the upper limit, respectively. In this specification, the term "step" not only indicates an independent step, but also includes steps that cannot be clearly distinguished from other steps as long as the expected effect of the step can be achieved. Regarding the marking of groups (atomic groups) in this specification, the marking of unsubstituted and unsubstituted includes both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, when simply described as "aliphatic group", "aliphatic alkyl group", "saturated aliphatic alkyl group", "alkyl group", "alkylene group", etc., unless otherwise specified, these groups may have at least one of a branched structure and a cyclic structure. For example, unless otherwise specified, "alkyl" includes straight-chain alkyl groups, branched-chain alkyl groups, cyclic alkyl groups, and alkyl groups represented by combinations thereof. In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, as the light used for exposure, the bright line spectrum of mercury lamp, far ultraviolet light represented by excimer laser, extreme ultraviolet light (EUV light), X-ray, electron beam and other actinic rays or radiation can be cited. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic acid" means both or either of "acrylic acid" and "methacrylic acid", and "(meth)acryl" means both or either of "acryl" and "methacryl". In this specification, Me in the structural formula represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl. In this specification, the total solid content refers to the total mass of all components of the composition except the solvent. In addition, in this specification, the solid content concentration is the mass percentage of the other components except the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using HLC-8220GPC (manufactured by TOSOH CORPORATION) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as the column. Unless otherwise specified, the molecular weights are measured using THF (tetrahydrofuran) as the washing liquid. Also, unless otherwise specified, the detection in the GPC measurement is performed using a UV (ultraviolet) detector with a wavelength of 254nm. In this specification, when the positional relationship of each layer constituting the laminate is recorded as "upper" or "lower", it is sufficient as long as other layers exist on the upper or lower side of the layer serving as the reference among the multiple layers concerned. In other words, a third layer or a third element may be further sandwiched between the layer serving as the reference and the other layers mentioned above, and the layer serving as the reference and the other layers mentioned above do not need to be in contact. Furthermore, unless otherwise specified, the direction of stacking layers on a substrate is referred to as "up", or in the case of a curable resin composition layer, the direction from the substrate toward the curable resin composition layer is referred to as "up", and the opposite direction is referred to as "down". In addition, the setting of the up and down directions is for the convenience of explaining this specification, and in actual forms, the "up" direction in this specification may also be different from the vertical direction. In this specification, unless otherwise specified, as each component contained in a composition, the composition may also contain two or more compounds corresponding to the component. Furthermore, unless otherwise specified, the content of each component in the composition represents the total content of all compounds corresponding to the component. In this manual, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325Pa (1 atmosphere), and the relative humidity is 50%RH. In this manual, the combination of the best state is the more preferred state.

（硬化性樹脂組成物） 本發明的硬化性樹脂組成物（以下，亦簡稱為“本發明的組成物”。）包括包含式（1-1）所表示之重複單元且包含選自包括式（2-1）所表示之重複單元、式（2-2）所表示之重複單元、下述式（2-3）所表示之重複單元及下述式（2-4）所表示之重複單元之群組中的至少一種重複單元之樹脂及溶劑。 以下，將包含式（1-1）所表示之重複單元且包含選自包括式（2-1）所表示之重複單元、式（2-2）所表示之重複單元、式（2-3）所表示之重複單元及下述式（2-4）所表示之重複單元之群組中的至少一種重複單元之樹脂亦稱為“特定樹脂”。 [化學式4] 式（1-1）中，Y1 表示2價連接基，Ar1 表示取代基或可以具有縮合環結構之芳香族烴基，Y2 表示單鍵或2價連接基； 式（2-1）中，X1 表示4價連接基，A1 及A2 分別獨立地表示氧原子或-NRN -，R1 及R2 分別獨立地表示1價有機基，RN 表示氫原子或烴基； 式（2-2）中，X2 表示4價連接基； 式（2-3）中，X3 表示3價連接基； 式（2-4）中，X4 表示3價連接基，A4 表示氧原子或-NRN -，R4 表示1價有機基，RN 表示氫原子或烴基。(Hardening resin composition) The hardening resin composition of the present invention (hereinafter, also referred to as "the composition of the present invention") comprises a resin including a repeating unit represented by formula (1-1) and at least one repeating unit selected from the group consisting of repeating units represented by formula (2-1), repeating units represented by formula (2-2), repeating units represented by the following formula (2-3) and repeating units represented by the following formula (2-4), and a solvent. Hereinafter, a resin including a repeating unit represented by formula (1-1) and at least one repeating unit selected from the group consisting of repeating units represented by formula (2-1), repeating units represented by formula (2-2), repeating units represented by formula (2-3) and repeating units represented by the following formula (2-4) is also referred to as a "specific resin". [Chemical formula 4] In formula (1-1), Y1 represents a divalent linking group, Ar1 represents a substituent or an aromatic alkyl group which may have a condensed ring structure, and Y2 represents a single bond or a divalent linking group; In formula (2-1), X1 represents a tetravalent linking group, A1 and A2 each independently represent an oxygen atom or -NR N -, R1 and R2 each independently represent a monovalent organic group, and RN represents a hydrogen atom or a alkyl group; In formula (2-2), X2 represents a tetravalent linking group; In formula (2-3), X3 represents a trivalent linking group; In formula (2-4), X4 represents a trivalent linking group, A4 represents an oxygen atom or -NR N -, R4 represents a monovalent organic group, and RN represents a hydrogen atom or a alkyl group.

本發明的硬化性樹脂組成物為負型硬化性樹脂組成物為較佳。 負型硬化性樹脂組成物是指在對由硬化性樹脂組成物形成之層進行了曝光之情況下，未曝光部分（非曝光部）被顯影液去除之組成物。The curable resin composition of the present invention is preferably a negative curable resin composition. A negative curable resin composition refers to a composition in which the unexposed portion (non-exposed portion) is removed by a developer when a layer formed by the curable resin composition is exposed.

由本發明的硬化性樹脂組成物獲得之硬化膜的耐藥品性優異。 可以獲得上述效果之機理尚不明確，但是推測為如下。The cured film obtained from the curable resin composition of the present invention has excellent chemical resistance. The mechanism by which the above effect can be achieved is not yet clear, but it is speculated as follows.

本發明的硬化性樹脂組成物包含特定樹脂。 其中，不同於先前所使用的聚醯亞胺樹脂或聚醯亞胺前驅物，特定樹脂包含式（1-1）所表示之重複單元。 式（1-1）所表示之重複單元包含芳香族烴環與㗁唑環縮合而形成之縮合環結構。上述縮合環結構的溶劑溶解性低，因此推測由包括包含式（1-1）所表示之重複單元之特定樹脂之硬化性樹脂組成物所獲得之硬化膜的耐藥品性優異。 又，在式（2-1）中，R1 及R2 分別獨立地為1價有機基。 認為與R1 或R2 為氫原子之情況相比，R1 及R2 為1價有機基之結構對極性溶劑、鹼性水溶液等藥品之溶解性低，因此耐藥品性優異。因此，推測即使在所獲得之硬化膜中殘存有R1 及R2 中的至少一者之情況下，亦可以獲得耐藥品性優異之硬化膜。 認為由於硬化膜的耐藥品性優異，因此例如在藉由將本發明的硬化性樹脂組成物硬化而成之硬化膜上還適用包含溶劑之其他硬化性樹脂組成物並使其硬化而製作積層體之情況下等，即使硬化膜接觸到顯影液或其他硬化性樹脂組成物，亦抑制硬化膜的溶解。 認為依據本發明，可以獲得一種硬化膜，該硬化膜例如對二甲基亞碸（DMSO）、N-甲基吡咯啶酮（NMP）等極性溶劑、氫氧化四甲基銨（TMAH）水溶液等鹼性水溶液或上述極性溶劑與上述鹼性水溶液的混合液的溶解性得到抑制，並且耐藥品性優異。The curable resin composition of the present invention includes a specific resin. Unlike the polyimide resin or polyimide precursor used previously, the specific resin includes a repeating unit represented by formula (1-1). The repeating unit represented by formula (1-1) includes a condensed ring structure formed by condensing an aromatic hydrocarbon ring with an oxazole ring. The solvent solubility of the above-mentioned condensed ring structure is low, so it is estimated that the cured film obtained by the curable resin composition including the specific resin including the repeating unit represented by formula (1-1) has excellent chemical resistance. In addition, in formula (2-1), R1 and R2 are each independently a monovalent organic group. Compared with the case where R1 or R2 is a hydrogen atom, the structure where R1 and R2 are monovalent organic groups is considered to have lower solubility in polar solvents, alkaline aqueous solutions and other chemicals, and therefore has excellent chemical resistance. Therefore, it is inferred that even when at least one of R1 and R2 remains in the obtained cured film, a cured film with excellent chemical resistance can be obtained. It is considered that due to the excellent chemical resistance of the cured film, when, for example, another curable resin composition containing a solvent is applied to the cured film formed by curing the curable resin composition of the present invention and cured to prepare a laminate, even if the cured film contacts a developer or other curable resin compositions, the dissolution of the cured film is suppressed. It is believed that according to the present invention, a cured film can be obtained, the cured film having suppressed solubility in polar solvents such as dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP), alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solutions, or mixed solutions of the above polar solvents and the above alkaline aqueous solutions, and having excellent chemical resistance.

其中，在專利文獻1中，對包含式（1-1）所表示之重複單元且包含選自包括式（2-1）所表示之重複單元、式（2-2）所表示之重複單元、式（2-3）所表示之重複單元及式（2-4）所表示之重複單元之群組中的至少一種重複單元之樹脂沒有記載亦沒有建議。又，在專利文獻1中之硬化性樹脂組成物中，存在所獲得之硬化膜的耐藥品性低的問題。Among them, Patent Document 1 does not describe or suggest a resin comprising a repeating unit represented by Formula (1-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by Formula (2-1), a repeating unit represented by Formula (2-2), a repeating unit represented by Formula (2-3), and a repeating unit represented by Formula (2-4). In addition, in the curable resin composition in Patent Document 1, there is a problem that the chemical resistance of the obtained cured film is low.

＜特定樹脂＞ 本發明的硬化性樹脂組成物包含特定樹脂。 特定樹脂包含式（1-1）所表示之重複單元且包含選自包括式（2-1）所表示之重複單元、式（2-2）所表示之重複單元、式（2-3）所表示之重複單元及式（2-4）所表示之重複單元之群組中的至少一種重複單元。 特定樹脂可以在側鏈上具有式（1-1）所表示之重複單元，但是在主鏈上具有上述重複單元為較佳。 又，特定樹脂可以在側鏈上具有選自包括式（2-1）所表示之重複單元、式（2-2）所表示之重複單元、式（2-3）所表示之重複單元及式（2-4）所表示之重複單元之群組中的至少一種重複單元，但是在主鏈上具有上述重複單元為較佳。 在本說明書中，“主鏈”是指在構成樹脂之高分子化合物的分子中相對最長的鍵結鏈，“側鏈”是指除此以外的鍵結鏈。<Specific resin> The curable resin composition of the present invention includes a specific resin. The specific resin includes a repeating unit represented by formula (1-1) and includes at least one repeating unit selected from the group consisting of a repeating unit represented by formula (2-1), a repeating unit represented by formula (2-2), a repeating unit represented by formula (2-3), and a repeating unit represented by formula (2-4). The specific resin may have the repeating unit represented by formula (1-1) on the side chain, but it is preferred to have the above-mentioned repeating unit on the main chain. Furthermore, the specific resin may have at least one repeating unit selected from the group consisting of repeating units represented by formula (2-1), repeating units represented by formula (2-2), repeating units represented by formula (2-3) and repeating units represented by formula (2-4) on the side chain, but it is preferred to have the above repeating units on the main chain. In this specification, "main chain" refers to the longest bond chain in the molecule of the polymer compound constituting the resin, and "side chain" refers to other bond chains.

[式（1-1）所表示之重複單元] -Ar1 - 式（1-1）中，Ar1 表示取代基或可以具有縮合環結構之芳香族烴基。 上述Ar1 中之芳香族烴基為碳數6～30的芳香族烴基為較佳，從苯環或萘環去除三個氫原子而獲得之基團為更佳，從苯環去除三個氫原子而獲得之基團為更佳。 式（1-1）中的氮原子和氧原子均與Ar1 中之芳香族烴基中所包含之環員直接鍵結為較佳。 又，Ar1 中之式（1-1）中的與氮原子的鍵結部位和與氧原子的鍵結部位位於相鄰位置為較佳。 在本說明書中，兩個鍵結部位位於環結構中之相鄰位置是指，存在某一鍵結部位之上述環結構中之環員和存在另一鍵結部位之上述環結構中之環員在環結構中為相鄰環員。例如，在環結構為苯環結構之情況下，相鄰位置為鄰位。 作為Ar1 中之取代基，能夠無特別限定地使用公知的取代基，可以舉出烷基、環狀烷基、烷氧基、芳基、芳氧基、鹵化烷基、羥基、羧基、磺酸基、鹵素原子等。 作為形成Ar1 中之縮合環結構之環結構，能夠無特別限定地使用公知的環結構，可以舉出吡咯環、呋喃環、噻吩環、㗁唑環、咪唑環、吡唑環、異㗁唑環、噻唑環、異噻唑環等芳香族雜環結構、吡咯啶環、四氫呋喃環、四氫噻吩環、咪唑啶環、吡唑啶環、㗁唑啶環、異㗁唑啶環、噻唑啶環、異噻唑啶環、二氧雜環戊烷環、二硫雜環戊烷環等飽和雜環結構等。 又，在本發明中，能夠將Ar1 設為不具有縮合環的態樣，亦能夠設為不具有取代基及縮合環的態樣。[Repeating unit represented by formula (1-1)] -Ar 1 - In formula (1-1), Ar 1 represents a substituent or an aromatic hydrocarbon group which may have a condensed ring structure. The aromatic hydrocarbon group in Ar 1 is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a group obtained by removing three hydrogen atoms from a benzene ring or a naphthalene ring, and even more preferably a group obtained by removing three hydrogen atoms from a benzene ring. It is preferred that the nitrogen atom and the oxygen atom in formula (1-1) are both directly bonded to the ring members contained in the aromatic hydrocarbon group in Ar 1. It is preferred that the bonding site to the nitrogen atom and the bonding site to the oxygen atom in formula (1-1) in Ar 1 are located at adjacent positions. In this specification, two bonding sites are located at adjacent positions in the ring structure, which means that the ring member in the above ring structure existing at a certain bonding site and the ring member in the above ring structure existing at another bonding site are adjacent ring members in the ring structure. For example, when the ring structure is a benzene ring structure, the adjacent positions are adjacent positions. As a substituent in Ar 1 , a known substituent can be used without particular limitation, and alkyl, cyclic alkyl, alkoxy, aryl, aryloxy, halogenated alkyl, hydroxyl, carboxyl, sulfonic acid, halogen atom, etc. can be cited. As the ring structure forming the condensed ring structure in Ar1 , a known ring structure can be used without particular limitation, and examples thereof include aromatic heterocyclic structures such as a pyrrole ring, a furan ring, a thiophene ring, an oxadiazole ring, an imidazole ring, a pyrazole ring, an isoxadiazole ring, a thiazole ring, and an isothiazole ring; and saturated heterocyclic structures such as a pyrrolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, an imidazolidinyl ring, a pyrazolidine ring, an oxadiazole ring, an isoxadiazole ring, a thiazole ring, and an isothiazolidinyl ring. Furthermore, in the present invention, Ar 1 may be in an embodiment not having a condensed ring, or may be in an embodiment not having a substituent and a condensed ring.

-Y1 - 式（1-1）中，Y1 表示2價連接基，烴基、雜環基或者至少一個烴基或雜環基與選自包括-O-、-C（=O）-、-S-、-S（=O）2 -及-NRN -之群組中的至少一個結構鍵結而獲得之基團為較佳，烴基為更佳。上述RN 表示氫原子或烴基，氫原子、烷基或芳香族烴基為更佳，氫原子或烷基為進一步較佳，氫原子為特佳。 作為Y1 中之烴基，可以為脂肪族烴基，亦可以為芳香族烴基，但是從顯影性的觀點考慮，芳香族烴基為較佳。 作為上述脂肪族烴基，飽和脂肪族烴基為較佳。又，上述脂肪族烴基的碳數為1～30為較佳，1～20為更佳，2～10為進一步較佳。 上述脂肪族烴基可以具有公知的取代基。作為取代基，可以舉出芳香族基、烷氧基、芳氧基、鹵素原子等。 作為上述芳香族烴基，碳數6～30的芳香族烴基為較佳，碳數6～20的芳香族烴基為更佳，從苯環結構去除至少兩個氫原子而獲得之基團為更佳。 上述芳香族烴基可以具有公知的取代基。作為取代基，可以舉出脂肪族烴基、烷氧基、芳氧基、鹵素原子等。 作為上述雜環基，可以為脂肪族雜環基、芳香族雜環基中的任一個，但是從顯影性的觀點考慮，芳香族雜環基為較佳。 作為上述雜環基中之雜原子，可以舉出氮原子、氧原子、硫原子、硒原子、矽原子等。 作為上述脂肪族雜環基，5員環或6員環之脂肪族雜環基為較佳，可以舉出吡咯啶環、吡唑啶環、咪唑啶環、四氫呋喃環、四氫噻吩環、哌啶環、哌𠯤環、四氫哌喃環、二㗁烷環、噻喃環、二噻喃環、嗎啉環、㗁𠯤環、硫代嗎啉環等。 作為上述芳香族雜環基，可以舉出吡咯環、咪唑環、三唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、三𠯤環、呋喃環、噻吩環、㗁唑環、異㗁唑環、噻唑環、異噻唑環、噻二唑環等。-Y 1 - In formula (1-1), Y 1 represents a divalent linking group, preferably a alkyl group, a heterocyclic group, or a group obtained by bonding at least one alkyl group or heterocyclic group to at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) 2 -, and -NR N -, and a alkyl group is more preferred. The above-mentioned RN represents a hydrogen atom or a alkyl group, more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. The alkyl group in Y 1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but from the viewpoint of developing properties, an aromatic hydrocarbon group is preferred. As the above-mentioned aliphatic alkyl group, a saturated aliphatic alkyl group is preferred. In addition, the carbon number of the above-mentioned aliphatic alkyl group is preferably 1 to 30, more preferably 1 to 20, and further preferably 2 to 10. The above-mentioned aliphatic alkyl group may have a known substituent. As the substituent, an aromatic group, an alkoxy group, an aryloxy group, a halogen atom, etc. can be cited. As the above-mentioned aromatic alkyl group, an aromatic alkyl group having a carbon number of 6 to 30 is preferred, an aromatic alkyl group having a carbon number of 6 to 20 is more preferred, and a group obtained by removing at least two hydrogen atoms from a benzene ring structure is more preferred. The above-mentioned aromatic alkyl group may have a known substituent. As the substituent, an aliphatic alkyl group, an alkoxy group, an aryloxy group, a halogen atom, etc. can be cited. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group, but an aromatic heterocyclic group is preferred from the viewpoint of developing properties. Examples of the hetero atom in the heterocyclic group include nitrogen, oxygen, sulfur, selenium, and silicon atoms. As the above-mentioned aliphatic heterocyclic group, a 5-membered or 6-membered aliphatic heterocyclic group is preferred, and examples thereof include a pyrrolidine ring, a pyrazolidine ring, an imidazolidinyl ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a piperidine ring, a tetrahydropyran ring, a dioxane ring, a thiopyran ring, a dithiopyran ring, a morpholine ring, a pyridine ring, a thiophene ring, and a thiomorpholine ring. Examples of the aromatic heterocyclic group include a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a thiazolidine ring, a pyrimidine ring, a triazine ring, a furan ring, a thiophene ring, an oxadiazole ring, an isoxadiazole ring, a thiazole ring, an isothiazole ring, and a thiadiazole ring.

-Y2 - 式（1-1）中，Y2 表示單鍵或2價有機基，單鍵為較佳。 作為Y2 中之2價連接基，可以舉出與上述Y1 中之2價連接基相同的基團，較佳態樣亦相同。-Y 2 - In formula (1-1), Y 2 represents a single bond or a divalent organic group, and a single bond is preferred. As the divalent linking group in Y 2 , the same groups as those for the divalent linking group in Y 1 can be cited, and the preferred embodiments are also the same.

-含量- 特定樹脂中所包含之式（1-1）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～60質量%為較佳，3～30質量%為更佳。 又，特定樹脂可以僅包含一種式（1-1）所表示之重複單元，亦可以包含兩種以上的不同結構之式（1-1）所表示之重複單元。在包含兩種以上的式（1-1）所表示之重複單元之情況下，式（1-1）所表示之重複單元的合計含量在上述範圍內為較佳。-Content- The content of the repeating unit represented by formula (1-1) contained in the specific resin is preferably 0.1 to 60 mass % relative to the total mass of the specific resin, and more preferably 3 to 30 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (1-1), or may contain two or more repeating units represented by formula (1-1) of different structures. When containing two or more repeating units represented by formula (1-1), the total content of the repeating units represented by formula (1-1) is preferably within the above range.

又，下述式（1-1’）所表示之結構的莫耳量相對於特定樹脂1g為0.01～2mmol/g為較佳，0.05～1.5mmol/g為更佳，0.1～1mmol/g為進一步較佳。 [化學式5] 式（1-1’）中，Ar1 與式（1-1）中的Ar1 的含義相同，較佳態樣亦相同。 式（1-1’）中，兩個*分別獨立地表示與其他結構的鍵結部位。Furthermore, the molar amount of the structure represented by the following formula (1-1') is preferably 0.01 to 2 mmol/g, more preferably 0.05 to 1.5 mmol/g, and even more preferably 0.1 to 1 mmol/g, based on 1 g of the specific resin. [Chemical Formula 5] In formula (1-1'), Ar 1 has the same meaning as Ar 1 in formula (1-1), and a preferred embodiment is also the same. In formula (1-1'), two *s each independently represent a bonding site with other structures.

[式（2-1）所表示之重複單元] -X1 - 式（2-1）中，X1 表示4價連接基，可以例示直鏈狀或支鏈狀的脂肪族基、環狀的脂肪族基、芳香族基、雜芳族基團或者單鍵或藉由連接基將該等連接兩個以上而獲得之基團，碳數2～20的直鏈的脂肪族基、碳數3～20的支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族基或者單鍵或藉由連接基將該等組合兩個以上而獲得之基團為較佳，碳數6～20的芳香族基或者單鍵或藉由連接基將碳數6～20的芳香族基組合兩個以上而獲得之基團為更佳。 作為上述連接基，-O-、-S-、-C（=O）-、-S（=O）2 -、伸烷基、鹵化伸烷基、伸芳基或該等鍵結兩個以上而形成之連接基為較佳，-O-、-S-、伸烷基、鹵化伸烷基、芳香族基或該等鍵結兩個以上而形成之連接基為更佳。 作為上述伸烷基，碳數1～20的伸烷基為較佳，碳數1～10的伸烷基為更佳，碳數1～4的伸烷基為進一步較佳。 作為上述鹵化伸烷基，碳數1～20的鹵化伸烷基為較佳，碳數1～10的鹵化伸烷基為更佳，碳數1～4的鹵化伸烷基為更佳。又，作為上述鹵化伸烷基中之鹵素原子，可以舉出氟原子、氯原子、溴原子、碘原子等，氟原子為較佳。上述鹵化伸烷基可以具有氫原子，亦可以使所有氫原子經鹵素原子取代，但是所有氫原子經鹵素原子取代為較佳。作為較佳的鹵化伸烷基的例子，可以舉出（二三氟甲基）亞甲基等。 作為上述芳香族基，伸苯基或伸萘基為較佳，伸苯基為更佳，1,3-伸苯基或1,4-伸苯基為進一步較佳。[Repeating unit represented by formula (2-1)] -X 1 - In formula (2-1), X 1 represents a tetravalent linking group, and examples thereof include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group obtained by linking two or more of these groups via a single bond or via a linking group. Preferably, it is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups via a single bond or via a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or via a linking group. As the linking group, -O-, -S-, -C(=O)-, -S(=O) 2- , alkylene, halogenated alkylene, arylene or a linking group formed by two or more of these groups are preferred, and -O-, -S-, alkylene, halogenated alkylene, aromatic or a linking group formed by two or more of these groups are more preferred. As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is further preferred. As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferred, a halogenated alkylene group having 1 to 10 carbon atoms is more preferred, and a halogenated alkylene group having 1 to 4 carbon atoms is further preferred. In addition, as the halogen atom in the above-mentioned halogenated alkylene group, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. can be cited, and fluorine atom is preferred. The above-mentioned halogenated alkylene group may have a hydrogen atom, and all hydrogen atoms may be substituted by halogen atoms, but all hydrogen atoms are preferably substituted by halogen atoms. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene, etc. can be cited. As the above-mentioned aromatic group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is further preferred.

其中，X1 為下述式（5）或式（6）所表示之基團為較佳。 [化學式6] 式（5）中，R112 選自單鍵或可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO2 -及NHCO-以及該等組合中之基團為較佳，選自單鍵、可以經氟原子取代的碳數1～3的伸烷基、-O-、-CO-、-S-及SO2 -中之基團為更佳，選自包括-CH2 -、-C（CF3 ）2 -、-C（CH3 ）2 -、-O-、-CO-、-S-及SO2 -之群組中的2價基團為進一步較佳。 式（5）及式（6）中，*分別表示與其他結構的鍵結部位。Among them, X1 is preferably a group represented by the following formula (5) or formula (6). [Chemical Formula 6] In formula (5), R 112 is preferably selected from a single bond, an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO 2 -, NHCO-, and a combination thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, and SO 2 -, and even more preferably a divalent group selected from the group consisting of -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -O-, -CO-, -S-, and SO 2 -. In formula (5) and formula (6), * indicates a bonding site with other structures, respectively.

關於X1 ，具體而言，可以舉出從四羧酸二酐去除酐基之後所殘存之四羧酸殘基等。四羧酸二酐可以僅使用一種，亦可以使用兩種以上。 四羧酸二酐由下述式（O）表示為較佳。 [化學式7] 式（O）中，X1 表示4價連接基。X1 與式（2-1）中之X1 的含義相同，較佳範圍亦相同。Specifically, X 1 includes a tetracarboxylic acid residue remaining after removing anhydride groups from tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 7] In formula (O), X1 represents a 4-valent linking group. X1 has the same meaning as X1 in formula (2-1), and the preferred range is also the same.

作為四羧酸二酐的具體例，可以舉出均苯四甲酸二酐（PMDA）、3,3’,4,4’-聯苯四羧酸二酐、3,3’,4,4’-二苯硫醚四羧酸二酐、3,3’,4,4’-二苯基碸四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、3,3’,4,4’-二苯基甲烷四羧酸二酐、2,2’,3,3’-二苯基甲烷四羧酸二酐、2,3,3’,4’-聯苯四羧酸二酐、2,3,3’,4’-二苯甲酮四羧酸二酐、4,4’氧代二鄰苯二甲酸二酐、2,3,6,7-萘四羧酸二酐、1,4,5,7-萘四羧酸二酐、2,2-雙（3,4-二羧基苯基）丙烷二酐、2,2-雙（2,3-二羧基苯基）丙烷二酐、2,2-雙（3,4-二羧基苯基）六氟丙烷二酐、1,3-二苯基六氟丙烷-3,3,4,4-四羧酸二酐、1,4,5,6-萘四羧酸二酐、2,2’,3,3’-二苯基四羧酸二酐、3,4,9,10-苝四羧酸二酐、1,2,4,5-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、1,8,9,10-菲四羧酸二酐、1,1-雙（2,3-二羧基苯基）乙烷二酐、1,1-雙（3,4-二羧基苯基）乙烷二酐、1,2,3,4-苯四羧酸二酐及該等碳數1～6的烷基及碳數1～6的烷氧基衍生物。Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-6 alkyl and C1-6 alkoxy derivatives thereof.

又，亦可以舉出國際公開第2017/038598號的0038段中所記載的四羧酸二酐（DAA-1）～（DAA-5）作為較佳例。Furthermore, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be cited as preferred examples.

-A1 、A2 - 式（2-1）中，A1 及A2 分別獨立地表示氧原子或-NRN -，氧原子為較佳。 上述RN 表示氫原子或烴基，氫原子、烷基或芳香族烴基為更佳，氫原子或烷基為進一步較佳，氫原子為特佳。 -A1 , A2- In formula (2-1), A1 and A2 each independently represent an oxygen atom or -NRN- , preferably an oxygen atom. RN represents a hydrogen atom or a alkyl group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, further preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom.

-R1 、R2 - 式（2-1）中，R1 及R2 分別獨立地表示1價有機基。 作為R1 及R2 中之1價有機基，可以舉出包含聚合性基之基團或可以包含雜原子的有機基，從耐藥品性、顯影性及特定樹脂的溶劑溶解性的觀點考慮，包含聚伸烷氧基之基團為較佳。-R 1 , R 2 - In formula (2-1), R 1 and R 2 each independently represent a monovalent organic group. Examples of the monovalent organic group in R 1 and R 2 include a group containing a polymerizable group or an organic group that may contain a heteroatom. From the viewpoint of chemical resistance, developing properties, and solvent solubility of a specific resin, a group containing a polyalkylene oxide group is preferred.

＜＜包含聚合性基之基團＞＞ 作為R1 及R2 中之包含聚合性基之基團中所包含之聚合性基，包括包含乙烯性不飽和鍵之基團、環狀醚基、羥甲基或烷氧基甲基（較佳為，烷氧基的碳數為1～6之烷氧基甲基）之基團為較佳，乙烯基、（甲基）烯丙基、（甲基）丙烯醯胺基、（甲基）丙烯醯氧基、順丁烯二醯亞胺基、乙烯基苯基、環氧基、氧雜環丁基、羥甲基或烷氧基甲基為更佳，（甲基）丙烯醯氧基、（甲基）丙烯醯胺基、環氧基、羥甲基或烷氧基甲基為進一步較佳。 上述包含聚合性基之基團中所包含之聚合性基的數量為一個以上，1～15個為較佳，1～10個為更佳，1～5個為進一步較佳，一個或兩個為特佳，一個為最佳。＜＜Group containing a polymerizable group＞＞ The polymerizable group contained in the group containing a polymerizable group in R1 and R2 includes a group containing an ethylenic unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group (preferably an alkoxymethyl group having an alkoxy group with 1 to 6 carbon atoms), more preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a cis-butylenediamide group, a vinylphenyl group, an epoxy group, an oxocyclobutyl group, a hydroxymethyl group or an alkoxymethyl group, and further preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group. The number of polymerizable groups contained in the above-mentioned group containing a polymerizable group is one or more, preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, particularly preferably one or two, and most preferably one.

作為上述包含聚合性基之基團，乙烯基、烯丙基、（甲基）丙烯醯基或下述式（III）所表示之基團亦較佳。As the group containing a polymerizable group, a vinyl group, an allyl group, a (meth)acryl group or a group represented by the following formula (III) is also preferred.

[化學式8] [Chemical formula 8]

式（III）中，R200 表示氫原子或甲基，甲基為較佳。In formula (III), R 200 represents a hydrogen atom or a methyl group, preferably a methyl group.

式（III）中，R201 表示碳數2～12的伸烷基、-CH2 CH（OH）CH2 -或碳數4～30的（聚）伸烷氧基（作為伸烷基，碳數1～12為較佳，1～6為更佳，1～3為特佳；重複數為1～12為較佳，1～6為更佳，1～3為特佳）。另外，（聚）伸烷氧基表示伸烷氧基或聚伸烷氧基。 關於較佳的R201 的例子，可以舉出伸乙基、伸丙基、三亞甲基、四亞甲基、1,2-丁二基、1,3-丁二基、五亞甲基、六亞甲基、八亞甲基、十二亞甲基、-CH2 CH（OH）CH2 -，伸乙基、伸丙基、三亞甲基、-CH2 CH（OH）CH2 -為更佳。 特佳為，R200 為甲基，R201 為伸乙基。 式（III）中，*表示與其他結構的鍵結部位。In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2 -, or a (poly) alkoxylene group having 4 to 30 carbon atoms (the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms; and the number of repetitions is 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). In addition, the (poly) alkoxylene group represents an alkoxylene group or a polyalkoxylene group. Preferred examples of R 201 include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, and -CH 2 CH (OH) CH 2 -. More preferred are ethylene, propylene, trimethylene, and -CH 2 CH (OH) CH 2 -. Particularly preferably, R 200 is a methyl group and R 201 is an ethylene group. In formula (III), * represents a bonding site with other structures.

＜＜可以包含雜原子之有機基＞＞ 可以包含雜原子的有機基為不具有聚合性基的有機基為較佳。 作為可以包含上述雜原子的有機基中之雜原子，可以舉出氧原子、氮原子、硫原子、鹵素原子等，氧原子為較佳。 又，上述雜原子作為醚鍵（-O-）而包含為較佳。 作為可以包含上述雜原子的有機基，可以包含雜原子的碳數1～30的有機基為較佳，可以包含雜原子的碳數2～20的有機基為更佳。<<Organic group that can contain heteroatoms>> The organic group that can contain heteroatoms is preferably an organic group that does not have a polymerizable group. As the heteroatom in the organic group that can contain the above-mentioned heteroatom, oxygen atom, nitrogen atom, sulfur atom, halogen atom, etc. can be cited, and oxygen atom is preferred. Moreover, the above-mentioned heteroatom is preferably contained as an ether bond (-O-). As the organic group that can contain the above-mentioned heteroatom, an organic group having 1 to 30 carbon atoms that can contain the heteroatom is preferred, and an organic group having 2 to 20 carbon atoms that can contain the heteroatom is more preferred.

＜＜＜聚伸烷氧基＞＞＞ 其中，可以包含上述雜原子的有機基為具有聚伸烷氧基之有機基為較佳。＜＜＜Polyalkylene oxide＞＞＞ Among them, the organic group that may contain the above-mentioned heteroatom is preferably an organic group having a polyalkylene oxide group.

在本發明中，聚伸烷氧基是指直接鍵結兩個以上的伸烷氧基而獲得之基團。聚伸烷氧基中所包含之複數個伸烷氧基中之伸烷基可以分別相同，亦可以不同。 在聚伸烷氧基包含伸烷基不同之複數種伸烷氧基之情況下，聚伸烷氧基中之伸烷氧基的排列可以為無規排列，亦可以為具有嵌段之排列，還可以為具有交替等圖案之排列。 上述伸烷基的碳數（在伸烷基具有取代基之情況下，包含取代基的碳數）為2以上為較佳，2～10為更佳，2～6為更佳，2～5為進一步較佳，2～4為更進一步較佳，2或3為特佳，2為最佳。 又，上述伸烷基可以具有取代基。作為較佳的取代基，可以舉出烷基、芳基、鹵素原子等。 又，聚伸烷氧基中所包含之伸烷氧基的數量（聚伸烷氧基的重複數）為2～20個為較佳，2～10個為更佳，2～5個為進一步較佳，2～4個為特佳，兩個為最佳。 作為聚伸烷氧基，從兼顧溶劑溶解性及耐藥品性的觀點考慮，聚乙烯氧基、聚伸丙氧基、聚三亞甲氧基、聚四亞甲氧基或複數個乙烯氧基與複數個伸丙氧基鍵結而獲得之基團為較佳，聚乙烯氧基或聚伸丙氧基為更佳，聚乙烯氧基為進一步較佳。在上述複數個乙烯氧基與複數個伸丙氧基鍵結而獲得之基團中，乙烯氧基與伸丙氧基可以無規排列，亦可以形成嵌段而排列，還可以排列成交替等圖案狀。該等基團中之乙烯氧基等的重複數的較佳態樣如上所述。In the present invention, a polyalkoxyl group refers to a group obtained by directly bonding two or more alkoxyl groups. The alkylene groups in the multiple alkoxyl groups contained in the polyalkoxyl group may be the same or different. In the case where the polyalkoxyl group contains multiple alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, an arrangement with blocks, or an arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is further preferred, 2 or 3 is particularly preferred, and 2 is the best. In addition, the above-mentioned alkylene group may have a substituent. As preferred substituents, alkyl groups, aryl groups, halogen atoms, etc. can be cited. In addition, the number of alkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, more preferably 2 to 5, more preferably 2 to 4, and most preferably two. As the polyalkoxy group, from the perspective of both solvent solubility and drug resistance, polyethyleneoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group obtained by bonding a plurality of polyethyleneoxy groups to a plurality of propoxy groups is preferred, polyethyleneoxy or polypropoxy is more preferred, and polyethyleneoxy is further preferred. In the above-mentioned groups obtained by bonding a plurality of vinyloxy groups and a plurality of propoxy groups, the vinyloxy groups and propoxy groups may be arranged randomly, in blocks, or in alternating patterns. The preferred aspects of the number of repetitions of the vinyloxy groups in the above-mentioned groups are as described above.

具有聚伸烷氧基之有機基為下述式（PO-1）所表示之基團為較佳。 [化學式9] 式（PO-1）中，RP1 分別獨立地表示伸烷基，RP2 表示1價有機基，n表示2以上的整數，LP1 表示單鍵或2價連接基，*表示與式（2-1）中的R1 或R2 所鍵結之氧原子的鍵結部位。The organic group having a polyalkylene oxide group is preferably a group represented by the following formula (PO-1). [Chemical Formula 9] In the formula (PO-1), R P1 each independently represents an alkylene group, R P2 represents a monovalent organic group, n represents an integer greater than 2, L P1 represents a single bond or a divalent linking group, and * represents a bonding site to the oxygen atom to which R 1 or R 2 in the formula (2-1) is bonded.

式（PO-1）中，RP1 分別獨立地表示碳數2～10的伸烷基為較佳，碳數2～4的伸烷基為更佳，伸乙基（-CH2 -CH2 -）或伸丙基（-CH2 -CH（CH3 ）-或-CH（CH3 ）-CH2 -）為更佳，伸乙基為進一步較佳。In formula (PO-1), R and P1 each independently represent preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, more preferably an ethylene group ( -CH2 - CH2- ) or a propylene group ( -CH2- CH( CH3 )- or -CH( CH3 ) -CH2- ), and even more preferably an ethylene group.

式（PO-1）中，RP2 表示1價有機基，烷基、芳香族烴基、芳烷基或包含聚合性基之基團為較佳，烷基為更佳。 作為上述烷基，碳數1～10的烷基為較佳，碳數2～4的烷基為更佳，乙基為進一步較佳。 作為上述芳香族烴基，碳數6～20的芳香族烴基為較佳，苯基或萘基為更佳，苯基為進一步較佳。 作為上述芳烷基，碳數7～30的芳烷基為較佳，碳數7～20的芳烷基為更佳，苄基為進一步較佳。 作為上述包含聚合性基之基團中所包含之聚合性基，包括包含乙烯性不飽和鍵之基團、環狀醚基、羥甲基或烷氧基甲基（較佳為，烷氧基的碳數為1～6之烷氧基甲基）之基團為較佳，乙烯基、（甲基）烯丙基、（甲基）丙烯醯胺基、（甲基）丙烯醯氧基、順丁烯二醯亞胺基、乙烯基苯基、環氧基、氧雜環丁基、羥甲基或烷氧基甲基為更佳，（甲基）丙烯醯氧基、甲基）丙烯醯胺基、環氧基、羥甲基或烷氧基甲基為進一步較佳。 作為上述包含聚合性基之基團，後述式（P-1）所表示之基團為較佳，後述式（P-2）或後述式（P-3）所表示之基團為更佳。In the formula (PO-1), R P2 represents a monovalent organic group, preferably an alkyl group, an aromatic hydrocarbon group, an aralkyl group or a group containing a polymerizable group, and more preferably an alkyl group. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 2 to 4 carbon atoms is more preferred, and an ethyl group is further preferred. As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred, a phenyl group or a naphthyl group is further preferred, and a phenyl group is further preferred. As the above-mentioned aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferred, an aralkyl group having 7 to 20 carbon atoms is further preferred, and a benzyl group is further preferred. The polymerizable group contained in the above-mentioned group containing a polymerizable group includes a group containing an ethylenic unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group (preferably an alkoxymethyl group having an alkoxy group with 1 to 6 carbon atoms), more preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a cis-butylenediimide group, a vinylphenyl group, an epoxy group, an oxocyclobutyl group, a hydroxymethyl group or an alkoxymethyl group, and further preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group. As the group containing a polymerizable group, a group represented by the formula (P-1) described below is preferred, and a group represented by the formula (P-2) or the formula (P-3) described below is more preferred.

式（PO-1）中，n為2～20的整數為較佳，2～10的整數為更佳，2～5的整數為進一步較佳，2～4的整數為特佳，2為最佳。In the formula (PO-1), n is preferably an integer of 2 to 20, more preferably an integer of 2 to 10, further preferably an integer of 2 to 5, particularly preferably an integer of 2 to 4, and most preferably 2.

式（PO-1）中，LP1 表示單鍵或2價連接基，單鍵為較佳。 作為上述2價連接基，烴基、-O-、-C（=O）-、-S-、-S（=O）2 -、-NRN -或該等鍵結兩個以上而獲得之基團為較佳，烴基、-O-、-C（=O）-、-NRN -或該等鍵結兩個以上而獲得之基團為更佳，烴基、酯鍵、醯胺鍵、胺甲酸乙酯鍵、脲鍵或該等組合兩個以上而獲得之基團為進一步較佳。 在本說明書中，在簡單記載為“酯鍵（-C（=O）O-）”、“胺甲酸乙酯鍵（-O-C（=O）NR-）”、“醯胺鍵（-C（=O）NR-）”等之情況下，該等鍵的方向並不受限定。上述R表示氫原子或1價有機基，氫原子或烴基為較佳，氫原子、烷基或芳香族烴基為更佳，氫原子、碳數1～4的烷基或碳數6～20的芳香族烴基為進一步較佳，氫原子為特佳。 上述RN 表示氫原子或烴基，氫原子、烷基或芳基為更佳，氫原子或烷基為進一步較佳，氫原子為特佳。 作為上述LP1 中之烴基，碳數1～30的飽和脂肪族烴基、碳數6～30的芳香族烴基或由該等組合表示之基團為較佳，碳數1～10的飽和脂肪族烴基、從苯環去除兩個以上的氫原子而獲得之基團或由該等鍵結表示之基團為更佳。In formula (PO-1), L P1 represents a single bond or a divalent linking group, and a single bond is preferred. As the divalent linking group, a alkyl group, -O-, -C(=O)-, -S-, -S(=O) 2 -, -NR N -, or a group obtained by bonding two or more of these groups is preferred, a alkyl group, -O-, -C(=O)-, -NR N -, or a group obtained by bonding two or more of these groups is more preferred, and a alkyl group, an ester bond, an amide bond, a urethane bond, a urea bond, or a group obtained by combining two or more of these groups is further preferred. In the present specification, when simply described as "ester bond (-C(=O)O-)", "urethane bond (-OC(=O)NR-)", "amide bond (-C(=O)NR-)", etc., the directions of the bonds are not limited. The above R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, further preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and particularly preferably a hydrogen atom. The above RN represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aryl group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. The alkyl group in the above-mentioned L P1 is preferably a saturated aliphatic alkyl group having 1 to 30 carbon atoms, an aromatic alkyl group having 6 to 30 carbon atoms, or a group represented by these combinations. More preferably, it is a saturated aliphatic alkyl group having 1 to 10 carbon atoms, a group obtained by removing two or more hydrogen atoms from a benzene ring, or a group represented by these bonds.

＜＜＜被鹵素原子取代之烴基＞＞＞ 又，從溶劑溶解性及膜強度的觀點考慮，可以包含雜原子的有機基可以為經鹵素原子取代之烴基。 作為經鹵素原子取代之烴基中之鹵素原子，可以舉出氟原子、氯原子、溴原子、碘原子等，氟原子為較佳。 作為上述烴基，烷基或芳香族烴基為較佳，烷基為更佳。 作為上述烷基，碳數1～30的烷基為較佳，碳數1～10的烷基為更佳，碳數2～4的烷基為進一步較佳。 作為上述芳香族烴基，碳數6～30的芳香族烴基為較佳，碳數6～20的芳香族烴基為更佳，苯基為更佳。 亦即，經鹵素原子取代之烴基為至少一個氫原子經氟原子取代之烷基為較佳。 藉由包含經鹵素原子取代之烴基作為R1 或R2 ，所獲得之硬化膜的膜強度得到提高。＜＜＜Halogen atom-substituted alkyl group＞＞＞ In addition, from the viewpoint of solvent solubility and film strength, the organic group that may contain a heteroatom may be a halogen atom-substituted alkyl group. As the halogen atom in the halogen atom-substituted alkyl group, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. As the above-mentioned alkyl group, an alkyl group or an aromatic alkyl group is preferred, and an alkyl group is more preferred. As the above-mentioned alkyl group, an alkyl group having 1 to 30 carbon atoms is preferred, an alkyl group having 1 to 10 carbon atoms is more preferred, and an alkyl group having 2 to 4 carbon atoms is further preferred. As the above-mentioned aromatic alkyl group, an aromatic alkyl group having 6 to 30 carbon atoms is preferred, an aromatic alkyl group having 6 to 20 carbon atoms is more preferred, and a phenyl group is more preferred. That is, the halogen atom-substituted alkyl group is preferably an alkyl group in which at least one hydrogen atom is substituted by a fluorine atom. By including a halogen atom-substituted alkyl group as R 1 or R 2 , the film strength of the obtained cured film is improved.

＜＜其他取代基＞＞ R1 及R2 可以為其他取代基。 作為其他取代基，可以舉出具有酸基之烴基等。作為具有酸基之烴基，可以舉出具有酸基之烷基、具有酸基之芳香族烴基或具有酸基之芳烷基等。 作為上述具有酸基之烷基中之烷基，碳數1～30的烷基為較佳，碳數1～20的烷基為更佳，碳數1～10的烷基為進一步較佳。 作為上述具有酸基之烷基中之酸基，可以舉出羧基、磺酸基、磷酸基、膦酸基等，羧基為較佳。 作為上述具有酸基之芳香族烴基中之芳香族烴基，碳數6～20的芳香族烴基為較佳，苯基或萘基為更佳，苯基為進一步較佳。 作為上述具有酸基之芳烷基，碳數7～30的芳烷基為較佳，碳數7～20的芳烷基為更佳，苄基為進一步較佳。 作為上述具有酸基之芳香族烴基或上述具有酸基之芳烷基中之酸基，可以舉出酚性羥基、羧基、磺酸基、磷酸基、膦酸基等，酚性羥基或羧基為較佳，酚性羥基為更佳。 其中，具有酸基之芳香族烴基或具有酸基之芳烷基為較佳，具有酚性羥基之芳香族烴基或具有酚性羥基之芳烷基為更佳，具有酚性羥基之苯基或具有酚性羥基之芐基為進一步較佳。＜＜Other substituents＞＞ R1 and R2 may be other substituents. Examples of other substituents include alkyl groups having an acid group. Examples of alkyl groups having an acid group include alkyl groups having an acid group, aromatic alkyl groups having an acid group, and aralkyl groups having an acid group. As the alkyl group in the above-mentioned alkyl groups having an acid group, an alkyl group having 1 to 30 carbon atoms is preferred, an alkyl group having 1 to 20 carbon atoms is more preferred, and an alkyl group having 1 to 10 carbon atoms is further preferred. As the acid group in the above-mentioned alkyl groups having an acid group, examples include carboxyl groups, sulfonic acid groups, phosphoric acid groups, and phosphonic acid groups, and carboxyl groups are preferred. As the aromatic hydrocarbon group in the above-mentioned aromatic hydrocarbon groups having an acid group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred, a phenyl group or a naphthyl group is more preferred, and a phenyl group is further preferred. As the above-mentioned aralkyl group having an acid group, an aralkyl group having 7 to 30 carbon atoms is preferred, an aralkyl group having 7 to 20 carbon atoms is more preferred, and a benzyl group is further preferred. As the above-mentioned aromatic hydrocarbon group having an acid group or the acid group in the above-mentioned aralkyl group having an acid group, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, etc. can be cited, and a phenolic hydroxyl group or a carboxyl group is preferred, and a phenolic hydroxyl group is more preferred. Among them, an aromatic hydrocarbon group having an acid group or an aralkyl group having an acid group is preferred, an aromatic hydrocarbon group having a phenolic hydroxyl group or an aralkyl group having a phenolic hydroxyl group is more preferred, and a phenyl group having a phenolic hydroxyl group or a benzyl group having a phenolic hydroxyl group is further preferred.

從膜強度及耐藥品性的觀點考慮，作為包含乙烯性不飽和鍵之取代基之R1 及R2 的莫耳量相對於特定樹脂中所包含之所有式（2-1）所表示之重複單元中的R1 及R2 的總莫耳量的比例為0～30%為較佳。 從膜強度的觀點考慮，上述比例為0～10%為較佳，0～5%為更佳，0～3為進一步較佳。 從耐藥品性的觀點考慮，上述比例為10～30%為較佳，15～30%為更佳。From the viewpoint of film strength and chemical resistance, the molar amount of R1 and R2 as substituents containing ethylenic unsaturated bonds relative to the total molar amount of R1 and R2 in all repeating units represented by formula (2-1) contained in the specific resin is preferably 0 to 30%. From the viewpoint of film strength, the above ratio is preferably 0 to 10%, more preferably 0 to 5%, and even more preferably 0 to 3%. From the viewpoint of chemical resistance, the above ratio is preferably 10 to 30%, and even more preferably 15 to 30%.

從膜強度、耐藥品性及特定樹脂的溶劑溶解性的觀點考慮，作為可以包含雜原子的碳數1～30的有機基之R1 及R2 的莫耳量相對於上述樹脂中所包含之所有上述式（2-1）所表示之重複單元中的R1 及R2 的總莫耳量的比例為20～100%為較佳。 從膜強度的觀點考慮，上述比例的下限為30%以上為較佳，40%以上為更佳，50%以上為進一步較佳，60%以上為特佳，70%以上為最佳。 從耐藥品性的觀點考慮，上述比例的上限為95%以下為較佳，90%以下為更佳，85%以下為進一步較佳，80%以下為特佳，70%以下為最佳。From the viewpoint of film strength, chemical resistance and solvent solubility of a specific resin, the molar amount of R1 and R2 , which are organic groups having 1 to 30 carbon atoms and may contain a heteroatom, relative to the total molar amount of R1 and R2 in all the repeating units represented by the above formula (2-1) contained in the above resin is preferably 20 to 100%. From the viewpoint of film strength, the lower limit of the above ratio is preferably 30% or more, more preferably 40% or more, even more preferably 50% or more, particularly preferably 60% or more, and most preferably 70% or more. From the viewpoint of chemical resistance, the upper limit of the above ratio is preferably 95% or less, more preferably 90% or less, even more preferably 85% or less, particularly preferably 80% or less, and most preferably 70% or less.

-含量- 在特定樹脂包含式（2-1）所表示之重複單元之情況下，式（2-1）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，20～60質量%為更佳。 又，特定樹脂可以僅包含一種式（2-1）所表示之重複單元，亦可以包含兩種以上的不同結構之式（2-1）所表示之重複單元。在包含兩種以上的式（2-1）所表示之重複單元之情況下，式（2-1）所表示之重複單元的合計含量在上述範圍內為較佳。-Content- When the specific resin contains the repeating unit represented by formula (2-1), the content of the repeating unit represented by formula (2-1) is preferably 0.1 to 80 mass % relative to the total mass of the specific resin, and more preferably 20 to 60 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (2-1), or may contain two or more repeating units represented by formula (2-1) of different structures. When containing two or more repeating units represented by formula (2-1), the total content of the repeating units represented by formula (2-1) is preferably within the above range.

[式（2-2）所表示之重複單元] 式（2-2）中，X2 表示4價連接基。 式（2-2）中，X2 與式（2-1）中的X1 的含義相同，較佳態樣亦相同。[Repeating unit represented by formula (2-2)] In formula (2-2), X2 represents a 4-valent linking group. In formula (2-2), X2 has the same meaning as X1 in formula (2-1), and the preferred embodiment is also the same.

又，在特定樹脂包含式（2-2）所表示之重複單元之情況下，將特定樹脂的醯亞胺化率（閉環率）設為70%以上亦較佳。上述醯亞胺化率為80%以上為更佳，90%以上為進一步較佳。 上述醯亞胺化率的上限並無特別限定，只要為100%以下即可。 關於上述醯亞胺化率，例如藉由下述方法來進行測定。 測定特定樹脂的紅外吸收光譜，並求出作為源自醯亞胺結構的吸收峰之1377cm-1 附近的峰強度P1。接著，在350℃下對該特定樹脂進行1小時的熱處理之後，再次測定紅外吸收光譜，並求出1377cm-1 附近的峰強度P2。能夠使用所獲得之峰強度P1、P2，並依據下述式來求出特定樹脂的醯亞胺化率。 醯亞胺化率（%）=（峰強度P1/峰強度P2）×100Furthermore, when the specific resin contains the repeating unit represented by formula (2-2), it is also preferred that the imidization rate (ring closure rate) of the specific resin is set to 70% or more. The above-mentioned imidization rate is more preferably 80% or more, and more preferably 90% or more. There is no particular upper limit to the above-mentioned imidization rate, as long as it is 100% or less. The above-mentioned imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the specific resin is measured, and the peak intensity P1 near 1377 cm -1 , which is an absorption peak derived from the imide structure, is obtained. Next, the specific resin is heat treated at 350°C for 1 hour, and the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1377 cm -1 . The obtained peak intensities P1 and P2 can be used to determine the imidization rate of the specific resin according to the following formula. Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

-含量- 在特定樹脂包含式（2-2）所表示之重複單元之情況下，式（2-2）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，20～60質量%為更佳。 又，特定樹脂可以僅包含一種式（2-2）所表示之重複單元，亦可以包含兩種以上的不同結構之式（2-2）所表示之重複單元。在包含兩種以上的式（2-2）所表示之重複單元之情況下，式（2-2）所表示之重複單元的合計含量在上述範圍內為較佳。-Content- When the specific resin contains the repeating unit represented by formula (2-2), the content of the repeating unit represented by formula (2-2) is preferably 0.1 to 80 mass % relative to the total mass of the specific resin, and more preferably 20 to 60 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (2-2), or may contain two or more repeating units represented by formula (2-2) of different structures. When containing two or more repeating units represented by formula (2-2), the total content of the repeating units represented by formula (2-2) is preferably within the above range.

[式（2-3）所表示之重複單元] 式（2-3）中，X3 表示3價連接基。 X3 可以例示直鏈狀或支鏈狀的脂肪族基、環狀的脂肪族基、芳香族基、雜芳族基團或者單鍵或藉由連接基將該等連接兩個以上而獲得之基團，碳數2～20的直鏈的脂肪族基、碳數3～20的支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族基或者單鍵或藉由連接基將該等組合兩個以上而獲得之基團為較佳，碳數6～20的芳香族基或者單鍵或藉由連接基將碳數6～20的芳香族基組合兩個以上而獲得之基團為更佳，碳數6～20的芳香族基為進一步較佳，從苯環去除三個氫原子而獲得之基團為特佳。 作為上述連接基，-O-、-S-、-C（=O）-、-S（=O）2 -、伸烷基、鹵化伸烷基、伸芳基或該等鍵結兩個以上而形成之連接基為較佳，-O-、-S-、伸烷基、鹵化伸烷基、芳香族基或該等鍵結兩個以上而形成之連接基為更佳。 作為上述伸烷基，碳數1～20的伸烷基為較佳，碳數1～10的伸烷基為更佳，碳數1～4的伸烷基為進一步較佳。 作為上述鹵化伸烷基，碳數1～20的鹵化伸烷基為較佳，碳數1～10的鹵化伸烷基為更佳，碳數1～4的鹵化伸烷基為更佳。又，作為上述鹵化伸烷基中之鹵素原子，可以舉出氟原子、氯原子、溴原子、碘原子等，氟原子為較佳。上述鹵化伸烷基可以具有氫原子，亦可以使所有氫原子經鹵素原子取代，但是所有氫原子經鹵素原子取代為較佳。作為較佳的鹵化伸烷基的例子，可以舉出（二三氟甲基）亞甲基等。 作為上述芳香族基，伸苯基或伸萘基為較佳，伸苯基為更佳，1,3-伸苯基或1,4-伸苯基為進一步較佳。[Repeating unit represented by formula (2-3)] In formula (2-3), X3 represents a trivalent linking group. Examples of X3 include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group obtained by linking two or more of these groups by a single bond or via a linking group, a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a heteroaromatic group. A group obtained by combining two or more of these groups by a single bond or a linking group is preferred, an aromatic group having 6 to 20 carbon atoms or a group obtained by combining two or more of these groups by a single bond or a linking group is more preferred, an aromatic group having 6 to 20 carbon atoms is further preferred, and a group obtained by removing three hydrogen atoms from a benzene ring is particularly preferred. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) 2- , an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by two or more of these groups are preferred, and -O-, -S-, an alkylene group, a halogenated alkylene group, an aromatic group, or a linking group formed by two or more of these groups are more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is further preferred. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferred, a halogenated alkylene group having 1 to 10 carbon atoms is more preferred, and a halogenated alkylene group having 1 to 4 carbon atoms is further preferred. Moreover, as the halogen atom in the above-mentioned halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be cited, and a fluorine atom is preferred. The above-mentioned halogenated alkylene group may have a hydrogen atom, and all hydrogen atoms may be substituted with a halogen atom, but it is preferred that all hydrogen atoms are substituted with a halogen atom. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene and the like can be cited. As the aromatic group, a phenylene group or a naphthylene group is preferred, a phenylene group is more preferred, and a 1,3-phenylene group or a 1,4-phenylene group is further preferred.

又，X3 從至少一個羧基可以被鹵化的三羧酸化合物衍生為較佳。作為上述鹵化，氯化為較佳。 在本發明中，將具有三個羧基之化合物稱為三羧酸化合物。 上述三羧酸化合物的三個羧基中的兩個羧基可以被酸酐化。 作為用於聚醯胺醯亞胺前驅物的製造中之可以被鹵化的三羧酸化合物，可以舉出支鏈狀的脂肪族、環狀的脂肪族或芳香族的三羧酸化合物等。 該等三羧酸化合物可以僅使用一種，亦可以使用兩種以上。In addition, X3 is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group can be halogenated. As the above-mentioned halogenation, chlorination is preferred. In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups of the above-mentioned tricarboxylic acid compound can be anhydrided. As the tricarboxylic acid compound that can be halogenated in the production of polyamide imide precursors, branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds can be cited. Such tricarboxylic acid compounds can be used only one, or two or more can be used.

具體而言，作為三羧酸化合物，包含碳數2～20的直鏈的脂肪族基、碳數3～20的支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族基或者單鍵或藉由連接基將該等組合兩個以上而獲得之基團之三羧酸化合物為較佳，包含碳數6～20的芳香族基或者單鍵或藉由連接基將碳數6～20的芳香族基組合兩個以上而獲得之基團之三羧酸化合物為更佳。Specifically, as the tricarboxylic acid compound, a tricarboxylic acid compound comprising a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups by a single bond or via a linking group is preferred, and a tricarboxylic acid compound comprising an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms by a single bond or via a linking group is more preferred.

又，作為三羧酸化合物的具體例，可以舉出藉由單鍵、-O-、-CH2 -、-C（CH3 ）2 -、-C（CF3 ）2 -、-SO2 -或伸苯基連接1,2,3-丙烷三羧酸、1,3,5-戊烷三羧酸、檸檬酸、偏苯三甲酸、2,3,6-萘三羧酸、鄰苯二甲酸（或者，鄰苯二甲酸酐）與苯甲酸之化合物等。 該等化合物可以為兩個羧基被酐化之化合物（例如，偏苯三甲酸酐），亦可以為至少一個羧基被鹵化之化合物（例如，偏苯三甲酸酐）。Specific examples of tricarboxylic acid compounds include compounds in which 1,2,3- propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, -CH2-, -C( CH3 ) 2- , -C( CF3 ) 2- , -SO2- or a phenylene group. These compounds may be compounds in which two carboxyl groups are anhydrided (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride).

又，在特定樹脂包含式（2-3）所表示之重複單元之情況下，將上述特定樹脂的醯亞胺化率（閉環率）設為70%以上亦較佳。上述醯亞胺化率為80%以上為更佳，90%以上為進一步較佳。 上述醯亞胺化率的上限並無特別限定，只要為100%以下即可。Furthermore, when the specific resin contains the repeating unit represented by formula (2-3), it is also preferred that the imidization rate (ring closure rate) of the specific resin is set to 70% or more. It is more preferred that the imidization rate is 80% or more, and it is further preferred that it is 90% or more. The upper limit of the imidization rate is not particularly limited, as long as it is 100% or less.

-含量- 在特定樹脂包含式（2-3）所表示之重複單元之情況下，式（2-3）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，20～60質量%為更佳。 又，特定樹脂可以僅包含一種式（2-3）所表示之重複單元，亦可以包含兩種以上的不同結構之式（2-3）所表示之重複單元。在包含兩種以上的式（2-3）所表示之重複單元之情況下，式（2-3）所表示之重複單元的合計含量在上述範圍內為較佳。-Content- When the specific resin contains the repeating unit represented by formula (2-3), the content of the repeating unit represented by formula (2-3) is preferably 0.1 to 80 mass % relative to the total mass of the specific resin, and more preferably 20 to 60 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (2-3), or may contain two or more repeating units represented by formula (2-3) of different structures. When containing two or more repeating units represented by formula (2-3), the total content of the repeating units represented by formula (2-3) is preferably within the above range.

[式（2-4）所表示之重複單元] 式（2-4）中，X4 與式（2-3）中之X3 的含義相同，較佳態樣亦相同。 式（2-4）中，A4 與式（2-1）中之A1 的含義相同，較佳態樣亦相同。 式（2-4）中，R4 與式（2-1）中之R1 的含義相同，較佳態樣亦相同。[Repeating units represented by formula (2-4)] In formula (2-4), X4 has the same meaning as X3 in formula (2-3), and a preferred embodiment thereof is also the same. In formula (2-4), A4 has the same meaning as A1 in formula (2-1), and a preferred embodiment thereof is also the same. In formula (2-4), R4 has the same meaning as R1 in formula (2-1), and a preferred embodiment thereof is also the same.

-含量- 在特定樹脂包含式（2-4）所表示之重複單元之情況下，式（2-4）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，20～60質量%為更佳。 又，特定樹脂可以僅包含一種式（2-4）所表示之重複單元，亦可以包含兩種以上的不同結構之式（2-4）所表示之重複單元。在包含兩種以上的式（2-4）所表示之重複單元之情況下，式（2-4）所表示之重複單元的合計含量在上述範圍內為較佳。-Content- When the specific resin contains the repeating unit represented by formula (2-4), the content of the repeating unit represented by formula (2-4) is preferably 0.1 to 80 mass % relative to the total mass of the specific resin, and more preferably 20 to 60 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (2-4), or may contain two or more repeating units represented by formula (2-4) of different structures. When containing two or more repeating units represented by formula (2-4), the total content of the repeating units represented by formula (2-4) is preferably within the above range.

[式（3-1）、式（3-2）、式（3-3）或式（3-4）所表示之重複單元] 特定樹脂包含選自包括下述式（3-1）所表示之重複單元、下述式（3-2）所表示之重複單元、下述式（3-3）所表示之重複單元及下述式（3-4）所表示之重複單元之群組中的至少一種重複單元為較佳。 該等重複單元在結構中包含聚合性基。藉此，認為在硬化膜中形成基於聚合性之交聯結構，因此所獲得之硬化膜的耐藥品性進一步得到提高。 上述式（3-1）所表示之重複單元中所包含之聚合性基、上述式（3-2）所表示之重複單元中所包含之聚合性基、上述式（3-3）所表示之重複單元中所包含之聚合性基、上述式（3-4）所表示之重複單元中所包含之聚合性基包括包含乙烯性不飽和鍵之基團、環狀醚基、羥甲基或烷氧基甲基（較佳為，烷氧基的碳數為1～6之烷氧基甲基）之基團為較佳，乙烯基、（甲基）烯丙基、（甲基）丙烯醯胺基、（甲基）丙烯醯氧基、順丁烯二醯亞胺基、乙烯基苯基、環氧基、氧雜環丁基、羥甲基或烷氧基甲基為更佳，（甲基）丙烯醯氧基、（甲基）丙烯醯胺基、環氧基、羥甲基或烷氧基甲基為進一步較佳。 在特定樹脂包含式（2-1）所表示之重複單元之情況下，特定樹脂包含式（3-1）所表示之重複單元為較佳。 式（3-1）所表示之重複單元為在結構中包含式（2-1）所表示之重複單元之重複單元。 在特定樹脂包含式（2-2）所表示之重複單元之情況下，特定樹脂包含式（3-2）所表示之重複單元為較佳。 式（3-2）所表示之重複單元為在結構中包含式（2-2）所表示之重複單元之重複單元。 在特定樹脂包含式（2-3）所表示之重複單元之情況下，特定樹脂包含式（3-3）所表示之重複單元為較佳。 式（3-3）所表示之重複單元為在結構中包含兩個式（2-3）所表示之重複單元之重複單元。 在特定樹脂包含式（2-4）所表示之重複單元之情況下，特定樹脂包含式（3-4）所表示之重複單元為較佳。 式（3-4）所表示之重複單元為在結構中包含兩個式（2-4）所表示之重複單元之重複單元。 後述式（4-1）～式（4-4）中的任一個所表示之重複單元設為與式（3-1）～式（3-4）中的任一個所表示之重複單元不對應。 [化學式10] 式（3-1）中，X5 表示4價連接基，R3 及R4 分別獨立地表示1價有機基，Z1 表示2價連接基，R3 、R4 及Z1 中的至少一個包含聚合性基； 式（3-2）中，X6 表示4價連接基，Z2 表示具有聚合性基之2價連接基。 式（3-3）中，X7 及X8 分別獨立地表示3價連接基，Z3 及Z4 分別獨立地表示2價連接基，Z3 及Z4 中的至少一者表示具有聚合性基之2價連接基； 式（3-4）中，X7 及X8 分別獨立地表示3價連接基，Z3 及Z4 分別獨立地表示2價連接基，R5 及R6 分別獨立地表示1價有機基，Z3 及Z4 中的至少一者表示具有聚合性基之2價連接基，R5 、R6 、Z3 及Z4 中的至少一個包含聚合性基。[Repeating units represented by formula (3-1), formula (3-2), formula (3-3) or formula (3-4)] The specific resin preferably contains at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), a repeating unit represented by the following formula (3-3) and a repeating unit represented by the following formula (3-4). The repeating units contain a polymerizable group in the structure. It is believed that a cross-linked structure based on polymerizability is formed in the cured film, so that the chemical resistance of the obtained cured film is further improved. The polymerizable groups contained in the repeating units represented by the above formula (3-1), the polymerizable groups contained in the repeating units represented by the above formula (3-2), the polymerizable groups contained in the repeating units represented by the above formula (3-3), and the polymerizable groups contained in the repeating units represented by the above formula (3-4) include groups containing ethylenically unsaturated bonds, cyclic ether groups, hydroxymethyl groups or alkoxymethyl groups (preferably The specific resin is preferably a group of (meth)allyl, (meth)acrylamide, (meth)acryloxy, cis-butylenediamide, vinylphenyl, epoxy, cyclobutyl, hydroxymethyl or alkoxymethyl. (meth)acryloxy, (meth)acrylamide, epoxy, hydroxymethyl or alkoxymethyl are further preferred. When the specific resin contains the repeating unit represented by formula (2-1), the specific resin contains the repeating unit represented by formula (3-1). The repeating unit represented by formula (3-1) is a repeating unit containing the repeating unit represented by formula (2-1) in its structure. When the specific resin contains a repeating unit represented by formula (2-2), it is preferable that the specific resin contains a repeating unit represented by formula (3-2). The repeating unit represented by formula (3-2) is a repeating unit that contains the repeating unit represented by formula (2-2) in its structure. When the specific resin contains a repeating unit represented by formula (2-3), it is preferable that the specific resin contains a repeating unit represented by formula (3-3). The repeating unit represented by formula (3-3) is a repeating unit that contains two repeating units represented by formula (2-3) in its structure. When the specific resin contains a repeating unit represented by formula (2-4), it is preferable that the specific resin contains a repeating unit represented by formula (3-4). The repeating unit represented by formula (3-4) is a repeating unit including two repeating units represented by formula (2-4) in the structure. The repeating unit represented by any of formulas (4-1) to (4-4) described later is assumed to be not corresponding to the repeating unit represented by any of formulas (3-1) to (3-4). [Chemical formula 10] In formula (3-1), X5 represents a tetravalent linking group, R3 and R4 each independently represent a monovalent organic group, Z1 represents a divalent linking group, and at least one of R3 , R4 and Z1 contains a polymerizable group; In formula (3-2), X6 represents a tetravalent linking group, and Z2 represents a divalent linking group having a polymerizable group. In formula (3-3), X7 and X8 each independently represent a trivalent connecting group, Z3 and Z4 each independently represent a divalent connecting group, and at least one of Z3 and Z4 represents a divalent connecting group having a polymerizable group; In formula (3-4), X7 and X8 each independently represent a trivalent connecting group, Z3 and Z4 each independently represent a divalent connecting group, R5 and R6 each independently represent a monovalent organic group, and at least one of Z3 and Z4 represents a divalent connecting group having a polymerizable group, and at least one of R5 , R6 , Z3 and Z4 contains a polymerizable group.

[式（3-1）所表示之重複單元] -R3 、R4 、X5 - 式（3-1）中，R3 及R4 分別獨立地與式（2-1）中的R1 及R2 的含義相同，較佳態樣亦相同。 式（3-1）中，X5 與式（2-1）中的X1 的含義相同，較佳態樣亦相同。[Repeating units represented by formula (3-1)] -R 3 , R 4 , X 5 - In formula (3-1), R 3 and R 4 have the same meanings as R 1 and R 2 in formula (2-1), respectively, and preferably the same meanings. In formula (3-1), X 5 has the same meaning as X 1 in formula (2-1), and preferably the same meanings.

-Z1 - 式（3-1）中，Z1 為2價連接基。 Z1 為具有聚合性基之2價連接基為較佳。 在Z1 為不具有聚合性基的2價連接基之情況下，Z1 與後述式（6-1）中的Z5 的含義相同，較佳態樣亦相同。 在Z1 為不具有聚合性基的2價連接基之情況下，R3 及R4 中的至少一者為具有聚合性基之基團。 作為Z1 中之聚合性基，包括包含乙烯性不飽和鍵之基團、環狀醚基、羥甲基或烷氧基甲基（較佳為，烷氧基的碳數為1～6之烷氧基甲基）之基團為較佳，乙烯基、（甲基）烯丙基、（甲基）丙烯醯胺基、（甲基）丙烯醯氧基、順丁烯二醯亞胺基、乙烯基苯基、環氧基、氧雜環丁基、羥甲基或烷氧基甲基為更佳，（甲基）丙烯醯氧基、（甲基）丙烯醯胺基、環氧基、羥甲基或烷氧基甲基為進一步較佳。 Z1 中所包含之聚合性基的數量為一個以上，1～15個為較佳，1～10個為更佳，1～5個為進一步較佳，一個或兩個為特佳，一個為最佳。 又，從顯影性的觀點考慮，Z1 為包含芳香族烴基之基團為較佳，包含碳數6～30的芳香族烴基之基團為更佳，包含苯環結構或萘環結構之基團為進一步較佳，包含苯環結構之基團為特佳。-Z 1 - In formula (3-1), Z 1 is a divalent linking group. Z 1 is preferably a divalent linking group having a polymerizable group. When Z 1 is a divalent linking group not having a polymerizable group, Z 1 has the same meaning as Z 5 in formula (6-1) described later, and a preferred embodiment is also the same. When Z 1 is a divalent linking group not having a polymerizable group, at least one of R 3 and R 4 is a group having a polymerizable group. The polymerizable group in Z1 is preferably a group containing an ethylenic unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group (preferably an alkoxymethyl group having an alkoxy group with 1 to 6 carbon atoms), more preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a cis-butylenediamide group, a vinylphenyl group, an epoxy group, an oxacyclobutyl group, a hydroxymethyl group or an alkoxymethyl group, and still more preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group. The number of polymerizable groups contained in Z1 is one or more, preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, one or two are particularly preferred, and one is most preferred. In addition, from the viewpoint of developing properties, Z1 is preferably a group containing an aromatic hydrocarbon group, more preferably a group containing an aromatic hydrocarbon group having 6 to 30 carbon atoms, further preferably a group containing a benzene ring structure or a naphthalene ring structure, and particularly preferably a group containing a benzene ring structure.

＜＜式（Z-1）＞＞ 其中，Z1 為下述式（Z-1）所表示之基團為較佳。 [化學式11] 式（Z-1）中，Q1 表示碳數1～30的有機基，A1 表示包含聚合性基之基團，n1表示1以上的整數，*表示與其他結構的鍵結部位。＜＜Formula (Z-1)＞＞ Wherein, Z1 is preferably a group represented by the following formula (Z-1). [Chemical Formula 11] In formula (Z-1), Q1 represents an organic group having 1 to 30 carbon atoms, A1 represents a group containing a polymerizable group, n1 represents an integer greater than 1, and * represents a bonding site with other structures.

＜＜Q1 ＞＞ Q1 為包含芳香族烴基之n2+2價基團為較佳。 Q1 中之芳香族烴基為碳數6～30的芳香族烴基為較佳，碳數6～20的芳香族烴基為更佳，從苯環去除兩個以上的氫原子而獲得之基團為進一步較佳，從苯環去除三個以上的氫原子而獲得之基團為特佳。 式（Z-1）中，Q1 中之與式（Z-1）中所記載的兩個*的鍵結部位均為芳香族烴基為較佳。亦即，式（3-1）中所記載的兩個氮原子與Q1 中所包含之芳香族烴環結構直接鍵結為較佳。 又，式（Z-1）中，Q1 中之與A1 的鍵結部位均為芳香族烴基為較佳。亦即，A1 與Q1 中所包含之芳香族烴環結構直接鍵結為較佳。＜＜Q 1 ＞＞ Q 1 is preferably an n2+2 valent group containing an aromatic hydrocarbon group. The aromatic hydrocarbon group in Q 1 is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, further preferably a group obtained by removing two or more hydrogen atoms from a benzene ring, and particularly preferably a group obtained by removing three or more hydrogen atoms from a benzene ring. In formula (Z-1), it is preferred that the bonding sites of Q 1 to the two * described in formula (Z-1) are both aromatic hydrocarbon groups. That is, it is preferred that the two nitrogen atoms described in formula (3-1) are directly bonded to the aromatic hydrocarbon ring structure contained in Q 1 . In formula (Z-1), it is preferred that the bonding sites of Q1 and A1 are both aromatic hydrocarbon groups. In other words, it is preferred that A1 and the aromatic hydrocarbon ring structure contained in Q1 are directly bonded.

Q1 包含選自包括下述式（A2-1）～式（A2-5）所表示之結構之群組中的至少一種結構為較佳，選自包括式（A2-1）～式（A2-5）所表示之結構之群組中的至少一種結構為更佳。 [化學式12] 式（A2-1）～（A2-5）中，RA211 ～RA214 、RA221 ～RA224 、RA231 ～RA238 、RA241 ～RA248 及RA251 ～RA258 分別獨立地表示氫原子、烷基、環狀烷基、烷氧基、羥基、氰基、鹵化烷基或鹵素原子，LA231 及LA241 分別獨立地表示單鍵、羰基、磺醯基、2價飽和烴基、2價不飽和烴基、雜原子、雜環基或鹵化伸烷基，RA211 ～RA214 中的至少一個、RA221 ～RA224 中的至少一個、RA231 ～RA238 中的至少一個、RA241 ～RA248 中的至少一個及RA251 ～RA258 中的至少一個可以為與上述式（Z-1）中的A1 的鍵結部位，*分別獨立地表示與其他結構的鍵結部位。 Q1 preferably comprises at least one structure selected from the group consisting of structures represented by the following formula (A2-1) to (A2-5), and more preferably at least one structure selected from the group consisting of structures represented by the following formula (A2-1) to (A2-5). [Chemical Formula 12] In formulas (A2-1) to (A2-5), R A211 to R A214 , R A221 to R A224 , R A231 to R A238 , R A241 to R A248 and R A251 to R A258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group or a halogen atom, L A231 and L A241 each independently represent a single bond, a carbonyl group, a sulfonyl group, a divalent saturated alkyl group, a divalent unsaturated alkyl group, a heteroatom, a heterocyclic group or a halogenated alkylene group, and at least one of R A211 to R A214 , at least one of R A221 to R A224 , R A231 to R A238 , R A241 to R A248 and R A251 to R A258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group or a halogenated alkylene group. At least one of A238 , at least one of R A241 to R A248 , and at least one of R A251 to R A258 may be a bonding site with A1 in the above formula (Z-1), and * each independently represents a bonding site with other structures.

其中，從溶劑溶解性的觀點考慮，Q1 包含式（A2-1）～式（A2-4）中的任一個所表示之結構為較佳，包含式（A2-1）所表示之結構為更佳。Among them, from the viewpoint of solvent solubility, Q1 preferably includes a structure represented by any one of Formula (A2-1) to Formula (A2-4), and more preferably includes a structure represented by Formula (A2-1).

式（A2-1）中，RA211 ～RA214 分別獨立地表示氫原子、碳數1～6的烷基、碳數3～12的環狀烷基、碳數1～6的烷氧基、羥基、氰基、碳數1～3的鹵化烷基或鹵素原子為較佳，從溶劑溶解性的觀點考慮，氫原子、碳數1～6的烷基、碳數1～6的烷氧基、碳數1～3的鹵化烷基為更佳，氫原子或碳數1～6的烷基為更佳。 作為上述RA211 ～RA214 中之上述鹵化烷基中之鹵素原子或上述鹵素原子，可以舉出氟原子、氯原子、溴原子、碘原子等，氯原子或溴原子為較佳。 又，上述RA211 ～RA214 中的至少一個為與式（Z-1）中的A1 的鍵結部位為較佳，RA213 為與上述A1 的鍵結部位為更佳。In formula (A2-1), R A211 to R A214 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom. Preferably, from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms is selected. A hydrogen atom or an alkyl group having 1 to 6 carbon atoms is further preferred. Examples of the halogenated alkyl group or the halogenated atom in R A211 to R A214 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. Preferably, the chlorine atom or the bromine atom is selected. Furthermore, at least one of RA211 to RA214 is preferably a bonding site with A1 in formula (Z-1), and RA213 is more preferably a bonding site with A1 .

式（A2-2）中，RA221 ～RA224 分別與式（A2-1）中之RA211 ～RA214 的含義相同，較佳態樣亦相同。 又，上述RA211 ～RA214 中的至少一個為與式（Z-1）中的A1 的鍵結部位為較佳，一個或兩個為與上述A2 的鍵結部位為更佳。In formula (A2-2), R A221 to R A224 have the same meanings as R A211 to R A214 in formula (A2-1), and preferred embodiments thereof are also the same. In addition, at least one of the above R A211 to R A214 is preferably a bonding site with A 1 in formula (Z-1), and one or two are more preferably a bonding site with A 2 .

式（A2-3）中，RA231 ～RA238 分別與式（A2-1）中之RA211 ～RA214 的含義相同，較佳態樣亦相同。 式（A2-3）中，LA231 表示單鍵、碳數1～6的2價飽和烴基、碳數5～24的2價不飽和烴基、-O-、-S-、-NRN -、雜環基或碳數1～6的鹵化伸烷基為較佳，表示單鍵、碳數1～6的飽和烴基、-O-或雜環基為更佳，表示單鍵或-O-為進一步較佳。上述RN 如上所述，較佳態樣亦相同。 又，上述RA231 ～RA238 中的至少一個為與式（Z-1）中的A1 的鍵結部位為較佳，一個或兩個為與上述A2 的鍵結部位為更佳，RA231 ～RA234 中的一個和RA235 ～RA238 中的一個為與上述A1 的鍵結部位為進一步較佳。In formula (A2-3), R A231 to R A238 have the same meanings as R A211 to R A214 in formula (A2-1), respectively, and preferred embodiments are also the same. In formula (A2-3), L A231 preferably represents a single bond, a divalent saturated alkyl group having 1 to 6 carbon atoms, a divalent unsaturated alkyl group having 5 to 24 carbon atoms, -O-, -S-, -NR N -, a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms, more preferably represents a single bond, a saturated alkyl group having 1 to 6 carbon atoms, -O-, or a heterocyclic group, and even more preferably represents a single bond or -O-. The above-mentioned RN is as described above, and preferred embodiments are also the same. Furthermore, at least one of the above-mentioned R A231 to R A238 is preferably a bonding site with A 1 in formula (Z-1), one or two are more preferably a bonding site with A 2 , and one of R A231 to R A234 and one of R A235 to R A238 are even more preferably a bonding site with A 1 .

式（A2-4）中，RA241 ～RA248 及LA241 分別與式（A2-3）中之RA231 ～RA238 及LA231 的含義相同，較佳態樣亦相同。 又，上述RA241 ～RA248 中的至少一個為與式（Z-1）中的A1 的鍵結部位為較佳，一個或兩個為與上述A2 的鍵結部位為更佳，RA241 ～RA244 中的一個和RA245 ～RA248 中的一個為與上述A2 的鍵結部位為進一步較佳。In formula (A2-4), R A241 to R A248 and L A241 have the same meanings as R A231 to R A238 and L A231 in formula (A2-3), respectively, and preferred embodiments thereof are also the same. In addition, it is preferred that at least one of the above R A241 to R A248 is a bonding site with A 1 in formula (Z-1), and it is more preferred that one or two are bonding sites with A 2 , and it is further preferred that one of R A241 to R A244 and one of R A245 to R A248 are bonding sites with A 2 .

式（A2-5）中，RA251 ～RA258 分別與式（A2-1）中之RA211 ～RA214 的含義相同，較佳態樣亦相同。 又，上述RA251 ～RA258 中的至少一個為與式（Z-1）中的A1 的鍵結部位為較佳，一個或兩個為與上述A1 的鍵結部位為更佳，RA251 ～RA254 中的一個和RA255 ～RA258 中的一個為與上述A1 的鍵結部位為進一步較佳。In formula (A2-5), R A251 to R A258 have the same meanings as R A211 to R A214 in formula (A2-1), and preferred embodiments thereof are also the same. In addition, it is preferred that at least one of the above R A251 to R A258 is a bonding site with A 1 in formula (Z-1), and it is more preferred that one or two are bonding sites with A 1 , and it is further preferred that one of R A251 to R A254 and one of R A255 to R A258 are bonding sites with A 1 .

＜＜A1 ＞＞ 式（Z-1）中，A1 表示包含聚合性基之基團。 作為聚合性基，包括包含乙烯性不飽和鍵之基團、環狀醚基、羥甲基或烷氧基甲基（較佳為，烷氧基的碳數為1～6之烷氧基甲基）之基團為較佳，乙烯基、（甲基）烯丙基、（甲基）丙烯醯胺基、（甲基）丙烯醯氧基、順丁烯二醯亞胺基、乙烯基苯基、環氧基、氧雜環丁基或羥甲基為更佳，（甲基）丙烯醯氧基、（甲基）丙烯醯胺基、環氧基、羥甲基或烷氧基甲基為進一步較佳。 A2 中所包含之聚合性基的數量為一個以上，1～15個為較佳，1～10個為更佳，1～5個為進一步較佳，一個或兩個為特佳，一個為最佳。＜＜A 1 ＞＞ In formula (Z-1), A 1 represents a group containing a polymerizable group. As the polymerizable group, a group containing an ethylenic unsaturated bond, a cyclic ether group, a hydroxymethyl group or an alkoxymethyl group (preferably an alkoxymethyl group having 1 to 6 carbon atoms in the alkoxy group) is preferred, a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloxy group, a cis-butylenediamide group, a vinylphenyl group, an epoxy group, an oxocyclobutyl group or a hydroxymethyl group is more preferred, and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group or an alkoxymethyl group is further preferred. The number of polymerizable groups contained in A2 is one or more, preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, particularly preferably one or two, and most preferably one.

又，A1 為下述式（P-1）所表示之基團為較佳。 [化學式13] 式（P-1）中，L1 表示單鍵或m+1價連接基，A2 表示聚合性基，m表示1以上的整數，*表示與Q1 的鍵結部位。 式（P-1）中，L1 為單鍵或烴基、-O-、-C（=O）-、-S-、-S（=O）2 -、-NRN -或該等鍵結兩個以上而獲得之基團為較佳，單鍵或烴基、-O-、-C（=O）-、-NRN -或該等鍵結兩個以上而獲得之基團為更佳。 上述RN 表示氫原子或烴基，氫原子、烷基或芳基為更佳，氫原子或烷基為進一步較佳，氫原子為特佳。 作為上述L1 中之烴基，碳數1～30的飽和脂肪族烴基、碳數6～30的芳香族烴基或由該等組合表示之基團為較佳，碳數1～10的飽和脂肪族烴基、從苯環去除兩個以上的氫原子而獲得之基團或由該等鍵結表示之基團為更佳。Furthermore, A1 is preferably a group represented by the following formula (P-1). [Chemical Formula 13] In formula (P-1), L1 represents a single bond or an m+1 valent linking group, A2 represents a polymerizable group, m represents an integer greater than 1, and * represents a bonding site with Q1 . In formula (P-1), L1 is preferably a single bond or a alkyl group, -O-, -C(=O)-, -S-, -S(=O) 2- , -NRN- , or a group obtained by bonding two or more of these groups, and more preferably a single bond or a alkyl group, -O-, -C(=O)-, -NRN- , or a group obtained by bonding two or more of these groups. The above-mentioned RN represents a hydrogen atom or a alkyl group, more preferably a hydrogen atom, an alkyl group, or an aryl group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. As the alkyl group in the above L1 , a saturated aliphatic alkyl group having 1 to 30 carbon atoms, an aromatic alkyl group having 6 to 30 carbon atoms, or a group represented by a combination thereof is preferred, and a saturated aliphatic alkyl group having 1 to 10 carbon atoms, a group obtained by removing two or more hydrogen atoms from a benzene ring, or a group represented by such a bond is more preferred.

式（P-1）中，A2 為乙烯基、（甲基）烯丙基、（甲基）丙烯醯胺基、（甲基）丙烯醯氧基、順丁烯二醯亞胺基、乙烯基苯基、環氧基、氧雜環丁基、羥甲基或烷氧基甲基為較佳，（甲基）丙烯醯氧基、（甲基）丙烯醯胺基、環氧基、羥甲基或烷氧基甲基為更佳。In formula (P-1), A2 is preferably vinyl, (meth)allyl, (meth)acrylamide, (meth)acryloxy, cis-butylenediamide, vinylphenyl, epoxy, cyclohexyl, hydroxymethyl or alkoxymethyl, and more preferably (meth)acryloxy, (meth)acrylamide, epoxy, hydroxymethyl or alkoxymethyl.

式（P-1）中，m為1～15的整數為較佳，1～10的整數為更佳，1～5的整數為進一步較佳，1或2為特佳，1為最佳。In formula (P-1), m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, further preferably an integer of 1 to 5, particularly preferably 1 or 2, and most preferably 1.

又，A1 為下述式（P-2）或式（P-3）所表示之基團為較佳。 [化學式14] 式（P-2）中，A2 表示聚合性基，*表示與Q1 的鍵結部位。 式（P-2）中，A2 與式（P-1）中之A2 的含義相同，較佳態樣亦相同。 式（P-3）中，A2 表示聚合性基，L2 表示烴基、-O-、-C（=O）-、-S-、-S（=O）2 -、碳酸酯鍵、-NRN -或該等鍵結兩個以上而獲得之基團，Z1 表示醚鍵、酯鍵、胺甲酸乙酯鍵、脲鍵、碳酸酯鍵或醯胺鍵，*表示與Y1 的鍵結部位。RN 如上所述。 式（P-3）中，A2 與式（P-1）中之A2 的含義相同，較佳態樣亦相同。 式（P-3）中，L2 為烴基、（聚）伸烷氧基或由該等組合表示之基團為較佳，烴基為更佳。 在本說明書中，（聚）伸烷氧基表示伸烷氧基或聚伸烷氧基。又，在本發明中，聚伸烷氧基是指直接鍵結兩個以上的伸烷氧基而獲得之基團。聚伸烷氧基中所包含之複數個伸烷氧基中之伸烷基可以分別相同，亦可以不同。在聚伸烷氧基包含伸烷基不同之複數種伸烷氧基之情況下，聚伸烷氧基中之伸烷氧基的排列可以為無規排列，亦可以為具有嵌段之排列，還可以為具有交替等圖案之排列。 作為上述烴基，伸烷基、2價芳香族烴基或由該等組合表示之基團為較佳，伸烷基為更佳。 作為上述伸烷基，碳數1～30的伸烷基為較佳，碳數1～20的伸烷基為更佳，碳數1～10的伸烷基為進一步較佳。 在本發明中，在簡單記載為“脂肪族烴基”、“飽和脂肪族烴基”、“烷基”、“伸烷基”等之情況下，除非另有說明，則該等基團可以具有支鏈結構及環狀結構中的至少一者。例如，除非另有說明，則“烷基”中包括直鏈烷基、支鏈烷基、環狀烷基及由該等組合表示之烷基。 作為上述芳香族烴基，碳數6～30的芳香族烴基為較佳，碳數6～20的芳香族烴基為更佳，伸苯基或伸萘基為進一步較佳，伸苯基為特佳。 作為上述（聚）伸烷氧基中之伸烷基，碳數2～10的伸烷基為較佳，碳數2～4的伸烷基為更佳，伸乙基或伸丙基為更佳，伸乙基為進一步較佳。 又，聚伸烷氧基中所包含之伸烷氧基的數量（聚伸烷氧基的重複數）為2～20個為較佳，2～10個為更佳，2～5個為進一步較佳，2～4個為特佳。 式（P-3）中，Z1 表示醚鍵、酯鍵、胺甲酸乙酯鍵、脲鍵或醯胺鍵，酯鍵、胺甲酸乙酯鍵、脲鍵或醯胺鍵為更佳。 式（P-3）中，*表示與Q1 的鍵結部位。Furthermore, A1 is preferably a group represented by the following formula (P-2) or formula (P-3). [Chemical Formula 14] In formula (P-2), A 2 represents a polymerizable group, and * represents a bonding site with Q 1. In formula (P-2), A 2 has the same meaning as A 2 in formula (P-1), and a preferred embodiment is also the same. In formula (P-3), A 2 represents a polymerizable group, L 2 represents a alkyl group, -O-, -C(=O)-, -S-, -S(=O) 2 -, a carbonate bond, -NR N -, or a group obtained by bonding two or more of these groups, Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, a carbonate bond, or an amide bond, and * represents a bonding site with Y 1. RN is as described above. In formula (P-3), A 2 has the same meaning as A 2 in formula (P-1), and a preferred embodiment is also the same. In formula (P-3), L2 is preferably a alkyl group, a (poly)alkoxyl group, or a group represented by a combination thereof, and a alkyl group is more preferred. In the present specification, a (poly)alkoxyl group represents an alkoxyl group or a polyalkoxyl group. In addition, in the present invention, a polyalkoxyl group refers to a group obtained by directly bonding two or more alkoxyl groups. The alkylene groups in the multiple alkoxyl groups contained in the polyalkoxyl group may be the same or different. In the case where the polyalkoxyl group contains multiple alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, an arrangement with blocks, or an arrangement with alternating patterns. As the above-mentioned alkyl group, an alkylene group, a divalent aromatic alkyl group, or a group represented by a combination thereof is preferred, and an alkylene group is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 30 carbon atoms is preferred, an alkylene group having 1 to 20 carbon atoms is more preferred, and an alkylene group having 1 to 10 carbon atoms is further preferred. In the present invention, when simply described as "aliphatic alkyl group", "saturated aliphatic alkyl group", "alkyl group", "alkylene group", etc., unless otherwise specified, these groups may have at least one of a branched structure and a cyclic structure. For example, unless otherwise specified, "alkyl group" includes a straight chain alkyl group, a branched chain alkyl group, a cyclic alkyl group, and an alkyl group represented by a combination thereof. As the above-mentioned aromatic alkyl group, an aromatic alkyl group having 6 to 30 carbon atoms is preferred, an aromatic alkyl group having 6 to 20 carbon atoms is more preferred, a phenylene group or a naphthylene group is further preferred, and a phenylene group is particularly preferred. As the alkylene group in the above-mentioned (poly)alkoxylene group, an alkylene group having 2 to 10 carbon atoms is preferred, an alkylene group having 2 to 4 carbon atoms is more preferred, an ethylene group or a propylene group is more preferred, and an ethylene group is further preferred. Moreover, the number of alkoxylene groups contained in the polyalkoxylene group (the number of repetitions of the polyalkoxylene group) is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, and particularly preferably 2 to 4. In formula (P-3), Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, or an amide bond, and an ester bond, a urethane bond, a urea bond, or an amide bond is more preferred. In formula (P-3), * represents a bonding site with Q 1 .

又，從耐藥品性的觀點考慮，A1 中所包含之聚合性基與特定樹脂的主鏈的距離為0～15為較佳，0～10為更佳。 其中，A1 中所包含之聚合性基與特定樹脂的主鏈的距離是指在聚醯亞胺的主鏈中所包含之原子與聚合性基之間所包含之原子數中的最小的數。例如，在後述實施例中之式（PZ-3）所表示之樹脂中，甲基丙烯醯氧基與主鏈的距離為4。 亦即，在聚醯亞胺在主鏈內部具有環結構之情況下，“上述聚醯亞胺的主鏈中所包含之原子”包含上述環結構的環員。 又，在A1 包含複數個聚合性基之情況下，A1 中所包含之聚合性基中的最靠近主鏈的聚合性基與聚醯亞胺的主鏈的距離為0～15為較佳，0～10為更佳。進而，在A1 包含複數個聚合性基之情況下，A1 中所包含之所有聚合性基與聚醯亞胺的主鏈的距離為0～15為進一步較佳，0～10為特佳。Furthermore, from the viewpoint of drug resistance, the distance between the polymerizable group contained in A1 and the main chain of the specific resin is preferably 0 to 15, and more preferably 0 to 10. The distance between the polymerizable group contained in A1 and the main chain of the specific resin refers to the smallest number of atoms contained between the atoms contained in the main chain of the polyimide and the polymerizable group. For example, in the resin represented by formula (PZ-3) in the embodiment described below, the distance between the methacryloyloxy group and the main chain is 4. That is, when the polyimide has a ring structure inside the main chain, "the atoms contained in the main chain of the above-mentioned polyimide" includes the ring members of the above-mentioned ring structure. Furthermore, when A1 contains a plurality of polymerizable groups, the distance between the polymerizable group closest to the main chain among the polymerizable groups contained in A1 and the main chain of the polyimide is preferably 0 to 15, and more preferably 0 to 10. Furthermore, when A1 contains a plurality of polymerizable groups, the distance between all the polymerizable groups contained in A1 and the main chain of the polyimide is further preferably 0 to 15, and particularly preferably 0 to 10.

＜＜n1＞＞ 式（Z-1）中，n1表示1以上的整數，1～20的整數為較佳，1～10的整數為更佳，1～4的整數為進一步較佳，1或2為特佳，1為最佳。 又，在n1為2以上的整數之情況下，n1個A1 分別可以相同，亦可以不同。＜＜n1＞＞ In formula (Z-1), n1 represents an integer greater than or equal to 1, preferably an integer from 1 to 20, more preferably an integer from 1 to 10, further preferably an integer from 1 to 4, particularly preferably 1 or 2, and most preferably 1. When n1 is an integer greater than or equal to 2, the n1 A1s may be the same or different.

-含量- 在特定樹脂包含式（3-1）所表示之重複單元之情況下，式（3-1）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，20～60質量%為更佳。 又，特定樹脂可以僅包含一種式（3-1）所表示之重複單元，亦可以包含兩種以上的不同結構之式（3-1）所表示之重複單元。在包含兩種以上的式（3-1）所表示之重複單元之情況下，式（3-1）所表示之重複單元的合計含量在上述範圍內為較佳。-Content- When the specific resin contains the repeating unit represented by formula (3-1), the content of the repeating unit represented by formula (3-1) is preferably 0.1 to 80 mass % relative to the total mass of the specific resin, and more preferably 20 to 60 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (3-1), or may contain two or more repeating units represented by formula (3-1) of different structures. When containing two or more repeating units represented by formula (3-1), the total content of the repeating units represented by formula (3-1) is preferably within the above range.

[式（3-2）所表示之重複單元] -X6 - 式（3-1）中，X6 與式（2-2）中的X2 的含義相同，較佳態樣亦相同。[Repeating unit represented by formula (3-2)] -X 6 - In formula (3-1), X 6 has the same meaning as X 2 in formula (2-2), and preferred embodiments are also the same.

-Z2 - 式（3-2）中，Z2 與式（3-1）中的Z1 的含義相同，較佳態樣亦相同。-Z 2 - In formula (3-2), Z 2 has the same meaning as Z 1 in formula (3-1), and the preferred embodiment is also the same.

-含量- 在特定樹脂包含式（3-2）所表示之重複單元之情況下，式（3-2）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，20～60質量%為更佳。 又，特定樹脂可以僅包含一種式（3-2）所表示之重複單元，亦可以包含兩種以上的不同結構之式（3-2）所表示之重複單元。在包含兩種以上的式（3-2）所表示之重複單元之情況下，式（3-2）所表示之重複單元的合計含量在上述範圍內為較佳。-Content- When the specific resin contains the repeating unit represented by formula (3-2), the content of the repeating unit represented by formula (3-2) is preferably 0.1 to 80 mass % relative to the total mass of the specific resin, and more preferably 20 to 60 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (3-2), or may contain two or more repeating units represented by formula (3-2) of different structures. When containing two or more repeating units represented by formula (3-2), the total content of the repeating units represented by formula (3-2) is preferably within the above range.

[式（3-3）所表示之重複單元] 式（3-3）中，X7 及X8 分別獨立地與式（2-3）中的X3 的含義相同，較佳態樣亦相同。 式（3-3）中，Z3 及Z4 中的至少一者表示具有聚合性基之2價連接基，Z3 及Z4 均為具有聚合性基之2價連接基為較佳。 在Z3 為具有聚合性基之2價連接基之情況下，Z3 與式（3-1）中的Z1 的含義相同，較佳態樣亦相同。 在Z4 為具有聚合性基之2價連接基之情況下，Z4 與式（3-1）中的Z1 的含義相同，較佳態樣亦相同。 在Z3 為不具有聚合性基的2價連接基之情況下，Z3 與後述式（6-1）中的Z5 的含義相同，較佳態樣亦相同。 在Z4 為不具有聚合性基的2價連接基之情況下，Z4 與後述式（6-1）中的Z5 的含義相同，較佳態樣亦相同。[Repeating unit represented by formula (3-3)] In formula (3-3), X7 and X8 are independently the same as X3 in formula (2-3), and the preferred embodiment is the same. In formula (3-3), at least one of Z3 and Z4 represents a divalent connecting group having a polymerizable group, and it is preferred that both Z3 and Z4 are divalent connecting groups having a polymerizable group. When Z3 is a divalent connecting group having a polymerizable group, Z3 has the same meaning as Z1 in formula (3-1), and the preferred embodiment is the same. When Z4 is a divalent connecting group having a polymerizable group, Z4 has the same meaning as Z1 in formula (3-1), and the preferred embodiment is the same. When Z3 is a divalent linking group having no polymerizable group, Z3 has the same meaning as Z5 in the formula (6-1) described later, and a preferred embodiment thereof is also the same. When Z4 is a divalent linking group having no polymerizable group, Z4 has the same meaning as Z5 in the formula (6-1) described later, and a preferred embodiment thereof is also the same.

-含量- 在特定樹脂包含式（3-3）所表示之重複單元之情況下，式（3-3）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，20～60質量%為更佳。 又，特定樹脂可以僅包含一種式（3-3）所表示之重複單元，亦可以包含兩種以上的不同結構之式（3-3）所表示之重複單元。在包含兩種以上的式（3-3）所表示之重複單元之情況下，式（3-3）所表示之重複單元的合計含量在上述範圍內為較佳。-Content- When the specific resin contains the repeating unit represented by formula (3-3), the content of the repeating unit represented by formula (3-3) is preferably 0.1 to 80 mass % relative to the total mass of the specific resin, and more preferably 20 to 60 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (3-3), or may contain two or more repeating units represented by formula (3-3) of different structures. When containing two or more repeating units represented by formula (3-3), the total content of the repeating units represented by formula (3-3) is preferably within the above range.

[式（3-4）所表示之重複單元] 式（3-4）中，X7 及X8 分別獨立地與式（2-4）中的X4 的含義相同，較佳態樣亦相同。 式（3-4）中，Z3 及Z4 中的至少一者表示具有聚合性基之2價連接基為較佳，Z3 及Z4 均為具有聚合性基之2價連接基為更佳。 在Z3 為具有聚合性基之2價連接基之情況下，Z3 與式（3-1）中的Z1 的含義相同，較佳態樣亦相同。 在Z4 為具有聚合性基之2價連接基之情況下，Z4 與式（3-1）中的Z1 的含義相同，較佳態樣亦相同。 在Z3 為不具有聚合性基的2價連接基之情況下，Z3 與後述式（6-1）中的Z5 的含義相同，較佳態樣亦相同。 在Z4 為不具有聚合性基的2價連接基之情況下，Z4 與後述式（6-1）中的Z5 的含義相同，較佳態樣亦相同。 式（3-4）中，R5 及R6 分別與式（3-1）中的R3 及R4 的含義相同，較佳態樣亦相同。[Repeating unit represented by formula (3-4)] In formula (3-4), X7 and X8 are independently the same as X4 in formula (2-4), and the preferred embodiment is the same. In formula (3-4), at least one of Z3 and Z4 is preferably a divalent linking group having a polymerizable group, and Z3 and Z4 are more preferably both divalent linking groups having a polymerizable group. When Z3 is a divalent linking group having a polymerizable group, Z3 has the same meaning as Z1 in formula (3-1), and the preferred embodiment is the same. When Z4 is a divalent linking group having a polymerizable group, Z4 has the same meaning as Z1 in formula (3-1), and the preferred embodiment is the same. When Z3 is a divalent linking group without a polymerizable group, Z3 has the same meaning as Z5 in the formula (6-1) described later, and a preferred embodiment thereof is also the same. When Z4 is a divalent linking group without a polymerizable group, Z4 has the same meaning as Z5 in the formula (6-1) described later, and a preferred embodiment thereof is also the same. In formula (3-4), R5 and R6 have the same meanings as R3 and R4 in formula (3-1), respectively, and a preferred embodiment thereof is also the same.

-含量- 在特定樹脂包含式（3-4）所表示之重複單元之情況下，式（3-4）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，20～60質量%為更佳。 又，特定樹脂可以僅包含一種式（3-4）所表示之重複單元，亦可以包含兩種以上的不同結構之式（3-4）所表示之重複單元。在包含兩種以上的式（3-4）所表示之重複單元之情況下，式（3-4）所表示之重複單元的合計含量在上述範圍內為較佳。-Content- When the specific resin contains the repeating unit represented by formula (3-4), the content of the repeating unit represented by formula (3-4) is preferably 0.1 to 80 mass % relative to the total mass of the specific resin, and more preferably 20 to 60 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (3-4), or may contain two or more repeating units represented by formula (3-4) of different structures. When containing two or more repeating units represented by formula (3-4), the total content of the repeating units represented by formula (3-4) is preferably within the above range.

[式（4-1）、式（4-2）、式（4-3）、式（4-4）] 特定樹脂包含選自包括式（4-1）所表示之重複單元、式（4-2）所表示之重複單元及式（4-3）所表示之重複單元之群組中的至少一種重複單元為較佳。 在特定樹脂包含式（2-1）所表示之重複單元之情況下，特定樹脂包含式（4-1）所表示之重複單元為較佳。 式（4-1）所表示之重複單元為包含式（1-1）所表示之重複單元及式（2-1）所表示之重複單元之重複單元。 在特定樹脂包含式（2-2）所表示之重複單元之情況下，特定樹脂包含式（4-2）所表示之重複單元為較佳。 式（4-2）所表示之重複單元為包含式（1-1）所表示之重複單元及式（2-2）所表示之重複單元之重複單元。 在特定樹脂包含式（2-3）所表示之重複單元之情況下，特定樹脂包含式（4-3）所表示之重複單元為較佳。 式（4-3）所表示之重複單元為包含式（1-1）所表示之重複單元及式（2-3）所表示之重複單元之重複單元。 在特定樹脂包含式（2-4）所表示之重複單元之情況下，特定樹脂包含式（4-4）所表示之重複單元為較佳。 式（4-4）所表示之重複單元為包含式（1-1）所表示之重複單元及式（2-4）所表示之重複單元之重複單元。 [化學式15] [Formula (4-1), Formula (4-2), Formula (4-3), Formula (4-4)] The specific resin preferably includes at least one repeating unit selected from the group consisting of a repeating unit represented by Formula (4-1), a repeating unit represented by Formula (4-2), and a repeating unit represented by Formula (4-3). When the specific resin includes a repeating unit represented by Formula (2-1), the specific resin preferably includes a repeating unit represented by Formula (4-1). The repeating unit represented by Formula (4-1) is a repeating unit including a repeating unit represented by Formula (1-1) and a repeating unit represented by Formula (2-1). When the specific resin includes a repeating unit represented by formula (2-2), it is preferable that the specific resin includes a repeating unit represented by formula (4-2). The repeating unit represented by formula (4-2) is a repeating unit including a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-2). When the specific resin includes a repeating unit represented by formula (2-3), it is preferable that the specific resin includes a repeating unit represented by formula (4-3). The repeating unit represented by formula (4-3) is a repeating unit including a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-3). When the specific resin contains a repeating unit represented by formula (2-4), it is preferable that the specific resin contains a repeating unit represented by formula (4-4). The repeating unit represented by formula (4-4) is a repeating unit containing a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-4). [Chemical Formula 15]

式（4-1）中，X5 表示4價有機基，R3 及R4 分別獨立地表示1價有機基，L41 為下述式（L-1）所表示之結構。 式（4-1）中，X5 、R3 及R4 分別與式（3-1）中的X5 、R3 及R4 的含義相同，較佳態樣亦相同。 式（4-2）中，X6 表示4價基團，L42 為下述式（L-1）所表示之結構。 式（4-2）中，X6 與式（3-2）中的X6 的含義相同，較佳態樣亦相同。 式（4-3）中，X7 及X8 分別獨立地表示3價連接基，L44 表示2價連接基，L43 為下述式（L-1）所表示之結構。 式（4-3）中，X7 及X8 分別與式（3-3）中的X7 及X8 的含義相同，較佳態樣亦相同。 式（4-3）中，L44 表示2價連接基，並且為與式（3-3）中的Z3 中之具有聚合性基之2價連接基或不具有聚合性基的2價連接基相同的基團為較佳，為與式（3-3）中的Z3 中之具有聚合性基之2價連接基相同的基團為更佳。 式（4-4）中，X7 及X8 分別獨立地表示3價連接基，L46 表示2價連接基，L45 為下述式（L-1）所表示之結構。 式（4-4）中，X7 及X8 分別與式（3-4）中的X7 及X8 的含義相同，較佳態樣亦相同。 式（4-4）中，R5 及R6 分別與式（3-4）中的R5 及R6 的含義相同，較佳態樣亦相同。 式（4-4）中，L46 表示2價連接基，並且為與式（3-4）中的Z3 中之具有聚合性基之2價連接基或不具有聚合性基的2價連接基相同的基團為較佳，為與式（3-4）中的Z3 中之具有聚合性基之2價連接基相同的基團為更佳。 [化學式16] 式（L-1）中，Y1 表示2價連接基，Ar1 表示取代基或可以具有縮合環結構之芳香族烴基，Y2 表示單鍵或2價連接基，*表示與其他結構的鍵結部位。 式（L-1）中之Y1 、Ar1 及Y2 分別與式（1-1）中之Y1 、Ar1 及Y2 的含義相同，較佳態樣亦相同。In formula (4-1), X5 represents a 4-valent organic group, R3 and R4 each independently represent a 1-valent organic group, and L41 is a structure represented by the following formula (L-1). In formula (4-1), X5 , R3 and R4 have the same meanings as X5 , R3 and R4 in formula (3-1), and a preferred embodiment thereof is also the same. In formula (4-2), X6 represents a 4-valent group, and L42 is a structure represented by the following formula (L-1). In formula (4-2), X6 has the same meaning as X6 in formula (3-2), and a preferred embodiment thereof is also the same. In formula (4-3), X7 and X8 each independently represent a 3-valent linking group, L44 represents a 2-valent linking group, and L43 is a structure represented by the following formula (L-1). In formula (4-3), X7 and X8 have the same meanings as X7 and X8 in formula (3-3), and preferred embodiments are also the same. In formula (4-3), L44 represents a divalent linking group, and is preferably the same group as the divalent linking group having a polymerizable group or the divalent linking group not having a polymerizable group in Z3 in formula (3-3), and is more preferably the same group as the divalent linking group having a polymerizable group in Z3 in formula (3-3). In formula (4-4), X7 and X8 each independently represent a trivalent linking group, L46 represents a divalent linking group, and L45 is a structure represented by the following formula (L-1). In formula (4-4), X7 and X8 have the same meanings as X7 and X8 in formula (3-4), and preferred embodiments are the same. In formula (4-4), R5 and R6 have the same meanings as R5 and R6 in formula (3-4), and preferred embodiments are the same. In formula (4-4), L46 represents a divalent linking group, and is preferably the same group as the divalent linking group having a polymerizable group or the divalent linking group not having a polymerizable group in Z3 in formula (3-4), and is more preferably the same group as the divalent linking group having a polymerizable group in Z3 in formula (3-4). [Chemical Formula 16] In formula (L-1), Y1 represents a divalent linking group, Ar1 represents a substituent or an aromatic hydrocarbon group which may have a condensed ring structure, Y2 represents a single bond or a divalent linking group, and * represents a bonding site with other structures. Y1 , Ar1 and Y2 in formula (L-1) have the same meanings as Y1 , Ar1 and Y2 in formula (1-1), respectively, and the preferred embodiments are also the same.

在特定樹脂包含式（4-1）所表示之重複單元之情況下，式（4-1）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，20～60質量%為更佳。 又，特定樹脂可以僅包含一種式（4-1）所表示之重複單元，亦可以包含兩種以上的不同結構之式（4-1）所表示之重複單元。在包含兩種以上的式（4-1）所表示之重複單元之情況下，式（4-1）所表示之重複單元的合計含量在上述範圍內為較佳。 在特定樹脂包含式（4-2）所表示之重複單元之情況下，式（4-2）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，20～60質量%為更佳。 又，特定樹脂可以僅包含一種式（4-2）所表示之重複單元，亦可以包含兩種以上的不同結構之式（4-2）所表示之重複單元。在包含兩種以上的式（4-2）所表示之重複單元之情況下，式（4-2）所表示之重複單元的合計含量在上述範圍內為較佳。 在特定樹脂包含式（4-3）所表示之重複單元之情況下，式（4-3）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，20～60質量%為更佳。 又，特定樹脂可以僅包含一種式（4-3）所表示之重複單元，亦可以包含兩種以上的不同結構之式（4-3）所表示之重複單元。在包含兩種以上的式（4-3）所表示之重複單元之情況下，式（4-3）所表示之重複單元的合計含量在上述範圍內為較佳。 在特定樹脂包含式（4-4）所表示之重複單元之情況下，式（4-4）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，20～60質量%為更佳。 又，特定樹脂可以僅包含一種式（4-4）所表示之重複單元，亦可以包含兩種以上的不同結構之式（4-4）所表示之重複單元。在包含兩種以上的式（4-3）所表示之重複單元之情況下，式（4-4）所表示之重複單元的合計含量在上述範圍內為較佳。When the specific resin contains the repeating unit represented by formula (4-1), the content of the repeating unit represented by formula (4-1) is preferably 0.1 to 80 mass % relative to the total mass of the specific resin, and more preferably 20 to 60 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (4-1), or may contain two or more repeating units represented by formula (4-1) of different structures. When containing two or more repeating units represented by formula (4-1), the total content of the repeating units represented by formula (4-1) is preferably within the above range. When the specific resin contains the repeating unit represented by formula (4-2), the content of the repeating unit represented by formula (4-2) is preferably 0.1 to 80 mass % relative to the total mass of the specific resin, and more preferably 20 to 60 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (4-2), or may contain two or more repeating units represented by formula (4-2) of different structures. When containing two or more repeating units represented by formula (4-2), the total content of the repeating units represented by formula (4-2) is preferably within the above range. When the specific resin contains the repeating unit represented by formula (4-3), the content of the repeating unit represented by formula (4-3) is preferably 0.1 to 80 mass % relative to the total mass of the specific resin, and more preferably 20 to 60 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (4-3), or may contain two or more repeating units represented by formula (4-3) of different structures. When containing two or more repeating units represented by formula (4-3), the total content of the repeating units represented by formula (4-3) is preferably within the above range. When the specific resin contains the repeating unit represented by formula (4-4), the content of the repeating unit represented by formula (4-4) is preferably 0.1 to 80 mass % relative to the total mass of the specific resin, and more preferably 20 to 60 mass %. In addition, the specific resin may contain only one repeating unit represented by formula (4-4), or may contain two or more repeating units represented by formula (4-4) of different structures. When containing two or more repeating units represented by formula (4-3), the total content of the repeating units represented by formula (4-4) is preferably within the above range.

[式（5-1）] 特定樹脂包含式（5-1）所表示之重複單元亦較佳。 式（5-1）所表示之重複單元為包含式（1-1）所表示之重複單元之基團。 特定樹脂包含式（5-1）所表示之重複單元及選自包括式（3-1）所表示之重複單元、式（3-2）所表示之重複單元、式（3-3）所表示之重複單元及式（3-4）所表示之重複單元之群組中的至少一種重複單元為較佳，包含式（5-1）所表示之重複單元及式（3-1）所表示之重複單元或者包含式（5-1）所表示之重複單元及式（3-4）所表示之重複單元為更佳。 [化學式17] 式（5-1）中，L51 為上述式（L-1）所表示之結構，L52 表示2價有機基。 式（5-1）中，L52 與式（3-1）中的Z1 的含義相同，較佳態樣亦相同。[Formula (5-1)] The specific resin preferably contains a repeating unit represented by formula (5-1). The repeating unit represented by formula (5-1) is a group containing a repeating unit represented by formula (1-1). The specific resin preferably contains a repeating unit represented by formula (5-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by formula (3-1), a repeating unit represented by formula (3-2), a repeating unit represented by formula (3-3) and a repeating unit represented by formula (3-4), and more preferably contains a repeating unit represented by formula (5-1) and a repeating unit represented by formula (3-1) or contains a repeating unit represented by formula (5-1) and a repeating unit represented by formula (3-4). [Chemical Formula 17] In formula (5-1), L51 is the structure represented by the above formula (L-1), and L52 is a divalent organic group. In formula (5-1), L52 has the same meaning as Z1 in formula (3-1), and the preferred embodiment is also the same.

在特定樹脂包含式（5-1）所表示之重複單元之情況下，式（5-1）所表示之重複單元的含量相對於特定樹脂的總質量為0.1～80質量%為較佳，10～50質量%為更佳。 特定樹脂可以僅包含一種式（5-1）所表示之重複單元，亦可以包含兩種以上的不同結構之式（5-1）所表示之重複單元。在包含兩種以上的式（5-1）所表示之重複單元之情況下，式（5-1）所表示之重複單元的合計含量在上述範圍內為較佳。When the specific resin contains the repeating unit represented by formula (5-1), the content of the repeating unit represented by formula (5-1) is preferably 0.1 to 80 mass %, and more preferably 10 to 50 mass % relative to the total mass of the specific resin. The specific resin may contain only one repeating unit represented by formula (5-1), or may contain two or more repeating units represented by formula (5-1) of different structures. When containing two or more repeating units represented by formula (5-1), the total content of the repeating units represented by formula (5-1) is preferably within the above range.

[其他重複單元] 特定樹脂還可以包含其他重複單元。 作為其他重複單元，例如可以舉出式（6-1）～式（6-4）中的任一個所表示之重複單元。 與上述式（3-1）～式（3-4）、式（4-1）～式（4-4）及式（5-1）中的任一個對應之重複單元設為與式（6-1）～式（6-4）中的任一個所表示之重複單元不對應。 [化學式18] 式（6-1）中，X5 表示4價連接基，R3 及R4 分別獨立地表示不具有聚合性基的1價有機基，Z1 表示不具有聚合性基及上述式（L-1）所表示之結構中的任一個2價連接基； 式（6-2）中，X6 表示4價連接基，Z6 表示不具有聚合性基及上述式（L-1）所表示之結構中的任一個2價連接基； 式（6-3）中，X7 及X8 分別獨立地表示3價連接基，Z7 及Z8 分別獨立地表示不具有聚合性基及上述式（L-1）所表示之結構的2價連接基。 式（6-4）中，X7 及X8 分別獨立地表示3價連接基，R5 及R6 分別獨立地表示不具有聚合性基的1價有機基，Z7 及Z8 分別獨立地表示不具有聚合性基及上述式（L-1）所表示之結構的2價連接基。[Other repeating units] The specific resin may also contain other repeating units. As other repeating units, for example, a repeating unit represented by any one of Formulas (6-1) to (6-4) can be cited. The repeating unit corresponding to any one of Formulas (3-1) to (3-4), Formulas (4-1) to (4-4), and Formula (5-1) is set to not correspond to the repeating unit represented by any one of Formulas (6-1) to (6-4). [Chemical Formula 18] In formula (6-1), X5 represents a tetravalent connecting group, R3 and R4 each independently represent a monovalent organic group having no polymerizable group, and Z1 represents a divalent connecting group having no polymerizable group and any one of the structures represented by formula (L-1) above; In formula (6-2), X6 represents a tetravalent connecting group, and Z6 represents a divalent connecting group having no polymerizable group and any one of the structures represented by formula (L-1) above; In formula (6-3), X7 and X8 each independently represent a trivalent connecting group, and Z7 and Z8 each independently represent a divalent connecting group having no polymerizable group and the structure represented by formula (L-1) above. In formula (6-4), X7 and X8 each independently represent a trivalent linking group, R5 and R6 each independently represent a monovalent organic group having no polymerizable group, and Z7 and Z8 each independently represent a divalent linking group having no polymerizable group and the structure represented by formula (L-1).

式（6-1）中，X5 與式（3-1）中的X5 的含義相同，較佳態樣亦相同。 式（6-1）中，R3 及R4 分別獨立地為式（2-1）中的R1 及R2 中之具有雜原子之取代基中不具有聚合性基的取代基為較佳。上述具有雜原子之取代基的較佳態樣與式（2-1）中的R1 及R2 中之具有雜原子之取代基中不具有聚合性基的取代基的較佳態樣相同。 式（6-1）中，Z5 為脂肪族烴基、芳香族烴基或該等基團中的至少一個與-O-、-C（=O）-、-S-、-S（=O）2 -及-NRN -中的至少一個鍵結而獲得之基團為較佳。RN 如上所述。 作為上述脂肪族烴基，碳數2～30的脂肪族飽和烴基為較佳，碳數2～10的脂肪族飽和烴基為更佳。 又，作為上述脂肪族烴基，環員數為6～20的飽和脂肪族烴環基為較佳。 作為上述芳香族烴基，碳數6～20的芳香族烴基為較佳，碳數6～12的芳香族烴基為較佳，碳數6的芳香族烴基為更佳。 其中，從溶劑溶解性的觀點考慮，Z5 為包含脂肪族烴環基或芳香族烴環基之基團為較佳，包含芳香族烴環基之基團為更佳。In formula (6-1), X5 has the same meaning as X5 in formula (3-1), and the preferred embodiment is also the same. In formula (6-1), R3 and R4 are preferably independently a substituent having a heteroatom in R1 and R2 in formula (2-1) that does not have a polymerizable group. The preferred embodiment of the above-mentioned substituent having a heteroatom is the same as the preferred embodiment of the substituent having a heteroatom in R1 and R2 in formula (2-1) that does not have a polymerizable group. In formula (6-1), Z5 is preferably an aliphatic alkyl group, an aromatic alkyl group, or a group obtained by bonding at least one of these groups with at least one of -O-, -C(=O)-, -S-, -S(=O) 2- , and -NRN- . R N is as described above. As the above-mentioned aliphatic alkyl group, an aliphatic saturated alkyl group having 2 to 30 carbon atoms is preferred, and an aliphatic saturated alkyl group having 2 to 10 carbon atoms is more preferred. Furthermore, as the above-mentioned aliphatic alkyl group, a saturated aliphatic alkyl ring group having 6 to 20 ring members is preferred. As the above-mentioned aromatic alkyl group, an aromatic alkyl group having 6 to 20 carbon atoms is preferred, an aromatic alkyl group having 6 to 12 carbon atoms is preferred, and an aromatic alkyl group having 6 carbon atoms is more preferred. Among them, from the viewpoint of solvent solubility, Z 5 is preferably a group containing an aliphatic alkyl ring group or an aromatic alkyl ring group, and a group containing an aromatic alkyl ring group is more preferred.

又，從所獲得之硬化膜的柔軟性的觀點考慮，式（6-1）中之Z5 由-Ar0 -L0 -Ar0 -表示為較佳。Ar0 分別獨立地為芳香族烴基（碳數6～22為較佳，6～18為更佳，6～10為特佳），伸苯基為較佳。L0 與上述式（A2-3）中之LA231 的含義相同，較佳態樣亦相同。In view of the flexibility of the obtained cured film, Z5 in formula (6-1) is preferably represented by -Ar0 - L0 - Ar0- . Ar0 is independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms), preferably a phenylene group. L0 has the same meaning as L231 in formula (A2-3), and the preferred embodiment is also the same.

從i射線透過率的觀點考慮，式（6-1）中之Z5 為下述式（51）或式（61）所表示之2價有機基為較佳。尤其，從i射線透過率、易獲得的觀點考慮，式（61）所表示之2價有機基為更佳。From the viewpoint of i-ray transmittance, Z5 in formula (6-1) is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred.

[化學式19] [Chemical formula 19]

式（51）中，R50 ～R57 分別獨立地為氫原子、氟原子或1價有機基，R50 ～R57 中的至少一個為氟原子、甲基、氟甲基、二氟甲基或三氟甲基，*分別獨立地表示與其他結構的鍵結部位。In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, at least one of R 50 to R 57 is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group, and * each independently represents a bonding site with other structures.

作為R50 ～R57 的1價有機基，可以舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。Examples of the monovalent organic group for R 50 to R 57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like.

[化學式20] [Chemical formula 20]

式（61）中，R58 及R59 分別獨立地為氟原子、氟甲基、二氟甲基或三氟甲基。In formula (61), R 58 and R 59 are independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group.

式（6-1）中之Z5 為來自於二胺之結構為較佳。 作為上述二胺，可以舉出選自1,2-二胺基乙烷、1,2-二胺基丙烷、1,3-二胺基丙烷、1,4-二胺基丁烷、1,6-二胺基己烷；1,2-二胺基環戊烷或1,3-二胺基環戊烷、1,2-二胺基環己烷、1,3-二胺基環己烷或1,4-二胺基環己烷、1,2-雙（胺基甲基）環己烷、1,3-雙（胺基甲基）環己烷或1,4-雙（胺基甲基）環己烷、雙-（4-胺基環己基）甲烷、雙-（3-胺基環己基）甲烷、4,4’-二胺基-3,3’-二甲基環己基甲烷或異佛爾酮二胺；間苯二胺或對苯二胺、二胺基甲苯、4,4’-二胺基聯苯或3,3’-二胺基聯苯、4,4’-二胺基二苯醚、3,3’-二胺基二苯醚、4,4’-二胺基二苯基甲烷或3,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基碸或3,3-二胺基二苯基碸、4,4’-二胺基二苯硫醚或3,3’-二胺基二苯硫醚、4,4’-二胺基二苯甲酮或3,3’-二胺基二苯甲酮、3,3’-二甲基-4,4’-二胺基聯苯、2,2’-二甲基-4,4’-二胺基聯苯（4,4’-二胺基-2,2’-二甲基聯苯）、3,3’-二甲氧基-4,4’-二胺基聯苯、雙（4-胺基-3-羧基苯基）甲烷、2,2-雙（4-胺基苯基）丙烷、2,2-雙（4-胺基苯基）六氟丙烷、2,2-雙（3-羥基-4-胺基苯基）丙烷、2,2-雙（3-羥基-4-胺基苯基）六氟丙烷、2,2-雙（3-胺基-4-羥基苯基）丙烷、2,2-雙（3-胺基-4-羥基苯基）六氟丙烷、雙（3-胺基-4-羥基苯基）碸、雙（4-胺基-3-羥基苯基）碸、4,4’-二胺基對聯三苯、4,4’-雙（4-胺基苯氧基）聯苯、雙[4-（4-胺基苯氧基）苯基]碸、雙[4-（3-胺基苯氧基）苯基]碸、雙[4-（2-胺基苯氧基）苯基]碸、1,4-雙（4-胺基苯氧基）苯、9,10-雙（4-胺基苯基）蒽、3,3’-二甲基-4,4’-二胺基二苯基碸、1,3-雙（4-胺基苯氧基）苯、1,3-雙（3-胺基苯氧基）苯、1,3-雙（4-胺基苯基）苯、3,3’-二乙基-4,4’-二胺基二苯基甲烷、3,3’-二甲基-4,4’-二胺基二苯基甲烷、4,4’-二胺基八氟聯苯、2,2-雙[4-（4-胺基苯氧基）苯基]丙烷、2,2-雙[4-（4-胺基苯氧基）苯基]六氟丙烷、9,9-雙（4-胺基苯基）-10-氫蒽、3,3’,4,4’-四胺基聯苯、3,3’,4,4’-四胺基二苯醚、1,4-二胺基蒽醌、1,5-二胺基蒽醌、3,3-二羥基-4,4’-二胺基聯苯、9,9’-雙（4-胺基苯基）茀、4,4’-二甲基-3,3’-二胺基二苯基碸、3,3’,5,5’-四甲基-4,4’-二胺基二苯基甲烷、2-（3’,5’-二胺基苯甲醯氧基）甲基丙烯酸乙酯、2,4-二胺基枯烯或2,5-二胺基枯烯、2,5-二甲基-對苯二胺、乙醯胍胺、2,3,5,6-四甲基-對苯二胺、2,4,6-三甲基-間苯二胺、4,6-二羥基-1,3-苯二胺、雙（3-胺基丙基）四甲基二矽氧烷、2,7-二胺基茀、2,5-二胺基吡啶、1,2-雙（4-胺基苯基）乙烷、二胺基苯甲醯苯胺、二胺苯甲酸、二胺苯甲酸的酯、1,5-二胺基萘、二胺基三氟甲苯、1,3-雙（4-胺基苯基）六氟丙烷、1,4-雙（4-胺基苯基）八氟丁烷、1,5-雙（4-胺基苯基）十氟戊烷、1,7-雙（4-胺基苯基）十四氟庚烷、2,2-雙[4-（3-胺基苯氧基）苯基]六氟丙烷、2,2-雙[4-（2-胺基苯氧基）苯基]六氟丙烷、2,2-雙[4-（4-胺基苯氧基）-3,5-二甲基苯基]六氟丙烷、2,2-雙[4-（4-胺基苯氧基）-3,5-雙（三氟甲基）苯基]六氟丙烷、對雙（4-胺基-2-三氟甲基苯氧基）苯、4,4’-雙（4-胺基-2-三氟甲基苯氧基）聯苯、4,4’-雙（4-胺基-3-三氟甲基苯氧基）聯苯、4,4’-雙（4-胺基-2-三氟甲基苯氧基）二苯基碸、4,4’-雙（3-胺基-5-三氟甲基苯氧基）二苯基碸、2,2-雙[4-（4-胺基-3-三氟甲基苯氧基）苯基]六氟丙烷、3,3’,5,5’-四甲基-4,4’-二胺基聯苯、4,4’-二胺基-2,2’-雙（三氟甲基）聯苯、2,2’,5,5’,6,6’-六氟聯甲苯胺及4,4’-二胺基四聯苯中之至少一種二胺。In formula (6-1), Z 5 is preferably a diamine. Examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,2-diaminocyclopentane, 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, or 1,6-diaminohexane. ,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane or isophorol Ketodiamine; meta-phenylenediamine or para-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone or 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diaminodiphenylsulfone) Amino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis(4-amino-3-carboxyphenyl)methane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfonate, bis(4-amino-3-hydroxyphenyl)sulfonate, 4,4'-diaminobiphenyl Triphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl Phenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diamine diphenylmethane, 2-(3',5'-diaminobenzyloxy)ethyl methacrylate, 2,4-diaminocumene or 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, 4,6-dihydroxy-1,3-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, diaminobenzoic acid, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis( 4-aminophenyl) hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-aminophenoxy) At least one diamine selected from the group consisting of 2,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine and 4,4'-diaminoquaternaryl.

又，國際公開第2017/038598號的0030～0031段中所記載的二胺（DA-1）～（DA-18）亦較佳。 亦可以較佳地使用在主鏈上具有國際公開第2017/038598號的0032～0034段中所記載的兩個以上的伸烷基二醇單元之二胺。Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferred. Diamines having two or more alkylene glycol units described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 on the main chain can also be preferably used.

又，作為賦予上述式（51）或（61）的結構之二胺，可以舉出二甲基-4,4’-二胺基聯苯、2,2’-雙（三氟甲基）-4,4’-二胺基聯苯、2,2’-雙（氟）-4,4’-二胺基聯苯、4,4’-二胺基八氟聯苯等。可以使用其中一種，亦可以組合使用兩種以上。Furthermore, examples of the diamine that imparts the structure of the above formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. One of these may be used alone, or two or more may be used in combination.

又，亦能夠較佳地使用以下二胺。 [化學式21] In addition, the following diamine can also be preferably used. [Chemical Formula 21]

又，以提高與基材的密接性為目的，作為二胺成分，可以使用雙（3-胺基丙基）四甲基二矽氧烷、雙（對胺基苯基）八甲基五矽氧烷等具有矽氧烷結構之二胺。In order to improve the adhesion to the substrate, a diamine having a siloxane structure such as bis(3-aminopropyl)tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane can be used as the diamine component.

式（6-2）中，X6 與式（3-2）中的X6 的含義相同，較佳態樣亦相同。 式（6-2）中，Z6 與式（6-1）中的Z5 的含義相同，較佳態樣亦相同。In formula (6-2), X6 has the same meaning as X6 in formula (3-2), and a preferred embodiment thereof is also the same. In formula (6-2), Z6 has the same meaning as Z5 in formula (6-1), and a preferred embodiment thereof is also the same.

式（6-3）中，X7 及X8 與式（3-3）中的X7 及X8 的含義相同，較佳態樣亦相同。 式（6-3）中，Z7 及Z8 分別獨立地與式（6-1）中的Z5 的含義相同，較佳態樣亦相同。In formula (6-3), X7 and X8 have the same meanings as X7 and X8 in formula (3-3), and preferred embodiments thereof are also the same. In formula (6-3), Z7 and Z8 have the same meanings as Z5 in formula (6-1), and preferred embodiments thereof are also the same.

式（6-4）中，X7 及X8 與式（3-4）中的X7 及X8 的含義相同，較佳態樣亦相同。 式（6-4）中，Z7 及Z8 分別獨立地與式（6-1）中的Z5 的含義相同，較佳態樣亦相同。 式（6-4）中，R5 及R6 分別獨立地與式（6-1）中的R3 及R4 的含義相同，較佳態樣亦相同。In formula (6-4), X7 and X8 have the same meanings as X7 and X8 in formula (3-4), and a preferred embodiment thereof is also the same. In formula (6-4), Z7 and Z8 have the same meanings as Z5 in formula (6-1), and a preferred embodiment thereof is also the same. In formula (6-4), R5 and R6 have the same meanings as R3 and R4 in formula (6-1), and a preferred embodiment thereof is also the same.

又，作為其他重複單元，還可以包含下述式（PAI-1）所表示之重複單元。 與上述式（5-1）對應之重複單元設為與式（PAI-1）所表示之重複單元不對應。 [化學式22] 式（PAI-1）中，R116 表示2價有機基，R111 表示2價有機基。 式（PAI-1）中，R116 可以例示直鏈狀或支鏈狀的脂肪族基、環狀的脂肪族基及芳香族基、雜芳族基團或者單鍵或藉由連接基將該等連接兩個以上而獲得之基團，碳數2～20的直鏈的脂肪族基、碳數3～20的支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族基或者單鍵或藉由連接基將該等組合兩個以上而獲得之基團為較佳，碳數6～20的芳香族基或者單鍵或藉由連接基將碳數6～20的芳香族基組合兩個以上而獲得之基團為更佳。 作為上述連接基，-O-、-S-、-C（=O）-、-S（=O）2 -、伸烷基、鹵化伸烷基、伸芳基或該等鍵結兩個以上而形成之連接基為較佳，-O-、-S-、伸烷基、鹵化伸烷基、伸芳基或該等鍵結兩個以上而形成之連接基為更佳。 作為上述伸烷基，碳數1～20的伸烷基為較佳，碳數1～10的伸烷基為更佳，碳數1～4的伸烷基為進一步較佳。 作為上述鹵化伸烷基，碳數1～20的鹵化伸烷基為較佳，碳數1～10的鹵化伸烷基為更佳，碳數1～4的鹵化伸烷基為更佳。又，作為上述鹵化伸烷基中之鹵素原子，可以舉出氟原子、氯原子、溴原子、碘原子等，氟原子為較佳。上述鹵化伸烷基可以具有氫原子，亦可以使所有氫原子經鹵素原子取代，但是所有氫原子經鹵素原子取代為較佳。作為較佳的鹵化伸烷基的例子，可以舉出（二三氟甲基）亞甲基等。 作為上述伸芳基，伸苯基或伸萘基為較佳，伸苯基為更佳，1,3-伸苯基或1,4-伸苯基為進一步較佳。Furthermore, as other repeating units, repeating units represented by the following formula (PAI-1) may also be included. The repeating units corresponding to the above formula (5-1) are set to be non-corresponding to the repeating units represented by the formula (PAI-1). [Chemical Formula 22] In the formula (PAI-1), R 116 represents a divalent organic group, and R 111 represents a divalent organic group. In formula (PAI-1), R 116 can be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, a heteroaromatic group, or a group obtained by linking two or more of these groups via a single bond or via a linking group. Preferably, it is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups via a single bond or via a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or via a linking group. As the linking group, -O-, -S-, -C(=O)-, -S(=O) 2- , alkylene, halogenated alkylene, arylene, or a linking group formed by two or more of these groups are preferred, and -O-, -S-, alkylene, halogenated alkylene, arylene, or a linking group formed by two or more of these groups are more preferred. As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, and an alkylene group having 1 to 4 carbon atoms is further preferred. As the halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferred, a halogenated alkylene group having 1 to 10 carbon atoms is more preferred, and a halogenated alkylene group having 1 to 4 carbon atoms is further preferred. In addition, as the halogen atom in the above-mentioned halogenated alkylene group, fluorine atom, chlorine atom, bromine atom, iodine atom, etc. can be cited, and fluorine atom is preferred. The above-mentioned halogenated alkylene group may have hydrogen atoms, and all hydrogen atoms may be substituted by halogen atoms, but all hydrogen atoms are preferably substituted by halogen atoms. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene, etc. can be cited. As the above-mentioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is further preferred.

又，R116 從二羧酸化合物或二羧酸二鹵化物衍生為較佳。 在本發明中，將具有兩個羧基之化合物稱為二羧酸化合物，且將具有兩個被鹵化之羧基之化合物稱為二羧酸二鹵化物。 二羧酸二鹵化物中之羧基只要被鹵化即可，例如被氯化為較佳。亦即，二羧酸二鹵化物為二羧酸二氯化物化合物為較佳。 作為用於聚醯胺醯亞胺前驅物的製造中之可以被鹵化的二羧酸化合物或二羧酸二鹵化物，可以舉出直鏈狀或支鏈狀的脂肪族、環狀的脂肪族或芳香族二羧酸化合物或二羧酸二鹵化物等。 該等二羧酸化合物或二羧酸二鹵化物可以僅使用一種，亦可以使用兩種以上。In addition, R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide. In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide. The carboxyl groups in the dicarboxylic acid dihalide only need to be halogenated, for example, preferably chlorinated. That is, the dicarboxylic acid dihalide is preferably a dicarboxylic acid dichloride compound. As the dicarboxylic acid compound or dicarboxylic acid dihalide that can be halogenated and used in the preparation of the polyamide imide precursor, there can be cited linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides. Such dicarboxylic acid compounds or dicarboxylic acid dihalides may be used alone or in combination of two or more.

具體而言，作為二羧酸化合物或二羧酸二鹵化物，包含碳數2～20的直鏈的脂肪族基、碳數3～20的支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族基或者單鍵或藉由連接基將該等組合兩個以上而獲得之基團之二羧酸化合物或二羧酸二鹵化物為較佳，包含碳數6～20的芳香族基或者單鍵或藉由連接基將碳數6～20的芳香族基組合兩個以上而獲得之基團之二羧酸化合物或二羧酸二鹵化物為更佳。Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more of these groups by a single bond or via a linking group. More preferably, the dicarboxylic acid compound or dicarboxylic acid dihalide contains an aromatic group having 6 to 20 carbon atoms, or a group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms by a single bond or via a linking group.

又，作為二羧酸化合物的具體例，可以舉出丙二酸、二甲基丙二酸、乙基丙二酸、異丙基丙二酸、二正丁基丙二酸、琥珀酸、四氟琥珀酸、甲基琥珀酸、2,2-二甲基琥珀酸、2,3-二甲基琥珀酸、二甲基甲基琥珀酸、戊二酸、六氟戊二酸、2-甲基戊二酸、3-甲基戊二酸、2,2-二甲基戊二酸、3,3-二甲基戊二酸、3-乙基-3-甲基戊二酸、己二酸、八氟己二酸、3-甲基己二酸、庚二酸、2,2,6,6-四甲基庚二酸、辛二酸、十二氟辛二酸、壬二酸、癸二酸、十六氟癸二酸、1,9-壬二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十七烷二酸、十八烷二酸、十九烷二酸、二十烷二酸、二十一烷二酸、二十二烷二酸、二十三烷二酸、二十四烷二酸、二十五烷二酸、二十六烷二酸、二十七烷二酸、二十八烷二酸、二十九烷二酸、三十烷二酸、三十一烷二酸、三十二烷二酸、二乙醇酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、4,4’-聯苯羧酸、4,4’-聯苯羧酸、4,4’-二羧基二苯醚、二苯甲酮-4,4’-二羧酸等。 作為二羧酸二鹵化物的具體例，可以舉出將上述二羧酸化合物的具體例中之兩個羧基進行鹵化而形成之結構的化合物。Specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecanoic acid, and 2,6,7-tetramethylpimelic acid. Diacid, 1,9-nonanediacid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, dotacosanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxy diphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. As specific examples of dicarboxylic acid dihalides, compounds having a structure in which two carboxyl groups in the specific examples of the above-mentioned dicarboxylic acid compounds are halogenated can be cited.

式（PAI-1）中，R111 與上述式（3-1）中之Z1 的含義相同，較佳態樣亦相同。In formula (PAI-1), R 111 has the same meaning as Z 1 in the above formula (3-1), and the preferred embodiment is also the same.

在特定樹脂包含其他重複單元之情況下，其他重複單元的含量相對於特定樹脂的總質量為0.1～40質量%為較佳，5～30質量%為更佳。 又，亦能夠將特定樹脂設為實質上不包含其他重複單元的態樣。在上述態樣中，其他重複單元的含量相對於特定樹脂的總質量為20質量%以下為較佳，10質量%以下為較佳，5質量%以下為進一步較佳，1質量%以下為進一步較佳。上述含量的下限並無特別限定，可以為0質量%。 又，特定樹脂可以僅包含一種其他重複單元，亦可以包含兩種以上不同結構之其他重複單元。在包含兩種以上的其他重複單元之情況下，其他重複單元的合計含量在上述範圍內為較佳。When the specific resin contains other repeating units, the content of the other repeating units is preferably 0.1 to 40 mass % relative to the total mass of the specific resin, and 5 to 30 mass % is more preferably. In addition, the specific resin can also be set to a state that substantially does not contain other repeating units. In the above state, the content of other repeating units is preferably 20 mass % or less relative to the total mass of the specific resin, preferably 10 mass % or less, further preferably 5 mass % or less, and further preferably 1 mass % or less. The lower limit of the above content is not particularly limited and can be 0 mass %. In addition, the specific resin can contain only one other repeating unit, or it can contain two or more other repeating units of different structures. When two or more other repeating units are included, the total content of the other repeating units is preferably within the above range.

-特定樹脂的較佳態樣- 特定樹脂為下述（1）～（5）中的任一個態樣為較佳。 （1）包含式（3-1）所表示之重複單元及式（4-1）所表示之重複單元。 （2）包含式（3-2）所表示之重複單元及式（4-2）所表示之重複單元。 （3）包含式（3-3）所表示之重複單元及式（4-3）所表示之重複單元。 （4）包含式（3-4）所表示之重複單元及式（4-4）所表示之重複單元。 （5）包含選自包括式（3-1）所表示之重複單元、式（3-2）所表示之重複單元、式（3-3）所表示之重複單元及式（3-4）所表示之重複單元之群組中的至少一種重複單元及式（5-1）所表示之重複單元。-Preferred embodiment of specific resin- The specific resin is preferably any one of the following (1) to (5). (1) Contains the repeating unit represented by formula (3-1) and the repeating unit represented by formula (4-1). (2) Contains the repeating unit represented by formula (3-2) and the repeating unit represented by formula (4-2). (3) Contains the repeating unit represented by formula (3-3) and the repeating unit represented by formula (4-3). (4) Contains the repeating unit represented by formula (3-4) and the repeating unit represented by formula (4-4). (5) comprising at least one repeating unit selected from the group consisting of a repeating unit represented by formula (3-1), a repeating unit represented by formula (3-2), a repeating unit represented by formula (3-3) and a repeating unit represented by formula (3-4) and a repeating unit represented by formula (5-1).

在上述（1）中，特定樹脂還可以包含其他重複單元。 例如，在上述（1）中，特定樹脂還可以包含式（5-1）所表示之重複單元。 在上述（1）中，式（3-1）所表示之重複單元及式（4-1）所表示之重複單元的合計含量相對於特定樹脂的總質量為50質量%以上為較佳，60質量%以上為更佳，70質量%以上為進一步較佳，80質量%以上為特佳。上述合計含量的上限並無特別限定，可以為100質量%。In the above (1), the specific resin may also contain other repeating units. For example, in the above (1), the specific resin may also contain the repeating unit represented by formula (5-1). In the above (1), the total content of the repeating unit represented by formula (3-1) and the repeating unit represented by formula (4-1) relative to the total mass of the specific resin is preferably 50 mass% or more, 60 mass% or more is more preferably, 70 mass% or more is further preferably, and 80 mass% or more is particularly preferably. The upper limit of the above total content is not particularly limited and can be 100 mass%.

在上述（2）中，特定樹脂還可以包含其他重複單元。 例如，在上述（2）中，特定樹脂還可以包含選自包括式（3-1）所表示之重複單元及式（4-1）所表示之重複單元之群組中的至少一種。 又，例如，在上述（2）中，特定樹脂還可以包含式（5-1）所表示之重複單元。 在上述（2）中，式（3-2）所表示之重複單元及式（4-2）所表示之重複單元的合計含量相對於特定樹脂的總質量為50質量%以上為較佳，60質量%以上為更佳，70質量%以上為進一步較佳，80質量%以上為特佳。上述合計含量的上限並無特別限定，可以為100質量%。In the above (2), the specific resin may also contain other repeating units. For example, in the above (2), the specific resin may also contain at least one selected from the group consisting of repeating units represented by formula (3-1) and repeating units represented by formula (4-1). Also, for example, in the above (2), the specific resin may also contain repeating units represented by formula (5-1). In the above (2), the total content of the repeating units represented by formula (3-2) and the repeating units represented by formula (4-2) relative to the total mass of the specific resin is preferably 50% by mass or more, 60% by mass or more is more preferably, 70% by mass or more is further preferably, and 80% by mass or more is particularly preferably. The upper limit of the above total content is not particularly limited and may be 100% by mass.

在上述（3）中，特定樹脂還可以包含其他重複單元。 例如，在上述（3）中，特定樹脂還可以包含選自包括式（3-4）所表示之重複單元及式（4-4）所表示之重複單元之群組中的至少一種。 在上述（3）中，特定樹脂還可以包含式（5-1）所表示之重複單元。 在上述（3）中，式（3-3）所表示之重複單元及式（4-3）所表示之重複單元的合計含量相對於特定樹脂的總質量為50質量%以上為較佳，60質量%以上為更佳，70質量%以上為進一步較佳，80質量%以上為特佳。上述合計含量的上限並無特別限定，可以為100質量%。In the above (3), the specific resin may also contain other repeating units. For example, in the above (3), the specific resin may also contain at least one selected from the group consisting of repeating units represented by formula (3-4) and repeating units represented by formula (4-4). In the above (3), the specific resin may also contain repeating units represented by formula (5-1). In the above (3), the total content of the repeating units represented by formula (3-3) and the repeating units represented by formula (4-3) relative to the total mass of the specific resin is preferably 50% by mass or more, 60% by mass or more is more preferably, 70% by mass or more is further preferably, and 80% by mass or more is particularly preferably. The upper limit of the above total content is not particularly limited and may be 100% by mass.

在上述（4）中，特定樹脂還可以包含其他重複單元。 例如，在上述（4）中，特定樹脂還可以包含式（5-1）所表示之重複單元。 在上述（4）中，式（3-4）所表示之重複單元及式（4-4）所表示之重複單元的合計含量相對於特定樹脂的總質量為50質量%以上為較佳，60質量%以上為更佳，70質量%以上為進一步較佳，80質量%以上為特佳。上述合計含量的上限並無特別限定，可以為100質量%。In the above (4), the specific resin may also contain other repeating units. For example, in the above (4), the specific resin may also contain the repeating unit represented by formula (5-1). In the above (4), the total content of the repeating unit represented by formula (3-4) and the repeating unit represented by formula (4-4) relative to the total mass of the specific resin is preferably 50 mass% or more, 60 mass% or more is more preferably, 70 mass% or more is further preferably, and 80 mass% or more is particularly preferably. The upper limit of the above total content is not particularly limited and can be 100 mass%.

在上述（5）中，特定樹脂還可以包含其他重複單元。 在上述（5）中，式（3-1）所表示之重複單元、式（3-2）所表示之重複單元、式（3-3）所表示之重複單元、式（3-4）所表示之重複單元及式（5-1）所表示之重複單元的合計含量相對於特定樹脂的總質量為50質量%以上為較佳，60質量%以上為更佳，70質量%以上為進一步較佳，80質量%以上為特佳。上述合計含量的上限並無特別限定，可以為100質量%。In the above (5), the specific resin may also contain other repeating units. In the above (5), the total content of the repeating unit represented by formula (3-1), the repeating unit represented by formula (3-2), the repeating unit represented by formula (3-3), the repeating unit represented by formula (3-4) and the repeating unit represented by formula (5-1) relative to the total mass of the specific resin is preferably 50 mass% or more, 60 mass% or more is more preferably, 70 mass% or more is further preferably, and 80 mass% or more is particularly preferably. The upper limit of the above total content is not particularly limited and can be 100 mass%.

-末端結構- 特定樹脂的末端結構並無特別限定，但是為了提高組成物的保存穩定性，可以用單胺、酸酐、一元羧酸、單醯氯化合物、單活性酯化合物等封端劑來密封。該等封端劑中，使用單胺為較佳。作為單胺，可以舉出苯胺、2-乙炔基苯胺、3-乙炔基苯胺、4-乙炔基苯胺、5-胺基-8-羥基喹啉、1-羥基-7-胺基萘、1-羥基-6-胺基萘、1-羥基-5-胺基萘、1-羥基-4-胺基萘、2-羥基-7-胺基萘、2-羥基-6-胺基萘、2-羥基-5-胺基萘、1-羧基-7-胺基萘、1-羧基-6-胺基萘、1-羧基-5-胺基萘、2-羧基-7-胺基萘、2-羧基-6-胺基萘、2-羧基-5-胺基萘、2-胺基安息香酸、3-胺基安息香酸、4-胺基安息香酸、4-胺基水楊酸、5-胺基水楊酸、6-胺基水楊酸、2-胺基苯磺酸、3-胺基苯磺酸、4-胺基苯磺酸、3-胺基-4，6-二羥基嘧啶、2-胺基酚、3-胺基酚、4-胺基酚、2-胺基苯硫酚、3-胺基苯硫酚、4-胺基苯硫酚、4-胺基苯乙烯等。該等可以使用兩種以上，亦可以藉由使複數個封端劑進行反應而導入複數個不同之末端基。-Terminal structure- The terminal structure of the specific resin is not particularly limited, but in order to improve the storage stability of the composition, it can be sealed with a capping agent such as a monoamine, anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound. Among these capping agents, monoamine is preferably used. As the monoamine, there can be mentioned aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, The terminal groups include naphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 4-aminostyrene, etc. Two or more of these can be used, and a plurality of different terminal groups can be introduced by reacting a plurality of end-capping agents.

[含量] 從提高所獲得之硬化膜的斷裂伸長率之觀點考慮，本發明的硬化性樹脂組成物中之特定樹脂的含量相對於硬化性樹脂組成物的總固體成分為20質量%以上為較佳，30質量%以上為更佳，40質量%以上為進一步較佳。 作為上述含量的上限，從提高硬化性樹脂組成物的解析度的觀點考慮，99.5質量%以下為較佳，99質量%以下為更佳，98質量%以下為進一步較佳，97質量%以下為更進一步較佳，95質量%以下為又更進一步較佳。[Content] From the viewpoint of improving the elongation at break of the obtained cured film, the content of the specific resin in the curable resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more relative to the total solid content of the curable resin composition. As the upper limit of the above content, from the viewpoint of improving the resolution of the curable resin composition, 99.5% by mass or less is preferably, 99% by mass or less is more preferably, 98% by mass or less is even more preferably, 97% by mass or less is even more preferably, and 95% by mass or less is even more preferably.

[特定樹脂的物理性質] -分子量- 特定樹脂的重量平均分子量（Mw）為2,000～500,000為較佳，5,000～200,000為更佳，10,000～100,000為進一步較佳。 特定樹脂的數量平均分子量（Mn）為800～250,000為較佳，2,000～100,000為更佳，4,000～50,000為進一步較佳。 關於特定樹脂的分子量的分散度，1.5～3.5為較佳，2～3為更佳。 在本說明書中，分子量的分散度表示重量平均分子量除以數量平均分子量而獲得之值（重量平均分子量/數量平均分子量）。[Physical properties of specific resin] -Molecular weight- The weight average molecular weight (Mw) of the specific resin is preferably 2,000 to 500,000, more preferably 5,000 to 200,000, and more preferably 10,000 to 100,000. The number average molecular weight (Mn) of the specific resin is preferably 800 to 250,000, more preferably 2,000 to 100,000, and more preferably 4,000 to 50,000. Regarding the molecular weight dispersion of the specific resin, 1.5 to 3.5 is preferred, and 2 to 3 is more preferred. In this specification, the molecular weight dispersion means the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

-酸值- 特定樹脂的酸值為0～2.0mmol/g為較佳，0～1.5mmol/g為更佳，0～1.0mmol/g為進一步較佳。 在將硬化性樹脂組成物用於後述鹼性顯影之情況下，特定樹脂的酸值為1.2～7mmol/g為較佳，1.5～6mmol/g為更佳，2～5mmol/g為進一步較佳。 在本發明中，酸值是指特定樹脂1g中所包含之酸基的量（mmol）。 酸基是指被pH12以上的鹼（例如氫氧化鈉）中和之基團。又，上述酸基係pKa為10以下的基團為較佳。 關於上述酸值，藉由公知的方法來進行測定，例如藉由JIS K 0070：1992中所記載的方法來進行測定。 作為上述酸基，可以舉出酚性羥基、羧基、磺酸基等，羧基為較佳。-Acid value- The acid value of the specific resin is preferably 0 to 2.0 mmol/g, more preferably 0 to 1.5 mmol/g, and further preferably 0 to 1.0 mmol/g. When the curable resin composition is used for alkaline development described later, the acid value of the specific resin is preferably 1.2 to 7 mmol/g, more preferably 1.5 to 6 mmol/g, and further preferably 2 to 5 mmol/g. In the present invention, the acid value refers to the amount (mmol) of acid groups contained in 1 g of the specific resin. The acid group refers to a group neutralized by an alkali (e.g., sodium hydroxide) at a pH of 12 or higher. In addition, the above-mentioned acid group is preferably a group having a pKa of 10 or less. The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992. As the acid group, phenolic hydroxyl group, carboxyl group, sulfonic acid group, etc. can be cited, and carboxyl group is preferred.

[聚合性基值] 1g的特定樹脂中所包含之聚合性基的莫耳量（聚合性基值、單位為mmol/g）為0.05～10mmol/g為較佳，0.1～5mmol/g為更佳。 在特定樹脂包含乙烯性不飽和鍵作為聚合性基之情況下，1g的特定樹脂中所包含之乙烯性不飽和鍵的莫耳量為0.05～10mmol/g為較佳，0.1～5mmol/g為更佳。 在特定樹脂包含環狀醚基、羥甲基、烷氧基甲基等聚合性基作為聚合性基之情況下，1g的特定樹脂中所包含之上述聚合性基的莫耳量為0.05～10mmol/g為較佳，0.1～5mmol/g為更佳。[Polymerization group value] The molar amount of the polymerizable group contained in 1 g of the specific resin (polymerization group value, unit: mmol/g) is preferably 0.05 to 10 mmol/g, and more preferably 0.1 to 5 mmol/g. When the specific resin contains ethylenic unsaturated bonds as polymerizable groups, the molar amount of ethylenic unsaturated bonds contained in 1 g of the specific resin is preferably 0.05 to 10 mmol/g, and more preferably 0.1 to 5 mmol/g. When the specific resin contains polymerizable groups such as cyclic ether groups, hydroxymethyl groups, alkoxymethyl groups, etc. as polymerizable groups, the molar amount of the above polymerizable groups contained in 1 g of the specific resin is preferably 0.05 to 10 mmol/g, and more preferably 0.1 to 5 mmol/g.

[具體例] 作為特定樹脂的具體例，可以舉出在後述實施例中所使用之特定樹脂。[Specific example] As a specific example of a specific resin, the specific resin used in the embodiment described below can be cited.

[製造方法（包含式（1-1）所表示之重複單元及式（2-1）所表示之重複單元之特定樹脂或包含式（1-1）所表示之重複單元及式（2-4）所表示之重複單元之特定樹脂的製造方法）] 在特定樹脂包含式（1-1）所表示之重複單元及式（2-1）所表示之重複單元或者包含式（1-1）所表示之重複單元及式（2-4）所表示之重複單元之情況下，特定樹脂例如藉由後述實施例中之合成例所示之合成方法進行合成。 又，上述特定樹脂的製造方法包括使二胺、4價羧酸化合物或其衍生物及含有與芳香環縮合而形成之㗁唑啉環結構之化合物進行反應之步驟（前驅物製造步驟）為較佳。[Production method (production method of a specific resin containing a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-1) or a specific resin containing a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-4))] When the specific resin contains a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-1) or contains a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-4), the specific resin is synthesized, for example, by the synthesis method shown in the synthesis example in the embodiment described later. Furthermore, the method for producing the specific resin preferably includes a step of reacting a diamine, a tetravalent carboxylic acid compound or a derivative thereof, and a compound containing an oxazoline ring structure formed by condensation with an aromatic ring (precursor production step).

-前驅物製造步驟- 作為在上述前驅物製造步驟中所使用之二胺，可以舉出下述式（DA-1）所表示之二胺。 [化學式23] 式（DA-1）中，L21 與式（3-1）中的Z1 的含義相同，較佳態樣亦相同。 作為在上述前驅物製造步驟中所使用之4價羧氧化合物，可以為羧酸二酐，亦可以為對四個羧基中的兩個進行了酯化、鹵化等改質之結構的化合物。較佳為，在後述式（DC-1）所表示之羧酸二酐或上述式（O）所表示之羧酸二酐中，可以舉出水解後的四個羧基中的兩個羧基被酯化之化合物。 藉由上述酯化而導入上述式（2-1）中之R1 及R2 為較佳。 又，在使用鹵化劑將上述四個羧基中的兩個被酯化之化合物鹵化之後，使其與二胺進行反應為較佳。 此外，關於前驅物製造步驟中之反應條件，能夠參閱公知的酯化條件而適當決定。-Precursor production step- As the diamine used in the above-mentioned precursor production step, there can be mentioned the diamine represented by the following formula (DA-1). [Chemical formula 23] In formula (DA-1), L 21 has the same meaning as Z 1 in formula (3-1), and the preferred embodiment is also the same. The tetravalent carboxylic acid oxide compound used in the above-mentioned precursor production step may be a carboxylic acid dianhydride, or a compound in which two of the four carboxyl groups are modified by esterification, halogenation, etc. Preferably, among the carboxylic acid dianhydride represented by the later-described formula (DC-1) or the carboxylic acid dianhydride represented by the above-mentioned formula (O), a compound in which two of the four carboxyl groups after hydrolysis are esterified can be cited. It is preferred that R 1 and R 2 in the above-mentioned formula (2-1) are introduced by the above-mentioned esterification. Furthermore, it is preferred that the compound in which two of the four carboxyl groups are esterified is halogenated using a halogenating agent and then reacted with a diamine. In addition, the reaction conditions in the precursor production step can be appropriately determined by referring to known esterification conditions.

作為在上述前驅物製造步驟中所使用之含有與芳香環縮合而形成之㗁唑啉環結構之化合物，可以舉出含有與芳香環縮合而形成之㗁唑啉環結構之二胺或含有與芳香環縮合而形成之㗁唑啉環結構之二羧酸。 含有與芳香環縮合而形成之㗁唑啉環結構之二羧酸中之羧基可以為鹵化物等被改質之羧酸。 作為含有與芳香環縮合而形成之㗁唑啉環結構之二胺，可以舉出下述式（ODA-1）所表示之化合物。 作為含有與芳香環縮合而形成之㗁唑啉環結構之二羧酸，可以舉出下述式（ODC-1）所表示之化合物。 [化學式24] 式（ODA-1）或式（ODC-1）中，Y1 、Ar1 、Y2 分別與式（1-1）中的Y1 、Ar1 、Y2 的含義相同，較佳態樣亦相同。 式（ODC-1）中，R表示-OH或取代基，表示-OH或鹵素原子為較佳。作為上述鹵素原子，可以舉出氟原子、氯原子、溴原子、碘原子等，氯原子為較佳。 藉由使用含有與芳香環縮合而形成之㗁唑啉環結構之二胺，將式（4-1）所表示之重複單元導入至特定樹脂。 藉由使用含有與芳香環縮合而形成之㗁唑啉環結構之二羧酸，將式（5-1）所表示之重複單元導入至特定樹脂。As the compound containing an oxazoline ring structure formed by condensation with an aromatic ring used in the above-mentioned precursor production step, there can be mentioned a diamine containing an oxazoline ring structure formed by condensation with an aromatic ring or a dicarboxylic acid containing an oxazoline ring structure formed by condensation with an aromatic ring. The carboxyl group in the dicarboxylic acid containing an oxazoline ring structure formed by condensation with an aromatic ring can be a carboxylic acid modified by a halogen or the like. As the diamine containing an oxazoline ring structure formed by condensation with an aromatic ring, there can be mentioned a compound represented by the following formula (ODA-1). As the dicarboxylic acid containing an oxazoline ring structure formed by condensation with an aromatic ring, there can be mentioned a compound represented by the following formula (ODC-1). [Chemical formula 24] In formula (ODA-1) or formula (ODC-1), Y 1 , Ar 1 , and Y 2 have the same meanings as Y 1 , Ar 1 , and Y 2 in formula (1-1), respectively, and preferred embodiments are also the same. In formula (ODC-1), R represents -OH or a substituent, preferably -OH or a halogen atom. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, iodine atom, etc., and chlorine atom is preferred. By using a diamine containing an oxazoline ring structure formed by condensation with an aromatic ring, the repeating unit represented by formula (4-1) is introduced into a specific resin. By using a dicarboxylic acid containing an oxazoline ring structure formed by condensation with an aromatic ring, the repeating unit represented by formula (5-1) is introduced into a specific resin.

又，在前驅物製造製程中，反應時使用有機溶劑為較佳。有機溶劑可以為一種，亦可以為兩種以上。 作為有機溶劑，能夠依據原料適當設定，但是可以例示吡啶、二乙二醇二甲醚（二甘二甲醚）、N-甲基-2-吡咯啶酮及N-乙基-2-吡咯啶酮。Furthermore, in the precursor manufacturing process, it is preferred to use an organic solvent during the reaction. The organic solvent may be one or more than two. As the organic solvent, it can be appropriately set according to the raw materials, but examples thereof include pyridine, diethylene glycol dimethyl ether (DGE), N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.

在前驅物製造步驟中，包括析出固體之步驟為較佳。具體而言，使反應液中的特定樹脂沉澱於水中，並使其溶解於四氫呋喃等可溶解聚醯亞胺前驅物之溶劑中，從而能夠析出固體。In the precursor preparation step, it is preferred to include a solid precipitation step. Specifically, the specific resin in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran that can dissolve the polyimide precursor, thereby being able to precipitate a solid.

-二胺製造步驟- 特定樹脂的製造方法可以包括如下步驟（二胺製造步驟），亦即，使具有兩個硝基、至少一個反應性基及芳香族烴基之化合物A和具有可以與上述反應性基形成鍵之基團及聚合性基之化合物B進行反應，在獲得鍵結有化合物A和化合物B之化合物C之後，將上述化合物C中之硝基進行還原，從而獲得二胺。 在二胺製造步驟中獲得之二胺被用作前驅物製造步驟中之二胺。-Diamine production step- The method for producing a specific resin may include the following step (diamine production step), that is, reacting a compound A having two nitro groups, at least one reactive group and an aromatic hydrocarbon group with a compound B having a group capable of forming a bond with the reactive group and a polymerizable group, and obtaining a compound C in which the compound A and the compound B are bonded, and then reducing the nitro group in the compound C to obtain a diamine. The diamine obtained in the diamine production step is used as the diamine in the precursor production step.

作為化合物A中之反應性基，並無特別限定，可以舉出胺基、羥基、羧基等。 化合物A為兩個硝基和至少一個反應性基與芳香族烴基直接鍵結而形成之結構為較佳。The reactive group in compound A is not particularly limited, and examples thereof include amino, hydroxyl, and carboxyl groups. It is preferred that compound A has a structure in which two nitro groups and at least one reactive group are directly bonded to an aromatic hydrocarbon group.

作為可以與化合物B中之反應性基形成鍵之基團，並無特別限定，可以舉出羥基、羧基、羧酸鹵化物基、環氧基、異氰酸酯基等。 作為化合物B中之聚合性基，可以舉出作為上述式（3-1）中之Z1 中所包含之基團所例示之基團。The group that can form a bond with the reactive group in compound B is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, a carboxylic acid halide group, an epoxy group, and an isocyanate group. Examples of the polymerizable group in compound B include the groups exemplified as the groups included in Z1 in the above formula (3-1).

化合物C為藉由化合物A和化合物B的反應而獲得之基團，且為具有兩個硝基和包含至少一個聚合性基之基團之化合物。 藉由還原化合物C中之硝基而獲得二胺化合物。 作為還原方法，能夠使用Bechamp還原，使用了鈀、鉑、鎳等金屬觸媒和氫氣、甲酸銨等氫源之氫化反應，將金屬氫化物作為還原劑之還原方法等公知的方法。Compound C is a group obtained by the reaction of compound A and compound B, and is a compound having two nitro groups and a group containing at least one polymerizable group. The diamine compound is obtained by reducing the nitro group in compound C. As a reduction method, Bechamp reduction, a hydrogenation reaction using a metal catalyst such as palladium, platinum, nickel and a hydrogen source such as hydrogen gas or ammonium formate, a reduction method using a metal hydride as a reducing agent, and other well-known methods can be used.

例如，後述實施例中之二硝基體（A-1）的合成為使作為化合物A之3,5-二硝基苯甲醯基氯與作為化合物B之甲基丙烯酸2-羥基乙酯進行反應而獲得作為化合物C之二硝基體（A-1）之反應。 又，後述實施例中之二胺（AA-1）的合成為將作為化合物C之二硝基體（A-1）中之兩個硝基進行還原而獲得二胺（AA-1）之反應。For example, the synthesis of the dinitro compound (A-1) in the following examples is a reaction in which 3,5-dinitrobenzoyl chloride as compound A is reacted with 2-hydroxyethyl methacrylate as compound B to obtain the dinitro compound (A-1) as compound C. In addition, the synthesis of the diamine (AA-1) in the following examples is a reaction in which two nitro groups in the dinitro compound (A-1) as compound C are reduced to obtain the diamine (AA-1).

-羧酸二酐製造步驟- 特定樹脂的製造方法可以包括使二胺化合物與具有一個羧酸酐基及一個羧基之化合物進行反應而獲得具有兩個以上的醯胺鍵之羧酸二酐之步驟（羧酸二酐製造步驟）。 上述一個羧基可以為羧酸鹵化物基。 關於上述反應的詳細內容，參閱公知的醯胺化方法來決定即可。 例如，後述實施例中之酐（MA-1）的合成為將作為二胺化合物之AA-1與作為具有一個羧酸酐基及一個羧酸鹵化物基之化合物之偏苯三甲酸酐氯化物進行反應而獲得具有兩個醯胺鍵之酐（MA-1）之反應。 作為所獲得之羧酸二酐，可以舉出下述式（DC-1）所表示之化合物。 [化學式25] 式（DC-1）中，X7 、X8 及Z3 分別與式（3-3）中的X7 、X8 及Z3 的含義相同，較佳態樣亦相同。-Carboxylic acid dianhydride production step- The production method of the specific resin may include a step of reacting a diamine compound with a compound having one carboxylic acid anhydride group and one carboxyl group to obtain a carboxylic acid dianhydride having two or more amide bonds (carboxylic acid dianhydride production step). The one carboxyl group may be a carboxylic acid halide group. The details of the above reaction may be determined by referring to a known amidation method. For example, the synthesis of anhydride (MA-1) in the embodiment described below is a reaction of reacting AA-1 as a diamine compound with trimellitic anhydride chloride as a compound having one carboxylic acid anhydride group and one carboxylic acid halide group to obtain anhydride (MA-1) having two amide bonds. As the obtained carboxylic acid dianhydride, there can be mentioned the compound represented by the following formula (DC-1). [Chemical formula 25] In formula (DC-1), X 7 , X 8 and Z 3 have the same meanings as X 7 , X 8 and Z 3 in formula (3-3), and preferred embodiments are also the same.

[製造方法（包含式（1-1）所表示之重複單元及式（2-2）所表示之重複單元之特定樹脂或包含式（1-1）所表示之重複單元及式（2-3）所表示之重複單元之特定樹脂的製造方法）] 關於包含式（1-1）所表示之重複單元以及選自包括式（2-2）所表示之重複單元及式（2-3）所表示之重複單元之群組中的至少一種重複單元之特定樹脂（以下，亦稱為閉環型特定樹脂。），例如藉由後述實施例中之合成例所示之合成方法進行合成。 又，閉環型特定樹脂的製造方法可以包括將包含上述式（1-1）所表示之重複單元及式（2-1）所表示之重複單元之特定樹脂或包含式（1-1）所表示之重複單元及式（2-4）所表示之重複單元之特定樹脂進行醯亞胺化之醯亞胺化步驟。[Production method (production method of a specific resin containing a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-2) or a specific resin containing a repeating unit represented by formula (1-1) and a repeating unit represented by formula (2-3))] Regarding a specific resin containing a repeating unit represented by formula (1-1) and at least one repeating unit selected from the group including a repeating unit represented by formula (2-2) and a repeating unit represented by formula (2-3) (hereinafter also referred to as a closed-ring specific resin), for example, it is synthesized by the synthesis method shown in the synthesis example in the embodiment described later. Furthermore, the method for producing a closed-ring specific resin may include an imidization step of imidizing a specific resin comprising a repeating unit represented by the above formula (1-1) and a repeating unit represented by the formula (2-1) or a specific resin comprising a repeating unit represented by the formula (1-1) and a repeating unit represented by the formula (2-4).

在醯亞胺化步驟中，在上述前驅物製造步驟等中所獲得之包含式（1-1）所表示之重複單元及式（2-1）所表示之重複單元之特定樹脂或包含式（1-1）所表示之重複單元及式（2-4）所表示之重複單元之特定樹脂被醯亞胺化，從而可以獲得閉環型特定樹脂。 醯亞胺化步驟可以為熱醯亞胺化（例如，基於加熱之醯亞胺化）、化學醯亞胺化（例如，使用了觸媒之醯亞胺化）及基於該等組合之醯亞胺化中的任一個，例如藉由在胺系化合物等觸媒的存在下加熱來進行。 又，在醯亞胺化步驟中，例如可以使用脫水劑。作為脫水劑，可以舉出乙酸酐等羧酸酐等。 此外，關於醯亞胺化的詳細內容，能夠藉由公知的方法來進行。In the imidization step, the specific resin containing the repeating unit represented by formula (1-1) and the repeating unit represented by formula (2-1) or the specific resin containing the repeating unit represented by formula (1-1) and the repeating unit represented by formula (2-4) obtained in the above-mentioned precursor production step is imidized, thereby obtaining a closed-ring specific resin. The imidization step may be any of thermal imidization (e.g., imidization based on heating), chemical imidization (e.g., imidization using a catalyst), and imidization based on a combination thereof, for example, by heating in the presence of a catalyst such as an amine compound. In the imidization step, for example, a dehydrating agent may be used. Examples of the dehydrating agent include carboxylic anhydrides such as acetic anhydride. In addition, the details of the imidization can be carried out by a known method.

-其他製造方法- 又，閉環型特定樹脂的製造方法可以為如下方法，亦即，在羧酸二酐及二胺化合物進行反應時，在高溫下進行加熱並使其脫水，從而一步合成樹脂。 作為羧酸二酐，例如可以舉出上述式（O）所表示之羧酸二酐、上述式（DC-1）所表示之羧酸二酐。 作為二胺化合物，能夠使用上述式（DA-1）所表示之二胺化合物。-Other production methods- In addition, the production method of the closed-ring specific resin may be a method in which carboxylic acid dianhydride and a diamine compound are heated at a high temperature and dehydrated during the reaction, thereby synthesizing the resin in one step. As carboxylic acid dianhydride, for example, carboxylic acid dianhydride represented by the above formula (O) and carboxylic acid dianhydride represented by the above formula (DC-1) can be cited. As the diamine compound, a diamine compound represented by the above formula (DA-1) can be used.

進而，在本發明中所使用之樹脂的製造方法可以為如下方法，亦即，在羧酸二酐及二異氰酸酯化合物進行反應時，在高溫下使其脫羧，從而一步合成樹脂。 作為羧酸二酐，例如可以舉出上述式（DC-1）所表示之羧酸二酐。上述羧酸二酐為在上述4價羧酸製造步驟中所獲得之化合物為較佳。 作為二異氰酸酯化合物，可以舉出將上述式（DA-1）所表示之化合物中之兩個胺基分別變更為異氰酸酯基之化合物。 關於該等製造方法的詳細內容，能夠參閱公知的聚醯亞胺的合成方法。Furthermore, the method for producing the resin used in the present invention may be a method in which a carboxylic acid dianhydride and a diisocyanate compound are decarboxylated at a high temperature during the reaction, thereby synthesizing the resin in one step. As the carboxylic acid dianhydride, for example, the carboxylic acid dianhydride represented by the above formula (DC-1) can be cited. The above carboxylic acid dianhydride is preferably a compound obtained in the above tetravalent carboxylic acid production step. As the diisocyanate compound, a compound in which two amino groups in the compound represented by the above formula (DA-1) are respectively changed to isocyanate groups can be cited. For details of such production methods, reference can be made to the known method for synthesizing polyimide.

＜溶劑＞ 本發明的硬化性樹脂組成物含有溶劑。 溶劑能夠任意使用公知的溶劑。溶劑較佳為有機溶劑。作為有機溶劑，可以舉出酯類、醚類、酮類亞碸類、醯胺類、脲類及醇類等化合物。<Solvent> The curable resin composition of the present invention contains a solvent. A known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, amides, ureas, and alcohols.

作為酯類，例如可以舉出乙酸乙酯、乙酸正丁酯、乙酸異丁酯、乙酸己酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯、ε-己內酯、δ-戊內酯、烷氧基乙酸烷基酯（例如，烷氧基乙酸甲酯、烷氧基乙酸乙酯、烷氧基乙酸丁酯（例如，甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等））、3-烷氧基丙酸烷基酯類（例如，3-烷氧基丙酸甲酯、3-烷氧基丙酸乙酯等（例如，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-乙氧基丙酸乙酯等））、2-烷氧基丙酸烷基酯類（例如，2-烷氧基丙酸甲酯、2-烷氧基丙酸乙酯、2-烷氧基丙酸丙酯等（例如，2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯））、2-烷氧基-2-甲基丙酸甲酯及2-烷氧基-2-甲基丙酸乙酯（例如，2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等）、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯、己酸乙酯、庚酸乙酯、丙二酸二甲酯、丙二酸二乙酯等作為較佳者。Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) ethyl ester, etc.)), alkyl 2-alkoxypropionates (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

作為醚類，例如可以舉出二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、乙二醇單丁醚、乙二醇單丁醚乙酸酯、二乙二醇乙基甲基醚、丙二醇單丙醚乙酸酯等作為較佳者。As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, etc. can be cited as preferred ones.

作為酮類，例如可以舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、3-甲基環己酮、左旋葡聚糖酮、二氫葡聚糖酮等作為較佳者。As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosanone, dihydroglucosanone and the like are preferably mentioned.

作為芳香族烴類，例如可以舉出甲苯、二甲苯、苯甲醚、檸檬烯等作為較佳者。Preferred examples of aromatic hydrocarbons include toluene, xylene, anisole, and limonene.

作為亞碸類，例如可以舉出二甲基亞碸作為較佳者。As the sulfoxides, for example, dimethyl sulfoxide can be preferably mentioned.

作為醯胺類，可以舉出N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N,N-二甲基異丁醯胺、3-甲氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、N-甲醯基嗎啉、N-乙醯基嗎啉等作為較佳者。As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like are preferably mentioned.

作為脲類，可以舉出N,N,N’,N’-四甲基脲、1,3-二甲基-2-咪唑啶酮等作為較佳者。As the urea, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferred.

作為醇類，可以舉出甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、1-戊醇、1-己醇、苯甲醇、乙二醇單甲基醚、1-甲氧基-2-丙醇、2-乙氧基乙醇、二乙二醇單乙醚、二乙二醇單二乙二醇單己醚、三乙二醇單甲基醚、丙二醇單丙二醇單乙醚、丙二醇單甲醚、聚乙二醇單甲基醚、聚丙二醇、四乙二醇、乙二醇單丁醚、乙二醇單乙二醇單芐醚、乙二醇單乙二醇單苯基醚、甲基苯基甲醇、正戊醇、甲基戊醇及雙丙酮醇等。Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monopropylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethylene glycol monobenzyl ether, ethylene glycol monoethylene glycol monophenyl ether, methyl phenyl carbinol, n-pentanol, methyl pentanol, and diacetone alcohol.

關於溶劑，從塗佈面性狀的改善等觀點考慮，混合兩種以上之形態亦較佳。Regarding solvents, from the perspective of improving the properties of the coated surface, a mixture of two or more solvents is also preferred.

在本發明中，選自3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基溶纖劑乙酸酯、乳酸乙酯、二乙二醇二甲醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、環戊酮、γ-丁內酯、二甲基亞碸、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、N-甲基-2-吡咯啶酮、丙二醇甲醚及丙二醇甲醚乙酸酯中之一種溶劑或由兩種以上構成之混合溶劑為較佳。同時使用二甲基亞碸和γ-丁內酯為特佳。又，N-甲基-2-吡咯啶酮和乳酸乙酯、二丙酮醇和乳酸乙酯、環戊酮和γ-丁內酯的組合亦分別較佳。In the present invention, a solvent selected from 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl solvent acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl ester, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, or a mixed solvent consisting of two or more of the above solvents is preferred. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone simultaneously. In addition, the combination of N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and γ-butyrolactone is also preferred.

從塗佈性的觀點考慮，將溶劑的含量設為本發明的硬化性樹脂組成物的總固體成分濃度成為5～80質量%之量為較佳，設為成為5～75質量%之量為更佳，設為成為10～70質量%之量為進一步較佳，設為成為40～70質量%為更進一步較佳。關於溶劑含量，只要依據塗膜的所期望厚度和塗佈方法進行調節即可。From the viewpoint of coating properties, the content of the solvent is preferably set to an amount of 5 to 80 mass % of the total solid content concentration of the curable resin composition of the present invention, more preferably 5 to 75 mass %, more preferably 10 to 70 mass %, and even more preferably 40 to 70 mass %. The content of the solvent can be adjusted according to the desired thickness of the coating film and the coating method.

溶劑可以僅含有一種，亦可以含有兩種以上。在含有兩種以上的溶劑之情況下，合計量在上述範圍內為較佳。The solvent may contain only one kind or two or more kinds. When two or more kinds of solvents are contained, it is preferable that the total amount is within the above range.

＜光敏劑＞ 本發明的硬化性樹脂組成物包含光敏劑為較佳。作為光敏劑，可以舉出光聚合起始劑為較佳。<Photosensitive agent> The curable resin composition of the present invention preferably contains a photosensitizer. As the photosensitizer, a photopolymerization initiator can be cited as a preferred example.

[光聚合起始劑] 本發明的硬化性樹脂組成物包含光聚合起始劑作為光敏劑為較佳。 光聚合起始劑為光自由基聚合起始劑為較佳。作為光自由基聚合起始劑，並無特別限制，能夠從公知的光自由基聚合起始劑中適當選擇。例如，對紫外線區域至可見區域的光線具有感光性之光自由基聚合起始劑為較佳。又，亦可以為與光激勵之敏化劑產生某些作用而生成活性自由基之活性劑。[Photopolymerization initiator] The curable resin composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer. The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet region to the visible region is preferred. In addition, it can also be an activator that generates active radicals by reacting with a photoexcited sensitizer.

光自由基聚合起始劑至少含有一種在約300～800nm（較佳為330～500nm）的範圍內至少具有約50L/mol-1 /cm-1 莫耳吸光係數之化合物為較佳。關於化合物的莫耳吸光係數，能夠使用公知的方法來測定。例如，藉由紫外可見分光光度計（Varian Medical Systems, Inc.製Cary-5 spectrophotometer），並使用乙酸乙酯溶劑在0.01g/L的濃度下進行測定為較佳。The photo-free radical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L/mol -1 /cm -1 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferably measured using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) and using an ethyl acetate solvent at a concentration of 0.01 g/L.

作為光自由基聚合起始劑，能夠任意使用公知的化合物。例如，可以舉出鹵化烴衍生物（例如具有三𠯤骨架之化合物、具有㗁二唑骨架之化合物、具有三鹵甲基之化合物等）、醯基氧化膦等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮化合物、羥基苯乙酮、偶氮系化合物、疊氮化合物、茂金屬化合物、有機硼化合物、鐵芳烴錯合物等。關於該等詳細內容，能夠參閱日本特開2016-027357號公報的0165～0182段、國際公開第2015/199219號的0138～0151段的記載，且該內容被編入本說明書中。As the photoradical polymerization initiator, any known compound can be used. For example, alkyl halides derivatives (e.g., compounds having a trioxane skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For the details, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, and the contents are incorporated into this specification.

作為酮化合物，例如可以例示日本特開2015-087611號公報的0087段中所記載的化合物，且該內容被編入本說明書中。市售品中，亦可以較佳地使用KAYACURE DETX（Nippon Kayaku Co.,Ltd.製）。Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, and the contents are incorporated herein. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

在本發明的一實施態樣中，作為光自由基聚合起始劑，能夠較佳地使用羥基苯乙酮化合物、胺基苯乙酮化合物及醯基膦化合物。更具體而言，例如能夠使用日本特開平10-291969號公報中所記載的胺基苯乙酮系起始劑、日本專利第4225898號中所記載的醯基氧化膦系起始劑。In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used.

作為羥基苯乙酮系起始劑，能夠使用IRGACURE 184（IRGACURE為註冊商標）、DAROCUR 1173、IRGACURE 500、IRGACURE-2959、IRGACURE 127、IRGACURE 727（產品名稱：均為BASF公司製）。As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127, and IRGACURE 727 (product names: all manufactured by BASF) can be used.

作為胺基苯乙酮系起始劑，能夠使用作為市售品之IRGACURE 907、IRGACURE 369及IRGACURE 379（產品名稱：均為BASF公司製）。As the aminoacetophenone-based initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all manufactured by BASF) can be used.

作為胺基苯乙酮系起始劑，亦能夠使用吸收極大波長與365nm或405nm等波長光源匹配之日本特開2009-191179號公報中所記載的化合物。As the aminoacetophenone-based initiator, the compound described in Japanese Patent Application Laid-Open No. 2009-191179, which has an absorption maximum wavelength matching a light source of wavelength such as 365 nm or 405 nm, can also be used.

作為醯基膦系起始劑，可以舉出2,4,6-三甲基苯甲醯基-二苯基-氧化膦等。又，能夠使用作為市售品之IRGACURE-819或IRGACURE-TPO（產品名稱：均為BASF公司製）。Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, etc. Commercially available products such as IRGACURE-819 and IRGACURE-TPO (product names: both manufactured by BASF Corporation) can also be used.

作為茂金屬化合物，可以例示IRGACURE-784（BASF公司製）等。Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF Corporation) and the like.

作為光自由基聚合起始劑，可以更佳地舉出肟化合物。藉由使用肟化合物，能夠更有效地提高曝光寬容度。肟化合物的曝光寬容度（曝光餘量）較廣，並且亦作為光硬化促進劑而起作用，因此為特佳。As a photo-radical polymerization initiator, an oxime compound can be more preferably cited. By using an oxime compound, the exposure tolerance can be more effectively improved. Oxime compounds have a wider exposure tolerance (exposure margin) and also function as a photohardening accelerator, so they are particularly preferred.

作為肟化合物的具體例，能夠使用日本特開2001-233842號公報中所記載的化合物、日本特開2000-080068號公報中所記載的化合物、日本特開2006-342166號公報中所記載的化合物。Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166.

作為較佳的肟化合物，例如可以舉出下述結構的化合物、3-苯甲醯氧基亞胺基丁烷-2-酮、3-乙醯氧基亞胺基丁烷-2-酮、3-丙醯氧基亞胺基丁烷-2-酮、2-乙醯氧基亞胺基戊烷-3-酮、2-乙醯氧基亞胺基-1-苯基丙烷-1-酮、2-苯甲醯氧基亞胺基-1-苯基丙烷-1-酮、3-（4-甲苯磺醯氧基）亞胺基丁烷-2-酮及2-乙氧基羰氧基亞胺基-1-苯基丙烷-1-酮等。在本發明的硬化性樹脂組成物中，尤其使用肟化合物（肟系光聚合起始劑）作為光自由基聚合起始劑為較佳。肟系光聚合起始劑在分子內具有＞C=N-O-C（=O）-的連接基。Preferred oxime compounds include, for example, compounds having the following structures: 3-benzoyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the curable resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. Oxime-based photopolymerization initiators have a linking group of >C=N-O-C(=O)- in the molecule.

[化學式26] [Chemical formula 26]

市售品中，亦可以較佳地使用IRGACURE OXE 01、IRGACURE OXE 02、IRGACURE OXE 03、IRGACURE OXE 04（以上為BASF公司製）、ADEKA OPTOMER N-1919（ADEKA CORPORATION製、日本特開2012-014052號公報中所記載的光自由基聚合起始劑2）。又，亦能夠使用TR-PBG-304（Changzhou Tronly New Electronic Materials CO., LTD.製）、ADEKA ARKLS NCI-831及ADEKA ARKLS NCI-930（ADEKA CORPORATION製）。又，能夠使用DFI-091（DAITO CHEMIX Co.,Ltd.製）。又，亦能夠使用下述結構的肟化合物。 [化學式27] Among the commercial products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. In addition, an oxime compound having the following structure can also be used. [Chemical Formula 27]

作為光聚合起始劑，亦能夠使用具有茀環之肟化合物。作為具有茀環之肟化合物的具體例，可以舉出日本特開2014-137466號公報中所記載的化合物、日本專利06636081號中所記載的化合物。As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in Japanese Patent Application Laid-Open No. 2014-137466 and the compounds described in Japanese Patent No. 06636081.

作為光聚合起始劑，亦能夠使用具有咔唑環的至少一個苯環成為萘環之骨架之肟化合物。作為該種肟化合物的具體例，可以舉出國際公開第2013/083505號中所記載的化合物。As the photopolymerization initiator, an oxime compound having a carbazole ring and at least one benzene ring being a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

又，亦能夠使用具有氟原子之肟化合物。作為該種肟化合物的具體例，可以舉出日本特開2010-262028號公報中所記載之化合物、日本特表2014-500852號公報的0345段中所記載之化合物24、36～40、日本特開2013-164471號公報的0101段中所記載之化合物（C-3）等。In addition, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Unexamined Patent Publication No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Unexamined Patent Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Unexamined Patent Publication No. 2013-164471.

作為最佳的肟化合物，可以舉出日本特開2007-269779號公報中所示之具有特定取代基之肟化合物或日本特開2009-191061號公報中所示之具有硫芳基之肟化合物等。As the most preferable oxime compound, there can be mentioned an oxime compound having a specific substituent as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 or an oxime compound having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

從曝光靈敏度的觀點考慮，光自由基聚合起始劑為選自包括三鹵甲基三𠯤化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯基-苯-鐵錯合物及其鹽、鹵甲基㗁二唑化合物、3-芳基取代香豆素化合物之群組中的化合物為較佳。From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyl trioxane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halogenated methyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

進一步較佳的光自由基聚合起始劑為三鹵甲基三𠯤化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、二苯甲酮化合物、苯乙酮化合物，選自包括三鹵甲基三𠯤化合物、α-胺基酮化合物、肟化合物、三芳基咪唑二聚體、二苯甲酮化合物之群組中的至少一種化合物為更進一步較佳，使用茂金屬化合物或肟化合物為又更進一步較佳，肟化合物為再更進一步較佳。Further preferred photoradical polymerization initiators are trihalogenomethyl trioxime compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of trihalogenomethyl trioxime compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds is further preferred. Using metallocene compounds or oxime compounds is further preferred, and oxime compounds are further preferred.

又，光自由基聚合起始劑亦能夠使用二苯甲酮、N,N’-四甲基-4,4’-二胺基二苯甲酮（米其勒酮（Michler’s ketone））等N,N’-四烷基-4,4’-二胺基二苯甲酮，2-苄基-2-二甲基胺基-1-（4-嗎啉基苯基）-丁酮-1,2-甲基-1-[4-（甲硫基）苯基]-2-嗎啉基-丙酮-1等芳香族酮、烷基蒽醌等與芳香環縮環而形成之醌類、安息香烷基醚等安息香醚化合物、安息香、烷基安息香等安息香化合物、苄基二甲基縮酮等苄基衍生物等。又，亦能夠使用下述式（I）所表示之化合物。In addition, the photoradical polymerization initiator may include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones formed by condensation of alkyl anthraquinone and aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin, benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. In addition, the compound represented by the following formula (I) may be used.

[化學式28] [Chemical formula 28]

式（I）中，RI00 為碳數1～20的烷基、藉由一個以上的氧原子而中斷之碳數2～20的烷基、碳數1～12的烷氧基、苯基或碳數1～20的烷基、碳數1～12的烷氧基、鹵素原子、環戊基、環己基、碳數2～12的烯基、經藉由一個以上的氧原子而中斷之碳數2～18的烷基及碳數1～4的烷基中的至少一個取代之苯基或聯苯基，RI01 為式（II）所表示之基團或者為與RI00 相同的基團，RI02 ～RI04 分別獨立地為碳數1～12的烷基、碳數1～12的烷氧基或鹵素。In formula (I), R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 1 to 4 carbon atoms; R I01 is a group represented by formula (II) or a group identical to R I00 ; and R I02 to R I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

[化學式29] [Chemical formula 29]

式中，RI05 ～RI07 與上述式（I）的RI02 ～RI04 相同。In the formula, R I05 to R I07 are the same as R I02 to R I04 in the above formula (I).

又，光自由基聚合起始劑亦能夠使用國際公開第2015/125469號的0048～0055段中所記載的化合物。Furthermore, the photoradical polymerization initiator may also include the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

在包含光聚合起始劑之情況下，其含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1～30質量%為較佳，更佳為0.1～20質量%，進一步較佳為0.5～15質量%，更進一步較佳為1.0～10質量%。光聚合起始劑可以僅含有一種，亦可以含有兩種以上。在含有兩種以上的光聚合起始劑之情況下，合計量在上述範圍內為較佳。When a photopolymerization initiator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and further preferably 1.0 to 10 mass % relative to the total solid content of the curable resin composition of the present invention. The photopolymerization initiator may be contained in one type or in two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

[光酸產生劑] 又，本發明的硬化性樹脂組成物可以包含光酸產生劑作為光敏劑。 作為光酸產生劑，只要為藉由曝光而產生酸者，則並無特別限定，可以舉出醌二疊氮化合物、重氮鹽、鏻鹽、鋶鹽、錪鎓鹽等鎓鹽化合物、醯亞胺磺酸鹽、肟磺酸鹽、重氮二碸、二碸、鄰硝基苄基磺酸鹽等磺酸鹽化合物等。[Photoacid generator] In addition, the curable resin composition of the present invention may contain a photoacid generator as a photosensitizer. The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include quinone diazonium compounds, onium salt compounds such as diazo salts, phosphonium salts, coronium salts, and iodonium salts, sulfonate compounds such as amide sulfonates, oxime sulfonates, diazo disulfonates, disulfonates, and o-nitrobenzyl sulfonates.

作為醌二疊氮化合物，可以舉出醌二疊氮的磺酸酯鍵結於聚羥基化合物而獲得者，醌二疊氮的磺酸磺醯胺鍵於聚胺化合物而獲得者，醌二疊氮的磺酸藉由酯鍵結及磺醯胺鍵結中的至少一者鍵結於聚羥基聚胺化合物而獲得者等。在本發明中，例如，該等聚羥基化合物或聚胺化合物的官能基整體的50莫耳%以上經醌二疊氮取代為較佳。Examples of the quinone diazide compound include those obtained by bonding sulfonic acid ester of quinone diazide to a polyhydroxy compound, those obtained by bonding sulfonic acid sulfonamide of quinone diazide to a polyamine compound, and those obtained by bonding sulfonic acid of quinone diazide to a polyhydroxy polyamine compound via at least one of an ester bond and a sulfonamide bond. In the present invention, for example, it is preferred that 50 mol% or more of the functional groups of the polyhydroxy compound or polyamine compound are substituted with quinone diazide.

在本發明中，醌二疊氮可以較佳地使用5-萘醌二疊氮磺醯基、4-萘醌二疊氮磺醯基中的至少一種。4-萘醌二疊氮磺醯酯化合物在水銀燈的i射線區域具有吸收性，適合於i射線曝光。5-萘醌二疊氮磺醯酯化合物的吸收延伸至水銀燈的g射線區域，適合於g射線曝光。在本發明中，依據曝光波長來選擇4-萘醌二疊氮磺醯酯化合物、5-萘醌二疊氮磺醯酯化合物為較佳。又，在同一分子中可以含有具有4-萘醌二疊氮磺醯基、5-萘醌二疊氮磺醯基之萘醌二疊氮磺醯酯化合物，亦可以含有4-萘醌二疊氮磺醯酯化合物和5-萘醌二疊氮磺醯酯化合物。In the present invention, the quinone diazide can preferably use at least one of 5-naphthoquinone diazide sulfonyl and 4-naphthoquinone diazide sulfonyl. The 4-naphthoquinone diazide sulfonyl compound has absorption in the i-ray region of a mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonyl compound extends to the g-ray region of a mercury lamp and is suitable for g-ray exposure. In the present invention, it is preferred to select the 4-naphthoquinone diazide sulfonyl compound and the 5-naphthoquinone diazide sulfonyl compound according to the exposure wavelength. Furthermore, a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group may be contained in the same molecule, and a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may also be contained.

上述萘醌二疊氮化合物能夠藉由具有酚性羥基之化合物與醌二疊氮磺氧化合物的酯化反應來合成，亦能夠藉由公知的方法來合成。藉由使用該等萘醌二疊氮化合物，進一步提高解析度、靈敏度、殘膜率。 作為上述萘醌二疊氮化合物，例如可以舉出1,2-萘醌-2-二疊氮-5-磺酸或1,2-萘醌-2-二疊氮-4-磺酸、該等化合物的鹽或酯化合物等。The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonyl compound, or by a known method. By using the naphthoquinone diazide compound, the resolution, sensitivity, and residual film rate are further improved. As the naphthoquinone diazide compound, for example, 1,2-naphthoquinone-2-diazido-5-sulfonic acid or 1,2-naphthoquinone-2-diazido-4-sulfonic acid, salts or ester compounds of the compounds, etc. can be cited.

作為鎓鹽化合物或磺酸鹽化合物，可以舉出日本特開2008-013646號公報的0064～0122段中所記載的化合物等。 此外，作為光酸產生劑，可以使用市售品。作為市售品，可以舉出WPAG-145、WPAG-149、WPAG-170、WPAG-199、WPAG-336、WPAG-367、WPAG-370、WPAG-469、WPAG-638、WPAG-699（均為FFUJIFILM Wako Pure Chemical Corporation製）等。As the onium salt compound or sulfonate salt compound, compounds described in paragraphs 0064 to 0122 of Japanese Patent Application Publication No. 2008-013646 can be cited. In addition, as the photoacid generator, commercially available products can be used. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by FFUJIFILM Wako Pure Chemical Corporation).

在包含光酸產生劑之情況下，其含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1～30質量%為較佳，0.1～20質量%為更佳，2～15質量%為進一步較佳。光酸產生劑可以僅含有一種，亦可以含有兩種以上。在含有兩種以上的光酸產生劑之情況下，其合計在上述範圍內為較佳。When a photoacid generator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and even more preferably 2 to 15 mass % relative to the total solid content of the curable resin composition of the present invention. The photoacid generator may contain only one type or two or more types. When two or more types of photoacid generators are contained, the total amount thereof is preferably within the above range.

＜熱聚合起始劑＞ 本發明的硬化性樹脂組成物可以包含熱聚合起始劑，尤其可以包含熱自由基聚合起始劑。熱自由基聚合起始劑為藉由熱的能量而產生自由基並起始或促進具有聚合性之化合物的聚合反應之化合物。藉由添加熱自由基聚合起始劑，在後述加熱步驟中，亦能夠進行特定樹脂及聚合性化合物的聚合反應，因此能夠進一步提高耐藥品性。<Thermal polymerization initiator> The curable resin composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by heat energy and initiates or promotes the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the specific resin and the polymerizable compound can also be carried out in the heating step described later, thereby further improving the chemical resistance.

作為熱自由基聚合起始劑，具體而言，可以舉出日本特開2008-063554號公報的0074～0118段中所記載之化合物。Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

在包含熱聚合起始劑之情況下，其含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1～30質量%為較佳，更佳為0.1～20質量%，進一步較佳為5～15質量%。熱聚合起始劑可以僅含有一種，亦可以含有兩種以上。在含有兩種以上的熱聚合起始劑之情況下，合計量在上述範圍內為較佳。When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 5 to 15 mass % relative to the total solid content of the curable resin composition of the present invention. The thermal polymerization initiator may be contained in one type or in two or more types. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.

＜熱酸產生劑＞ 本發明的硬化性樹脂組成物可以包含熱酸產生劑作為聚合起始劑。 熱酸產生劑具有如下效果，亦即，藉由加熱產生酸，且促進選自具有羥甲基、烷氧基甲基或醯氧基甲基之化合物、環氧化合物、氧雜環丁烷化合物及苯并㗁𠯤化合物中之至少一種化合物或特定樹脂中所包含之羥甲基等的交聯反應。 又，在本發明的硬化性樹脂組成物包含熱酸產生劑之情況下，特定樹脂包含羥甲基或烷氧基甲基作為聚合性基為較佳。<Thermal acid generator> The curable resin composition of the present invention may contain a thermal acid generator as a polymerization initiator. The thermal acid generator has the effect of generating an acid by heating and promoting a crosslinking reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxycyclobutane compound and a benzophenone compound, or a hydroxymethyl group contained in a specific resin. In addition, when the curable resin composition of the present invention contains a thermal acid generator, it is preferred that the specific resin contains a hydroxymethyl group or an alkoxymethyl group as a polymerizable group.

熱酸產生劑的熱分解開始溫度為50℃～270℃為較佳，50℃～250℃為更佳。又，若選擇一種在將硬化性樹脂組成物塗佈於基板之後進行乾燥（預烘烤：約70～140℃）時不產生酸，而在之後的曝光、顯影中圖案化之後進行最終加熱（硬化：約100～400℃）時產生酸者作為熱酸產生劑，則能夠抑制顯影時的靈敏度下降，因此為較佳。 關於熱分解開始溫度，在將熱酸產生劑在耐壓膠囊中以5℃/分鐘加熱至500℃之情況下，作為溫度最低的發熱峰的峰值溫度而求出。 作為測定熱分解開始溫度時使用之設備，可以舉出Q2000（TA Instruments.製）等。The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, and more preferably 50°C to 250°C. In addition, if a thermal acid generator is selected that does not generate acid when the curable resin composition is applied to the substrate and dried (pre-baking: about 70 to 140°C), but generates acid when finally heated (curing: about 100 to 400°C) after patterning in subsequent exposure and development, it is preferred because the sensitivity drop during development can be suppressed. Regarding the thermal decomposition start temperature, it is determined as the peak temperature of the lowest temperature heat peak when the thermal acid generator is heated to 500°C at 5°C/min in a pressure-resistant capsule. As an instrument used to measure the thermal decomposition starting temperature, Q2000 (manufactured by TA Instruments) and the like can be cited.

從熱酸產生劑產生之酸為強酸為較佳，例如對甲苯磺酸、苯磺酸等芳磺酸、甲磺酸、乙磺酸、丁磺酸等烷磺酸或三氟甲磺酸等鹵烷磺酸等為較佳。作為該種熱酸產生劑的例子，可以舉出日本特開2013-072935號公報的0055段中所記載者。The acid generated from the thermal acid generator is preferably a strong acid, for example, aromatic sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or halogen sulfonic acids such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of Japanese Patent Application Publication No. 2013-072935.

其中，從在硬化膜中殘留得少且不易降低硬化膜物理性質之觀點考慮，產生碳數1～4的烷磺酸或碳數1～4的鹵烷磺酸者為更佳，作為熱酸產生劑，甲磺酸（4-羥基苯基）二甲基鋶鹽、甲磺酸（4-（（甲氧基羰基）氧基）苯基）二甲基鋶鹽、甲磺酸苄基（4-羥基苯基）甲基鋶鹽、甲磺酸苄基（4-（（甲氧基羰基）氧基）苯基）甲基鋶鹽、甲磺酸（4-羥基苯基）甲基（（2-甲基苯基）甲基）鋶鹽、三氟甲磺酸（4-羥基苯基）二甲基鋶鹽、三氟甲磺酸（4-（（甲氧基羰基）氧基）苯基）二甲基鋶鹽、三氟甲磺酸苄基（4-羥基苯基）甲基鋶鹽、三氟甲磺酸苄基（4-（（甲氧基羰基）氧基）苯基）甲基鋶鹽、三氟甲磺酸（4-羥基苯基）甲基（（2-甲基苯基）甲基）鋶鹽、3-（5-（（（丙磺醯基）氧基）亞胺基）噻吩-2（5H）-亞基）-2-（鄰甲苯基）丙腈、2,2-雙（3-（甲磺醯基胺基）-4-羥基苯基）六氟丙烷為較佳。Among them, from the viewpoint of less residue in the cured film and less reduction in the physical properties of the cured film, the one that generates an alkanesulfonic acid having 1 to 4 carbon atoms or a halogen alkanesulfonic acid having 1 to 4 carbon atoms is more preferred. As the thermal acid generator, (4-hydroxyphenyl) dimethyl konjac salt of methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl) dimethyl konjac salt of methanesulfonate, benzyl (4-hydroxyphenyl) methyl konjac salt of methanesulfonate, benzyl (4-((methoxycarbonyl)oxy)phenyl) methyl konjac salt of methanesulfonate, (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) konjac salt of methanesulfonate, (4-hydroxyphenyl) trifluoromethanesulfonate, trifluoromethanesulfonate benzyl(4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copper salt, 3-(5-(((propylsulfonyl)oxy)imino)thiophene-2(5H)-ylidene)-2-(o-tolyl)propionitrile, and 2,2-bis(3-(methylsulfonylamino)-4-hydroxyphenyl)hexafluoropropane are preferred.

又，作為熱酸產生劑，日本特開2013-167742號公報的0059段中所記載的化合物亦較佳。Furthermore, as the thermal acid generator, the compound described in paragraph 0059 of JP-A-2013-167742 is also preferred.

熱酸產生劑的含量相對於特定樹脂100質量份為0.01質量份以上為較佳，0.1質量份以上為更佳。藉由含有0.01質量份以上，交聯反應獲得促進，因此能夠進一步提高硬化膜的機械特性及耐藥品性。又，從硬化膜的電絕緣性的觀點考慮，20質量份以下為較佳，15質量份以下為更佳，10質量份以下為進一步較佳。The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. In addition, from the viewpoint of the electrical insulation of the cured film, 20 parts by mass or less is preferably, 15 parts by mass or less is more preferably, and 10 parts by mass or less is even more preferably.

＜聚合性化合物＞ 本發明的硬化性樹脂組成物包含聚合性化合物為較佳。 在本說明書中，與上述特定樹脂對應之化合物設為與聚合性化合物不對應者。 作為聚合性化合物，多官能聚合性化合物為較佳。在本說明書中，多官能聚合性化合物是指具有兩個以上的聚合性基之化合物。 又，作為聚合性化合物，自由基聚合性化合物為較佳，具有兩個以上的自由基聚合性基之化合物為更佳。<Polymerizable compound> The curable resin composition of the present invention preferably contains a polymerizable compound. In this specification, the compound corresponding to the above-mentioned specific resin is set as a compound that does not correspond to the polymerizable compound. As the polymerizable compound, a polyfunctional polymerizable compound is preferred. In this specification, a polyfunctional polymerizable compound refers to a compound having two or more polymerizable groups. In addition, as the polymerizable compound, a free radical polymerizable compound is preferred, and a compound having two or more free radical polymerizable groups is more preferred.

[自由基聚合性化合物] 作為聚合性化合物，能夠使用自由基聚合性化合物。自由基聚合性化合物為具有自由基聚合性基之化合物。作為自由基聚合性基，可以舉出乙烯基、烯丙基、乙烯基苯基、（甲基）丙烯醯基等具有乙烯性不飽和鍵之基團。自由基聚合性基為（甲基）丙烯醯基為較佳，從反應性的觀點考慮，（甲基）丙烯醯氧基為更佳。[Free radical polymerizable compound] As the polymerizable compound, a free radical polymerizable compound can be used. The free radical polymerizable compound is a compound having a free radical polymerizable group. As the free radical polymerizable group, there can be mentioned groups having an ethylenic unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth)acryloyl group. The free radical polymerizable group is preferably a (meth)acryloyl group, and from the viewpoint of reactivity, a (meth)acryloyloxy group is more preferred.

自由基聚合性化合物所具有之自由基聚合性基的數量可以為一個，亦可以為兩個以上，自由基聚合性化合物具有兩個以上的自由基聚合性基為較佳，具有3個以上為更佳。上限為15個以下為較佳，10個以下為更佳，8個以下為進一步較佳。The number of radical polymerizable groups possessed by the radical polymerizable compound may be one or two or more. The radical polymerizable compound preferably has two or more radical polymerizable groups, and more preferably has three or more radical polymerizable groups. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

自由基聚合性化合物的分子量為2,000以下為較佳，1,500以下為更佳，900以下為進一步較佳。自由基聚合性化合物的分子量的下限為100以上為較佳。The molecular weight of the radical polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.

從顯影性的觀點考慮，本發明的硬化性樹脂組成物包含至少一種包含兩個以上的自由基聚合性基之2官能以上的自由基聚合性化合物為較佳，包含至少一種3官能以上的自由基聚合性化合物為更佳。又，亦可以為2官能自由基聚合性化合物與3官能以上的自由基聚合性化合物的混合物。例如，2官能以上的聚合性單體的官能基數量表示一分子中之自由基聚合性基的數量為兩個以上。From the viewpoint of developing properties, the curable resin composition of the present invention preferably contains at least one radically polymerizable compound having two or more radical polymerizable groups, and more preferably contains at least one radically polymerizable compound having three or more functional groups. In addition, it may be a mixture of a radically polymerizable compound having two or more functional groups and a radically polymerizable compound having three or more functional groups. For example, the number of functional groups of a polymerizable monomer having two or more functional groups means that the number of radically polymerizable groups in one molecule is two or more.

作為自由基聚合性化合物的具體例，可以舉出不飽和羧酸（例如，丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、異巴豆酸、順丁烯二酸等）或其酯類、醯胺類，較佳為不飽和羧酸與多元醇化合物的酯及不飽和羧酸與多元胺化合物的醯胺類。又，亦可以較佳地使用具有羥基或胺基、氫硫基等親和性取代基之不飽和羧酸酯或醯胺類與單官能或多官能異氰酸酯類或環氧類的加成反應物、與單官能或多官能羧酸的脫水縮合反應物等。又，具有異氰酸酯基或環氧基等親電子性取代基之不飽和羧酸酯或醯胺類與單官能或多官能醇類、胺類、硫醇類的加成反應物、以及具有鹵素基或甲苯磺醯氧基等脫離性取代基之不飽和羧酸酯或醯胺類與單官能或多官能醇類、胺類、硫醇類的取代反應物亦較佳。又，作為另一例，亦能夠使用替換成不飽和膦酸、苯乙烯等乙烯基苯衍生物、乙烯醚、烯丙醚等之化合物群組來代替上述不飽和羧酸。作為具體例，能夠參閱日本特開2016-027357號公報的0113～0122段的記載，且該等內容被編入本說明書中。Specific examples of free radical polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having an affinity substituent such as a hydroxyl group, an amino group, or a thiohydride group with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. Furthermore, addition reaction products of unsaturated carboxylates or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylates or amides with dissociative substituents such as halogen groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Furthermore, as another example, a compound group replaced with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can also be used to replace the above-mentioned unsaturated carboxylic acid. As a specific example, the description of paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357 can be referred to, and the contents are incorporated into this specification.

又，自由基聚合性化合物為在常壓下具有100℃以上的沸點之化合物亦較佳。作為其例，可以舉出聚乙二醇二（甲基）丙烯酸酯、三羥甲基乙烷三（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、新戊四醇四（甲基）丙烯酸酯、二新戊四醇五（甲基）丙烯酸酯、二新戊四醇六（甲基）丙烯酸酯、己二醇（甲基）丙烯酸酯、三羥甲基丙烷三（丙烯醯氧基丙基）醚、三（丙烯醯氧基乙基）異三聚氰酸酯、甘油或三羥甲基乙烷等在多官能醇中加成環氧乙烷或環氧丙烷之後進行（甲基）丙烯酸酯化而獲得之化合物、如日本特公昭48-041708號公報、日本特公昭50-006034號公報、日本特開昭51-037193號各公報中所記載之（甲基）丙烯酸胺甲酸乙酯類、日本特開昭48-064183號、日本特公昭49-043191號、日本特公昭52-030490號各公報中所記載之聚酯丙烯酸酯類，作為環氧樹脂與（甲基）丙烯酸的反應產物之環氧丙烯酸酯類等多官能丙烯酸酯或甲基丙烯酸酯及該等混合物。又，日本特開2008-292970號公報的0254～0257段中所記載的化合物亦較佳。又，亦可以舉出使（甲基）丙烯酸環氧丙酯等具有環狀醚基及乙烯性不飽和鍵之化合物與多官能羧酸進行反應而獲得之多官能（甲基）丙烯酸酯等。In addition, the radical polymerizable compound is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyletrol tri(meth)acrylate, neopentyletrol tetra(meth)acrylate, dipentyletrol penta(meth)acrylate, dipentyletrol hexa(meth)acrylate, hexanediol (meth)acrylate, trihydroxymethylpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, etc., which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the obtained compound. Compounds obtained by esterification, such as (meth)acrylic acid urethanes described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, epoxy acrylates as reaction products of epoxy resins and (meth)acrylic acid, and multifunctional acrylates or methacrylates, and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, polyfunctional (meth)acrylates obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate with a polyfunctional carboxylic acid may be mentioned.

又，作為除了上述以外的較佳的自由基聚合性化合物，亦能夠使用日本特開2010-160418號公報、日本特開2010-129825號公報、日本專利第4364216號公報等中所記載之具有茀環且具有兩個以上的含有乙烯性不飽和鍵的基團之化合物或卡多（cardo）樹脂。Furthermore, as preferred radical polymerizable compounds other than the above, compounds having a fluorene ring and two or more groups containing ethylenically unsaturated bonds, or cardo resins described in Japanese Patent Application Laid-Open Nos. 2010-160418, 2010-129825, and 4364216, etc., can also be used.

進而，作為其他例，亦可以舉出日本特公昭46-043946號公報、日本特公平01-040337號公報、日本特公平01-040336號公報中所記載的特定的不飽和化合物或日本特開平02-025493號公報中所記載的乙烯基膦酸系化合物等。又，亦能夠使用日本特開昭61-022048號公報中所記載的包含全氟烷基之化合物。進而，亦能夠使用在“Journal of the Adhesion Society of Japan”vol.20、No.7、300～308頁（1984年）中作為光聚合性單體及寡聚物所介紹者。Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, or vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can be cited. In addition, compounds containing perfluoroalkyl groups described in Japanese Patent Publication No. 61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

除了上述以外，亦能夠較佳地使用日本特開2015-034964號公報的0048～0051段中所記載的化合物、國際公開第2015/199219號的0087～0131段中所記載的化合物，且該等內容被編入本說明書中。In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of WO-2015/199219 can also be preferably used, and the contents are incorporated into the present specification.

又，在日本特開平10-062986號公報中，作為式（1）及式（2）而與其具體例一同記載的如下化合物亦能夠用作自由基聚合性化合物，該化合物為在多官能醇中加成環氧乙烷或環氧丙烷之後進行（甲基）丙烯酸酯化而獲得之化合物。In Japanese Patent Application Laid-Open No. 10-062986, the following compounds described as formula (1) and formula (2) together with their specific examples can also be used as radical polymerizable compounds. These compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resulting mixture.

進而，亦能夠使用日本特開2015-187211號公報的0104～0131段中所記載的化合物作為其他自由基聚合性化合物，且該等內容被編入本說明書中。Furthermore, compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as other radical polymerizable compounds, and these contents are incorporated into this specification.

作為自由基聚合性化合物，二新戊四醇三丙烯酸酯（作為市售品為KAYARAD D-330；Nippon Kayaku Co.,Ltd.製）、二新戊四醇四丙烯酸酯（作為市售品為KAYARAD D-320；Nippon Kayaku Co.,Ltd.製、A-TMMT：Shin-Nakamura Chemical Co.,Ltd.製）、二新戊四醇五（甲基）丙烯酸酯（作為市售品為KAYARAD D-310；Nippon Kayaku Co.,Ltd.製）、二新戊四醇六（甲基）丙烯酸酯（作為市售品為KAYARAD DPHA；Nippon Kayaku Co.,Ltd.製、A-DPH；Shin-Nakamura Chemical Co.,Ltd.製）及該等（甲基）丙烯醯基經由乙二醇殘基或丙二醇殘基鍵結之結構為較佳。亦能夠使用該等寡聚物類型。As the radical polymerizable compound, dipentatriol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and the structures in which the (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

作為自由基聚合性化合物的市售品，例如可以舉出Sartomer Company, Inc製的作為具有四個伸乙氧基鏈之4官能丙烯酸酯之SR-494、作為具有四個乙烯氧基鏈之2官能丙烯酸甲酯之Sartomer Company, Inc製SR-209、231、239、Nippon Kayaku Co.,Ltd.製的作為具有六個伸戊氧基鏈之6官能丙烯酸酯之DPCA-60、作為具有三個異伸丁氧基鏈之3官能丙烯酸酯之TPA-330、胺甲酸乙酯寡聚物UAS-10、UAB-140（NIPPON PAPER INDUSTRIES CO., LTD.製）、NK酯M-40G、NK酯4G、NK酯M-9300、NK酯A-9300、UA-7200（Shin-Nakamura Chemical Co., Ltd製）、DPHA-40H（Nippon Kayaku Co.,Ltd.製）、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600（Kyoeisha chemical Co.,Ltd.製）、BLEMMER PME400（NOF CORPORATION製）等。As commercially available products of the radical polymerizable compound, for example, SR-494 manufactured by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy chains, SR-209, 231, 239 manufactured by Sartomer Company, Inc. as a bifunctional methyl acrylate having four vinyloxy chains, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having six pentoxy chains, TPA-330 as a trifunctional acrylate having three isobutyloxy chains, urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

作為自由基聚合性化合物，如日本特公昭48-041708號公報、日本特開昭51-037193號公報、日本特公平02-032293號公報、日本特公平02-016765號公報中所記載之那樣的胺甲酸乙酯丙烯酸酯類、日本特公昭58-049860號公報、日本特公昭56-017654號公報、日本特公昭62-039417號公報、日本特公昭62-039418號公報中所記載的具有環氧乙烷系骨架之胺甲酸乙酯化合物類亦較佳。進而，作為自由基聚合性化合物，亦能夠使用日本特開昭63-277653號公報、日本特開昭63-260909號公報、日本特開平01-105238號公報中所記載之在分子內具有胺基結構或硫化物結構之化合物。As free radical polymerizable compounds, urethane acrylates such as those described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. Furthermore, as the radical polymerizable compound, a compound having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238 can also be used.

自由基聚合性化合物可以為具有羧基、磷酸基等酸基之自由基聚合性化合物。具有酸基之自由基聚合性化合物為脂肪族多羥基化合物與不飽和羧酸的酯為較佳，使非芳香族羧酸酐與脂肪族多羥基化合物的未反應的羥基進行反應而具有酸基之自由基聚合性化合物為更佳。特佳為在使非芳香族羧酸酐與脂肪族多羥基化合物的未反應的羥基進行反應而具有酸基之自由基聚合性化合物中，脂肪族多羥基化合物為新戊四醇或二新戊四醇之化合物。作為市售品，例如作為TOAGOSEI CO.,Ltd.製多元酸改質丙烯酸類寡聚物，可以舉出M-510、M-520等。The free radical polymerizable compound may be a free radical polymerizable compound having an acid group such as a carboxyl group or a phosphoric acid group. The free radical polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is more preferably a free radical polymerizable compound having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. Particularly preferred is a compound in which the aliphatic polyhydroxy compound is neopentyl triol or dipentyl triol among free radical polymerizable compounds having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. As commercially available products, for example, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd. include M-510 and M-520.

具有酸基之自由基聚合性化合物的較佳酸值為0.1～40mgKOH/g，特佳為5～30mgKOH/g。只要自由基聚合性化合物的酸值在上述範圍內，則製造上的操作性優異，進而顯影性優異。又，聚合性良好。另外，從鹼性顯影時的顯影速度的觀點考慮，具有酸基之自由基交聯劑的較佳酸值為0.1～300mgKOH/g，特佳為1～100mgKOH/g。關於上述酸值，依據JIS K 0070：1992的記載來測定。The preferred acid value of the radical polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, and the particularly preferred acid value is 5 to 30 mgKOH/g. As long as the acid value of the radical polymerizable compound is within the above range, the operability in manufacturing is excellent, and the developing property is excellent. In addition, the polymerizability is good. In addition, from the perspective of the developing speed during alkaline development, the preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mgKOH/g, and the particularly preferred acid value is 1 to 100 mgKOH/g. The above acid value is measured in accordance with the description of JIS K 0070:1992.

關於本發明的硬化性樹脂組成物，從伴隨硬化膜的彈性模數控制而抑制翹曲的觀點考慮，能夠較佳地使用單官能自由基聚合性化合物作為自由基聚合性化合物。作為單官能自由基聚合性化合物，可以較佳地使用正丁基（甲基）丙烯酸酯、2-乙基己基（甲基）丙烯酸酯、2-羥乙基（甲基）丙烯酸酯、丁氧基乙基（甲基）丙烯酸酯、卡必醇（甲基）丙烯酸酯、環己基（甲基）丙烯酸酯、芐基（甲基）丙烯酸酯、苯氧基乙基（甲基）丙烯酸酯、N-羥甲基（甲基）丙烯醯胺、環氧丙基（甲基）丙烯酸酯、聚乙二醇單（甲基）丙烯酸酯、聚丙二醇單（甲基）丙烯酸酯等（甲基）丙烯酸衍生物、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺等N-乙烯基化合物類、烯基環氧丙醚、鄰苯二甲酸二烯丙酯、偏苯三酸三烯丙酯等烯基化合物類等。作為單官能自由基聚合性化合物，為了抑制曝光前的揮發，在常壓下具有100℃以上的沸點之化合物亦較佳。又，從圖案的解析度和膜的伸縮性的觀點考慮，使用2官能甲基丙烯酸酯或丙烯酸酯亦較佳。 作為具體的化合物，能夠使用三乙二醇二丙烯酸酯、三乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、四乙二醇二丙烯酸酯、PEG200二丙烯酸酯、PEG200二甲基丙烯酸酯、PEG600二丙烯酸酯、PEG600二甲基丙烯酸酯、聚四乙二醇二丙烯酸酯、聚四乙二醇二甲基丙烯酸酯、新戊二醇二丙烯酸酯、新戊二醇二甲基丙烯酸酯、3-甲基-1,5-戊二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,6己二醇二甲基丙烯酸酯、二羥甲基三環癸烷二丙烯酸酯、二羥甲基三環癸烷二甲基丙烯酸酯、雙酚A的EO（環氧乙烷）加成物二丙烯酸酯、雙酚A的EO加成物二甲基丙烯酸酯、雙酚A的PO（環氧丙烷）加成物二丙烯酸酯、雙酚A的PO加成物二甲基丙烯酸酯、2羥基-3-丙烯醯氧基丙基甲基丙烯酸酯、異三聚氰酸EO改質二丙烯酸酯、異三聚氰酸改質二甲基丙烯酸酯、具有其他胺甲酸乙酯鍵之2官能丙烯酸酯、具有胺甲酸乙酯鍵之2官能甲基丙烯酸酯。該等依據需要能夠混合使用兩種以上。另外，例如PEG200二丙烯酸酯是指為聚乙二醇二丙烯酸酯且聚乙二醇鏈的式量為200左右者。In the curable resin composition of the present invention, from the viewpoint of suppressing warping accompanying control of the elastic modulus of the cured film, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound. As the monofunctional free radical polymerizable compound, (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, N-vinyl compounds such as N-vinyl pyrrolidone and N-vinyl caprolactam, alkenyl compounds such as alkenyl glycidyl ether, diallyl phthalate, and triallyl trimellitate can be preferably used. As a monofunctional free radical polymerizable compound, in order to suppress volatility before exposure, a compound having a boiling point of 100°C or more at normal pressure is also preferred. In addition, from the perspective of pattern resolution and film stretchability, it is also preferred to use a bifunctional methacrylate or acrylate. As a specific compound, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate can be used. Acid ester, dihydroxymethyl tricyclodecane diacrylate, dihydroxymethyl tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO modified diacrylate of isocyanuric acid, modified dimethacrylate of isocyanuric acid, bifunctional acrylate with other urethane bonds, bifunctional methacrylate with urethane bonds. Two or more of these can be used in combination as needed. In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain formula weight of about 200.

[除了上述自由基聚合性化合物以外的聚合性化合物] 本發明的硬化性樹脂組成物還能夠含有除了上述自由基聚合性化合物以外的聚合性化合物。作為除了上述自由基聚合性化合物以外的聚合性化合物，可以舉出具有羥甲基（Methylol group）、烷氧基甲基或醯氧基甲基之化合物；環氧化合物；氧雜環丁烷化合物；苯并㗁𠯤化合物。[Polymerizable compounds other than the above-mentioned free radical polymerizable compounds] The curable resin composition of the present invention may also contain polymerizable compounds other than the above-mentioned free radical polymerizable compounds. Examples of polymerizable compounds other than the above-mentioned free radical polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group, or an acyloxymethyl group; epoxy compounds; cyclohexane compounds; and benzophenone compounds.

-具有羥甲基、烷氧基甲基或醯氧基甲基之化合物- 作為具有羥甲基、烷氧基甲基或醯氧基甲基之化合物，下述式（AM1）、式（AM4）或式（AM5）所表示之化合物為較佳。-Compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group- As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, the compounds represented by the following formula (AM1), formula (AM4) or formula (AM5) are preferred.

[化學式30] （式中，t表示1～20的整數，R104 表示碳數1～200的t價有機基，R105 表示-OR106 或-OCO-R107 所表示之基團，R106 表示氫原子或碳數1～10的有機基，R107 表示碳數1～10的有機基。） [化學式31] （式中，R404 表示碳數1～200的2價有機基，R405 表示-OR406 或-OCO-R407 所表示之基團，R406 表示氫原子或碳數1～10的有機基，R407 表示碳數1～10的有機基。） [化學式32] （式中，u表示3～8的整數，R504 表示碳數1～200的u價有機基，R505 表示-OR506 或-OCO-R507 所表示之基團，R506 表示氫原子或碳數1～10的有機基，R507 表示碳數1～10的有機基。）[Chemical formula 30] (In the formula, t represents an integer of 1 to 20, R 104 represents a t-valent organic group having 1 to 200 carbon atoms, R 105 represents a group represented by -OR 106 or -OCO-R 107 , R 106 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R 107 represents an organic group having 1 to 10 carbon atoms.) [Chemical Formula 31] (In the formula, R 404 represents a divalent organic group having 1 to 200 carbon atoms, R 405 represents a group represented by -OR 406 or -OCO-R 407 , R 406 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R 407 represents an organic group having 1 to 10 carbon atoms.) [Chemical Formula 32] (In the formula, u represents an integer of 3 to 8, R 504 represents a u-valent organic group having 1 to 200 carbon atoms, R 505 represents a group represented by -OR 506 or -OCO-R 507 , R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R 507 represents an organic group having 1 to 10 carbon atoms.)

作為式（AM4）所表示之化合物的具體例，可以舉出46DMOC、46DMOEP（以上為產品名稱，ASAHI YUKIZAI CORPORATION製）、DML-MBPC、DML-MBOC、DML-OCHP、DML-PCHP、DML-PC、DML-PTBP、DML-34X、DML-EP、DML-POP、dimethylolBisOC-P、DML-PFP、DML-PSBP、DML-MTrisPC（以上為產品名稱，Honshu Chemical Industry Co.,Ltd.製）、NIKALAC MX-290（產品名稱，Sanwa Chemical Co.,Ltd.製）、2,6-dimethoxymethyl-4-t-butylphenol（2,6-二甲氧基甲基-4-第三丁基酚）、2,6-dimethoxymethyl-p-cresol（2,6-二甲氧基甲基-對甲酚）、2,6-diacetoxymethyl-p-cresol（2,6-二乙醯氧基甲基-對甲酚）等。Specific examples of the compound represented by formula (AM4) include 46DMOC, 46DMOEP (product names, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (product names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (product name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol (2,6-dimethoxymethyl-4-tert-butylphenol), 2,6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacetoxymethyl-p-cresol (2,6-diacetoxymethyl-p-cresol), etc.

又，作為式（AM5）所表示之化合物的具體例，可以舉出TriML-P、TriML-35XL、TML-HQ、TML-BP、TML-pp-BPF、TML-BPA、TMOM-BP、HML-TPPHBA、HML-TPHAP、HMOM-TPPHBA、HMOM-TPHAP（以上為產品名稱，Honshu Chemical Industry Co.,Ltd.製）、TM-BIP-A（產品名稱，ASAHI YUKIZAI CORPORATION製）、NIKALAC MX-280、NIKALAC MX-270、NIKALAC MW-100LM（以上為產品名稱，Sanwa Chemical Co.,Ltd.製）。Specific examples of the compound represented by formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (these are product names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (product name, manufactured by ASAHI YUKIZAI CORPORATION), NIKALAC MX-280, NIKALAC MX-270, and NIKALAC MW-100LM (these are product names, manufactured by Sanwa Chemical Co., Ltd.).

-環氧化合物（具有環氧基之化合物）- 作為環氧化合物，在一分子中具有兩個以上的環氧基之化合物為較佳。環氧基在200℃以下進行交聯反應，並且不會產生由交聯引起之脫水反應，因此不易引起膜收縮。因此，含有環氧化合物對抑制硬化性樹脂組成物的低溫硬化及翹曲係有效的。-Epoxy compounds (compounds having epoxy groups)- As epoxy compounds, compounds having two or more epoxy groups in one molecule are preferred. Epoxy groups undergo crosslinking reaction below 200°C, and dehydration reaction caused by crosslinking does not occur, so it is not easy to cause film shrinkage. Therefore, containing epoxy compounds is effective in suppressing low-temperature curing and warping of curable resin compositions.

環氧化合物含有聚環氧乙烷基為較佳。藉此，彈性模數進一步下降，並且能夠抑制翹曲。聚環氧乙烷基表示環氧乙烷的重複單元數為2以上者，重複單元數為2～15為較佳。The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and can suppress warping. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

作為環氧化合物的例子，可以舉出雙酚A型環氧樹脂；雙酚F型環氧樹脂；丙二醇二環氧丙基醚等伸烷基二醇型環氧樹脂；聚丙二醇二環氧丙基醚等聚伸烷基二醇型環氧樹脂；聚甲基（環氧丙基氧基丙基）矽氧烷等含環氧基的聚矽氧、作為縮水甘油基異氰尿酸酯等異三聚氰酸衍生物之環氧樹脂、作為N,N’,N’’,N’’’-四縮水甘油基甘脲等甘脲衍生物之環氧樹脂等，但是並不限定於該等。又，從耐藥品性的觀點考慮，上述異三聚氰酸衍生物或甘脲衍生物為較佳。推測這是因為，異三聚氰酸環結構、甘脲結構等環結構等的非質子性且高極性之結構對耐藥品性係有效的。 具體而言，可以舉出EPICLON（註冊商標）850-S、EPICLON（註冊商標）HP-4032、EPICLON（註冊商標）HP-7200、EPICLON（註冊商標）HP-820、EPICLON（註冊商標）HP-4700、EPICLON（註冊商標）EXA-4710、EPICLON（註冊商標）HP-4770、EPICLON（註冊商標）EXA-859CRP、EPICLON（註冊商標）EXA-1514、EPICLON（註冊商標）EXA-4880、EPICLON（註冊商標）EXA-4850-150、EPICLON（註冊商標）EXA-4850-1000、EPICLON（註冊商標）EXA-4816、EPICLON（註冊商標）EXA-4822、EPICLON（註冊商標）EXA-830LVP、EPICLON（註冊商標）EXA-8183、EPICLON（註冊商標）EXA-8169、EPICLON（註冊商標）N-660、EPICLON（註冊商標）N-665-EXP-S、EPICLON（註冊商標）N-740、RIKARESIN（註冊商標）BEO-20E（以上為產品名稱，DIC CORPORATION製）、RIKARESIN（註冊商標）BEO-60E、RIKARESIN（註冊商標）HBE-100、RIKARESIN（註冊商標）DME-100、RIKARESIN（註冊商標）L-200（產品名稱，New Japan Chemical Co., Ltd.）、EP-4003S、EP-4000S、EP-4088S、EP-3950S（以上為產品名稱，ADEKA CORPORATION製）、TG-G、MA-DGIC、DA-MGIC（以上為產品名稱，SHIKOKU CHEMICALS CORPORATION.製）等。其中，從抑制翹曲及耐熱性優異之觀點考慮，包含聚環氧乙烷基之環氧樹脂為較佳。例如，EPICLON（註冊商標）EXA-4880、EPICLON（註冊商標）EXA-4822、RIKARESIN（註冊商標）BEO-60E包含聚環氧乙烷基，因此為較佳。Examples of epoxy compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether, polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether, epoxy-containing polysiloxanes such as polymethyl (glycidyloxypropyl) siloxane, epoxy resins of isocyanuric acid derivatives such as glycidyl isocyanurate, and epoxy resins of glycoluril derivatives such as N,N',N'',N'''-tetraglycidyl glycoluril, but are not limited thereto. In terms of drug resistance, the above-mentioned isocyanuric acid derivatives or glycoluril derivatives are preferred. This is presumably because non-protonic and highly polar structures such as isocyanuric acid ring structures and glycoluril structures are effective against drug resistance. Specifically, we can cite EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-485 0-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740, RIKARESIN (registered trademark) BEO-20E (the above are product names, DIC CORPORATION), RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (product names, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, ADEKA CORPORATION), TG-G, MA-DGIC, DA-MGIC (the above are product names, SHIKOKU CHEMICALS CORPORATION), etc. Among them, epoxy resins containing polyethylene oxide groups are preferred from the viewpoint of suppressing warp and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups and are therefore preferred.

-氧雜環丁烷化合物（具有氧雜環丁基之化合物）- 作為氧雜環丁烷化合物，可以舉出在一分子中具有兩個以上的氧雜環丁烷環之化合物、3-乙基-3-羥甲氧雜環丁烷、1,4-雙｛[（3-乙基-3-氧雜環丁基）甲氧基]甲基}苯、3-乙基-3-（2-乙基己基甲基）氧雜環丁烷、1,4-苯二羧酸-雙[（3-乙基-3-氧雜環丁基）甲基]酯等。作為具體的例子，能夠較佳地使用TOAGOSEI CO.,LTD.製ARON OXETANE系列（例如，OXT-121、OXT-221、OXT-191、OXT-223），該等可以單獨使用或混合兩種以上使用。-Oxycyclobutane compounds (compounds having an oxycyclobutyl group)- Examples of oxycyclobutane compounds include compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethoxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl]ester. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

-苯并㗁𠯤化合物（具有聚苯并㗁唑基之化合物）- 由於由開環加成反應引起交聯反應，苯并㗁𠯤化合物在硬化時不產生脫氣，從而進一步減少熱收縮以抑制產生翹曲，因此為較佳。-Benzotriazole compounds (compounds having polybenzotriazole groups)- Since the cross-linking reaction is caused by the ring-opening addition reaction, the benzotriazole compound does not produce degassing during curing, thereby further reducing thermal shrinkage to suppress the occurrence of warping, so it is preferred.

作為苯并㗁𠯤化合物的較佳例，可以舉出B-a型苯并㗁𠯤、B-m型苯并㗁𠯤、P-d型苯并㗁𠯤、F-a型苯并㗁𠯤、（以上為產品名稱，Shikoku Chemicals Corporation製）、聚羥基苯乙烯樹脂的苯并㗁𠯤加成物、酚醛清漆型二氫苯并㗁𠯤化合物。該等可以單獨使用或者混合兩種以上使用。Preferred examples of benzophenone compounds include B-a type benzophenone, B-m type benzophenone, P-d type benzophenone, F-a type benzophenone (the above are product names, manufactured by Shikoku Chemicals Corporation), benzophenone adducts of polyhydroxystyrene resins, and novolac type dihydrobenzophenone compounds. These may be used alone or in combination of two or more.

聚合性化合物的含量相對於本發明的硬化性樹脂組成物的總固體成分超過0質量%且為60質量%以下為較佳。下限為5質量%以上為更佳。上限為50質量%以下為更佳，30質量%以下為進一步較佳。The content of the polymerizable compound is preferably more than 0 mass % and 60 mass % or less relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

聚合性化合物可以單獨使用一種，亦可以混合使用兩種以上。在同時使用兩種以上之情況下，合計量在上述範圍內為較佳。The polymerizable compound may be used alone or in combination of two or more. When two or more are used simultaneously, the total amount is preferably within the above range.

＜其他樹脂＞ 本發明的硬化性樹脂組成物亦可以包含與上述特定樹脂不同之其他樹脂（以下，亦簡稱為“其他樹脂”。）。 作為其他樹脂，可以舉出與特定樹脂不同種類的聚醯亞胺、與特定樹脂不同種類的聚醯亞胺前驅物、聚矽氧烷、包含矽氧烷結構之樹脂、環氧樹脂、丙烯酸樹脂等。 例如，藉由進一步添加丙烯酸樹脂，可以獲得塗佈性優異之組成物，並且可以獲得耐藥品性優異之硬化膜。 例如，代替後述聚合性化合物或除了後述聚合性化合物以外，將重量平均分子量為20,000以下的聚合性基值高的丙烯酸系樹脂添加至組成物中，從而能夠提高組成物的塗佈性、硬化膜的耐藥品性等。<Other resins> The curable resin composition of the present invention may also contain other resins different from the above-mentioned specific resin (hereinafter, also referred to as "other resins" for short). As other resins, polyimide of a different type from the specific resin, polyimide precursor of a different type from the specific resin, polysiloxane, resin containing a siloxane structure, epoxy resin, acrylic resin, etc. can be cited. For example, by further adding an acrylic resin, a composition with excellent coating properties can be obtained, and a cured film with excellent chemical resistance can be obtained. For example, by adding a high polymerizable acrylic resin having a weight average molecular weight of 20,000 or less to the composition instead of or in addition to the polymerizable compound described below, the coating properties of the composition and the chemical resistance of the cured film can be improved.

[聚醯亞胺（其他樹脂）] 從所獲得之硬化膜的膜強度的觀點考慮，作為其他樹脂之聚醯亞胺包含上述式（4）所表示之重複單元為較佳。 在聚醯亞胺中，式（4）所表示之重複單元可以為一種，亦可以為兩種以上。又，除了上述式（4）的重複單元以外，聚醯亞胺還可以包含其他種類的重複單元。[Polyimide (other resins)] From the viewpoint of the film strength of the obtained cured film, it is preferable that the polyimide as the other resin contains the repeating unit represented by the above formula (4). In the polyimide, the repeating unit represented by the formula (4) may be one type or two or more types. In addition to the repeating unit of the above formula (4), the polyimide may also contain other types of repeating units.

作為本發明中之聚醯亞胺的一實施形態，可以例示總重複單元的50莫耳%以上，進一步70莫耳%以上，尤其90莫耳%以上為式（4）所表示之重複單元之聚醯亞胺前驅物。作為上限，實際為100莫耳%以下。As an embodiment of the polyimide of the present invention, a polyimide precursor can be exemplified in which 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of the total repeating units are repeating units represented by formula (4). The upper limit is practically 100 mol% or less.

聚醯亞胺的重量平均分子量（Mw）較佳為2,000～500,000，更佳為5,000～100,000，進一步較佳為10,000～50,000。又，數量平均分子量（Mn）較佳為800～250,000，更佳為2,000～50,000，進一步較佳為4,000～25,000。The weight average molecular weight (Mw) of the polyimide is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

聚醯亞胺的分子量的分散度為1.5～3.5為較佳，2～3為更佳。The molecular weight dispersion of polyimide is preferably 1.5 to 3.5, more preferably 2 to 3.

關於聚醯亞胺，例如藉由加熱等將作為後述其他樹脂之聚醯亞胺前驅物環化而獲得。Polyimide can be obtained, for example, by cyclizing a polyimide precursor, which is another resin described later, by heating.

[聚醯亞胺前驅物（其他樹脂）] 從所獲得之硬化膜的膜強度的觀點考慮，聚醯亞胺前驅物包含上述式（1）所表示之重複單元為較佳。[Polyimide precursor (other resins)] From the viewpoint of the film strength of the obtained cured film, the polyimide precursor preferably contains the repeating unit represented by the above formula (1).

在聚醯亞胺前驅物中，式（1）所表示之重複單元可以為一種，亦可以為兩種以上。又，亦可以包含式（1）所表示之重複單元的結構異構物。又，除了上述式（1）的重複單元以外，聚醯亞胺前驅物還可以包含其他種類的重複單元。In the polyimide precursor, the repeating unit represented by formula (1) may be one type or two or more types. Furthermore, the polyimide precursor may contain structural isomers of the repeating unit represented by formula (1). Furthermore, in addition to the repeating unit of formula (1), the polyimide precursor may contain other types of repeating units.

作為本發明中之聚醯亞胺前驅物的一實施形態，可以例示總重複單元的50莫耳%以上，進一步70莫耳%以上，尤其90莫耳%以上為式（1）所表示之重複單元之聚醯亞胺前驅物。作為上限，實際為100莫耳%以下。As an embodiment of the polyimide precursor of the present invention, 50 mol% or more, further 70 mol% or more, and especially 90 mol% or more of the total repeating units are the repeating units represented by formula (1). The upper limit is practically 100 mol% or less.

聚醯亞胺前驅物的重量平均分子量（Mw）較佳為2,000～500,000，更佳為5,000～100,000，進一步較佳為10,000～50,000。又，數量平均分子量（Mn）較佳為800～250,000，更佳為2,000～50,000，進一步較佳為4,000～25,000。The weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

聚醯亞胺前驅物的分子量的分散度為1.5～3.5為較佳，2～3為更佳。The molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

關於聚醯亞胺前驅物，藉由使二羧酸或二羧酸衍生物與二胺進行反應而獲得。較佳為，在使用鹵化劑將二羧酸或二羧酸衍生物鹵化之後，使其與二胺進行反應而獲得。The polyimide precursor is obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine. Preferably, the dicarboxylic acid or a dicarboxylic acid derivative is halogenated with a halogenating agent and then reacted with diamine.

在聚醯亞胺前驅物的製造方法中，在進行反應時使用有機溶劑為較佳。有機溶劑可以為一種，亦可以為兩種以上。In the method for producing a polyimide precursor, it is preferred to use an organic solvent during the reaction. The organic solvent may be one or more.

作為有機溶劑，能夠依據原料適當設定，但是可以例示吡啶、二乙二醇二甲醚（二甘二甲醚）、N-甲基吡咯啶酮及N-乙基吡咯啶酮。The organic solvent can be appropriately set depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

在製造聚醯亞胺前驅物時，包括析出固體之步驟為較佳。具體而言，使反應液中的聚醯亞胺前驅物沉澱於水中並使其溶解於四氫呋喃等可溶解聚醯亞胺前驅物之溶劑中，從而能夠析出固體。When preparing the polyimide precursor, it is preferred to include a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran that can dissolve the polyimide precursor, thereby precipitating a solid.

在本發明的硬化性樹脂組成物包含其他樹脂之情況下，其他樹脂的含量相對於硬化性樹脂組成物的總固體成分為0.01質量%以上為較佳，0.05質量%以上為更佳，1質量%以上為進一步較佳，2質量%以上為更進一步較佳，5質量%以上為又更進一步較佳，10質量%以上為再更進一步較佳。 又，本發明的硬化性樹脂組成物中之其他樹脂的含量相對於硬化性樹脂組成物的總固體成分為80質量%以下為較佳，75質量%以下為更佳，70質量%以下為進一步較佳，60質量%以下為更進一步較佳，50質量%以下為又更進一步較佳。 又，作為本發明的硬化性樹脂組成物的較佳一態樣，亦能夠設為其他樹脂的含量為低含量之態樣。在上述態樣中，其他樹脂的含量相對於硬化性樹脂組成物的總固體成分為20質量%以下為較佳，15質量%以下為更佳，10質量%以下為進一步較佳，5量%以下為更進一步較佳，1質量%以下為又更進一步較佳。上述含量的下限並無特別限定，只要為0質量%以上即可。 本發明的硬化性樹脂組成物可以僅包含一種其他樹脂，亦可以包含兩種以上。在包含兩種以上之情況下，合計量在上述範圍內為較佳。When the curable resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more relative to the total solid content of the curable resin composition. In addition, the content of the other resins in the curable resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less relative to the total solid content of the curable resin composition. In addition, as a preferred embodiment of the curable resin composition of the present invention, the content of other resins can also be set to a low content. In the above embodiment, the content of other resins relative to the total solid content of the curable resin composition is preferably 20% by mass or less, 15% by mass or less is more preferably, 10% by mass or less is further preferably, 5% by mass or less is further preferably, and 1% by mass or less is further preferably. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more. The curable resin composition of the present invention may contain only one other resin, or may contain two or more. When containing two or more, it is preferred that the total amount is within the above range.

＜鎓鹽＞ 本發明的硬化性樹脂組成物包含鎓鹽為較佳。 尤其，在硬化性樹脂組成物包括包含式（2-1）所表示之重複單元或式（2-4）所表示之重複單元之樹脂作為特定樹脂之情況下，硬化性樹脂組成物包含熱鹼產生劑為較佳。 鎓鹽的種類等並無特別限定，可以較佳地舉出銨鹽、亞胺鹽、鋶鹽、錪鹽或鏻鹽。 其中，從熱穩定性高的觀點考慮，銨鹽或亞胺鹽為較佳，從與聚合物的相溶性的觀點考慮，鋶鹽、錪鹽或鏻鹽為較佳。<Onium salt> The curable resin composition of the present invention preferably contains an onium salt. In particular, when the curable resin composition includes a resin containing a repeating unit represented by formula (2-1) or a repeating unit represented by formula (2-4) as a specific resin, the curable resin composition preferably contains a thermal alkali generator. The type of onium salt is not particularly limited, and preferably includes ammonium salts, imide salts, cobalt salts, iodine salts or phosphonium salts. Among them, ammonium salts or imide salts are preferred from the viewpoint of high thermal stability, and cobalt salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with the polymer.

又，鎓鹽為具有鎓結構之陽離子與陰離子的鹽，上述陽離子與陰離子可以經由共價鍵而鍵結，亦可以不經由共價鍵而鍵結。 亦即，鎓鹽可以為在同一分子結構內具有陽離子部和陰離子部之分子內鹽，亦可以為作為分別不同的分子之陽離子分子與陰離子分子進行離子鍵結之分子間鹽，分子間鹽為較佳。又，在本發明的硬化性樹脂組成物中，上述陽離子部或陽離子分子與上述陰離子部或陰離子分子可以藉由離子鍵而鍵結，亦可以解離。 作為鎓鹽中之陽離子，銨陽離子、吡啶鎓陽離子、鋶陽離子、錪陽離子或鏻陽離子為較佳，選自包括四烷基銨陽離子、鋶陽離子及錪陽離子之群組中的至少一種陽離子為更佳。In addition, an onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may be bonded via covalent bonding or not. That is, an onium salt may be an intramolecular salt having a cation part and anion part in the same molecular structure, or an intermolecular salt in which a cation molecule and anion molecule that are separate molecules are ionically bonded, and an intermolecular salt is preferred. Furthermore, in the curable resin composition of the present invention, the cationic part or cationic molecule and the anionic part or anionic molecule can be bonded or dissociated by ionic bonding. As the cation in the onium salt, ammonium cation, pyridinium cation, coronium cation, iodine cation or phosphonium cation is preferred, and at least one cation selected from the group including tetraalkylammonium cation, coronium cation and iodine cation is more preferred.

在本發明中所使用之鎓鹽可以為熱鹼產生劑。 熱鹼產生劑是指藉由加熱產生鹼之化合物，例如可以舉出若加熱至40℃以上則產生鹼之酸性化合物等。The onium salt used in the present invention may be a thermal alkali generator. A thermal alkali generator refers to a compound that generates a base by heating, for example, an acidic compound that generates a base when heated to 40°C or above.

[銨鹽] 在本發明中，銨鹽表示銨陽離子與陰離子的鹽。[Ammonium salt] In the present invention, ammonium salt refers to a salt of ammonium cations and anions.

-銨陽離子- 作為銨陽離子，四級銨陽離子為較佳。 又，作為銨陽離子，下述式（101）所表示之陽離子為較佳。 [化學式33] 式（101）中，R1 ～R4 分別獨立地表示氫原子或烴基，R1 ～R4 中的至少兩個可以分別鍵結而形成環。-Ammonium cation- As the ammonium cation, a quaternary ammonium cation is preferred. Furthermore, as the ammonium cation, a cation represented by the following formula (101) is preferred. [Chemical formula 33] In formula (101), R 1 to R 4 each independently represents a hydrogen atom or a hydrocarbon group, and at least two of R 1 to R 4 may be bonded to form a ring.

式（101）中，R1 ～R4 分別獨立地為烴基為較佳，烷基或芳基為更佳，碳數1～10的烷基或碳數6～12的芳基為進一步較佳。R1 ～R4 亦可以具有取代基，作為取代基的例子，可以舉出羥基、芳基、烷氧基、芳氧基、芳基羰基、烷基羰基、烷氧基羰基、芳氧基羰基、醯氧基等。 在R1 ～R4 中的至少兩個分別鍵結而形成環之情況下，上述環亦可以包含雜原子。作為上述雜原子，可以舉出氮原子。In formula (101), R 1 to R 4 are each independently preferably a alkyl group, more preferably an alkyl group or an aryl group, and further preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms. R 1 to R 4 may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. When at least two of R 1 to R 4 are bonded to form a ring, the ring may include a heteroatom. Examples of the heteroatom include a nitrogen atom.

銨陽離子由下述式（Y1-1）及（Y1-2）中的任一個表示為較佳。 [化學式34] The ammonium cation is preferably represented by any one of the following formulas (Y1-1) and (Y1-2). [Chemical formula 34]

在式（Y1-1）及（Y1-2）中，R101 表示n價有機基，R1 與式（101）中之R1 的含義相同，Ar101 及Ar102 分別獨立地表示芳基，n表示1以上的整數。 在式（Y1-1）中，R101 為從脂肪族烴、芳香族烴或該等鍵結而形成之結構去除n個氫原子而獲得之基團為較佳，從碳數2～30的飽和脂肪族烴、苯或萘去除n個氫原子而獲得之基團為更佳。 在式（Y1-1）中，n為1～4為較佳，1或2為更佳，1為進一步較佳。 在式（Y1-2）中，Ar101 及Ar102 分別獨立地為苯基或萘基為較佳，苯基為更佳。In formula (Y1-1) and (Y1-2), R101 represents an n-valent organic group, R1 has the same meaning as R1 in formula (101), Ar101 and Ar102 each independently represent an aromatic group, and n represents an integer greater than 1. In formula (Y1-1), R101 is preferably a group obtained by removing n hydrogen atoms from an aliphatic hydrocarbon, an aromatic hydrocarbon, or a structure formed by such a bond, and more preferably a group obtained by removing n hydrogen atoms from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene, or naphthalene. In formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. In formula (Y1-2), Ar 101 and Ar 102 are each independently preferably a phenyl group or a naphthyl group, more preferably a phenyl group.

-陰離子- 作為銨鹽中之陰離子，選自羧酸根陰離子、酚陰離子、磷酸根陰離子及硫酸根陰離子中之一種為較佳，從能夠兼顧鹽的穩定性及熱分解性的理由考慮，羧酸根陰離子為更佳。亦即，銨鹽為銨陽離子與羧酸根陰離子的鹽為更佳。 羧酸根陰離子為具有兩個以上的羧基之2價以上的羧酸的陰離子為較佳，2價羧酸的陰離子為更佳。依據該態樣，能夠進一步提高硬化性樹脂組成物的穩定性、硬化性及顯影性。尤其，藉由使用2價羧酸的陰離子，能夠進一步提高硬化性樹脂組成物的穩定性、硬化性及顯影性。-Anions- As the anion in the ammonium salt, one selected from carboxylate anions, phenol anions, phosphate anions and sulfate anions is preferred, and carboxylate anions are more preferred from the viewpoint of being able to take both the stability and thermal decomposition of the salt into consideration. That is, the ammonium salt is preferably a salt of ammonium cation and carboxylate anions. The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, and an anion of a divalent carboxylic acid is more preferred. According to this aspect, the stability, curability and developing properties of the curable resin composition can be further improved. In particular, by using anions of divalent carboxylic acids, the stability, curability, and developing properties of the curable resin composition can be further improved.

羧酸根陰離子由下述式（X1）表示為較佳。 [化學式35] 在式（X1）中，EWG表示拉電子基團。The carboxylate anion is preferably represented by the following formula (X1). [Chemical Formula 35] In formula (X1), EWG represents an electron-withdrawing group.

在本實施形態中，拉電子基團表示哈密特取代基常數σm表示正的值者。其中，σm在都野雄甫總說、Journal of Synthetic Organic Chemistry, Japan第23卷第8號（1965）p.631-642中有詳細說明。另外，本實施形態中之拉電子基團並不限定於上述文獻中所記載之取代基。 作為σm表示正的值之取代基的例子，可以舉出CF3 基（σm=0.43）、CF3 C（=O）基（σm=0.63）、HC≡C基（σm=0.21）、CH2 =CH基（σm=0.06）、Ac基（σm=0.38）、MeOC（=O）基（σm=0.37）、MeC（=O）CH=CH基（σm=0.21）、PhC（=O）基（σm=0.34）、H2 NC（=O）CH2 基（σm=0.06）等。另外，Me表示甲基，Ac表示乙醯基，Ph表示苯基（以下，相同）。In the present embodiment, the electron-withdrawing group indicates a group whose Hammett substituent constant σm is a positive value. σm is described in detail in Yufu Mitsuno's Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965), p. 631-642. In addition, the electron-withdrawing group in the present embodiment is not limited to the substituents described in the above literature. Examples of substituents in which σm represents a positive value include CF 3 group (σm=0.43), CF 3 C (=O) group (σm=0.63), HC≡C group (σm=0.21), CH 2 =CH group (σm=0.06), Ac group (σm=0.38), MeOC (=O) group (σm=0.37), MeC (=O) CH=CH group (σm=0.21), PhC (=O) group (σm=0.34), H 2 NC (=O) CH 2 group (σm=0.06), etc. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same).

EWG為下述式（EWG-1）～（EWG-6）所表示之基團為較佳。 [化學式36] 式（EWG-1）～（EWG-6）中，Rx1 ～Rx3 分別獨立地表示氫原子、烷基、烯基、芳基、羥基或羧基，Ar表示芳香族基。EWG is preferably a group represented by the following formula (EWG-1) to (EWG-6). [Chemical Formula 36] In formulae (EWG-1) to (EWG-6), R x1 to R x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.

在本發明中，羧酸根陰離子由下述式（XA）表示為較佳。 [化學式37] 在式（XA）中，L10 表示單鍵或選自包括伸烷基、伸烯基、芳香族基、-NRX -及該等組合之群組中的2價連接基，RX 表示氫原子、烷基、烯基或芳基。In the present invention, the carboxylate anion is preferably represented by the following formula (XA). [Chemical Formula 37] In formula (XA), L 10 represents a single bond or a divalent linking group selected from the group consisting of an alkylene group, an alkenylene group, an aromatic group, -NR X -, and combinations thereof, and RX represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

作為羧酸根陰離子的具體例，可以舉出順丁烯二酸根陰離子、鄰苯二甲酸根陰離子、N-苯基亞胺基二乙酸根陰離子及草酸根陰離子。Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetate anion, and an oxalate anion.

從特定樹脂容易在低溫下進行環化且容易提高硬化性樹脂組成物的保存穩定性的觀點考慮，本發明中之鎓鹽包含銨陽離子作為陽離子，上述鎓鹽包含共軛酸的pKa（pKaH）為2.5以下之陰離子作為陰離子為較佳，包含1.8以下的陰離子為更佳。 上述pKa的下限並無特別限定，從所產生之鹼不易中和且改善特定樹脂等的環化效率之觀點考慮，-3以上為較佳，-2以上為更佳。 作為上述pKa，能夠參閱Determination of Organic Structures by Physical Methods（著者：Brown,H.C.,McDaniel,D.H.,Hafliger,O.,Nachod,F.C.；編著：Braude,E.A.,Nachod,F.C.；Academic Press,New York,1955）或Data for Biochemical Research（著者：Dawson,R.M.C.et al；Oxford,Clarendon Press,1959）中所記載的值。關於未記載於該等文獻中的化合物，採用利用ACD/pKa（ACD/Labs製）的軟體並藉由結構式計算之值。From the viewpoint that the specific resin is easy to be cyclized at low temperature and the storage stability of the curable resin composition is easy to be improved, the onium salt in the present invention contains ammonium cations as cations, and the onium salt contains anions with a pKa (pKaH) of the conjugated acid of 2.5 or less as anions, and more preferably contains anions of 1.8 or less. The lower limit of the above pKa is not particularly limited, and from the viewpoint that the generated base is not easy to neutralize and the cyclization efficiency of the specific resin is improved, -3 or more is preferred, and -2 or more is more preferred. As the pKa, the values described in Determination of Organic Structures by Physical Methods (author: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; editor: Braude, E.A., Nachod, F.C.; Academic Press, New York, 1955) or Data for Biochemical Research (author: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959) can be referred to. For compounds not described in these documents, values calculated from the structural formula using ACD/pKa (manufactured by ACD/Labs) software were used.

作為銨鹽的具體例，可以舉出以下化合物，但是本發明並不限定於此。 [化學式38] As specific examples of ammonium salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 38]

[亞胺鹽] 在本發明中，亞胺鹽表示亞胺陽離子與陰離子的鹽。作為陰離子，可以例示與上述銨鹽中之陰離子相同者，較佳態樣亦相同。[Imine salt] In the present invention, the imine salt refers to a salt of an imine cation and an anion. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and the preferred embodiment is also the same.

-亞胺陽離子- 作為亞胺陽離子，吡啶鎓陽離子為較佳。 又，作為亞胺陽離子，下述式（102）所表示之陽離子亦較佳。 [化學式39] -Imine cation- As the imine cation, pyridinium cation is preferred. Also, as the imine cation, the cation represented by the following formula (102) is also preferred. [Chemical Formula 39]

式（102）中，R5 及R6 分別獨立地表示氫原子或烴基，R7 表示烴基，R5 ～R7 中的至少兩個可以分別鍵結而形成環。 式（102）中，R5 及R6 與上述式（101）中之R1 ～R4 的含義相同，較佳態樣亦相同。 式（102）中，R7 與R5 及R6 中的至少一個鍵結而形成環為較佳。上述環亦可以包含雜原子。作為上述雜原子，可以舉出氮原子。又，作為上述環，吡啶環為較佳。In formula (102), R5 and R6 each independently represent a hydrogen atom or a alkyl group, R7 represents a alkyl group, and at least two of R5 to R7 may be bonded to form a ring. In formula (102), R5 and R6 have the same meanings as R1 to R4 in formula (101), and preferred embodiments are also the same. In formula (102), it is preferred that R7 is bonded to at least one of R5 and R6 to form a ring. The above ring may also contain a heteroatom. As the above heteroatom, a nitrogen atom may be cited. In addition, as the above ring, a pyridine ring is preferred.

亞胺陽離子由下述式（Y1-3）～（Y1-5）中的任一個表示為較佳。 [化學式40] 在式（Y1-3）～（Y1-5）中，R101 表示n價有機基，R5 與式（102）中之R5 的含義相同，R7 與式（102）中之R7 的含義相同，n表示1以上的整數，m表示0以上的整數。 在式（Y1-3）中，R101 為從脂肪族烴、芳香族烴或該等鍵結而形成之結構去除n個氫原子而獲得之基團為較佳，從碳數2～30的飽和脂肪族烴、苯或萘去除n個氫原子而獲得之基團為更佳。 在式（Y1-3）中，n為1～4為較佳，1或2為更佳，1為進一步較佳。 在式（Y1-5）中，m為0～4為較佳，1或2為更佳，1為進一步較佳。The imide cation is preferably represented by any one of the following formulas (Y1-3) to (Y1-5). [Chemical Formula 40] In formula (Y1-3) to (Y1-5), R101 represents an n-valent organic group, R5 has the same meaning as R5 in formula (102), R7 has the same meaning as R7 in formula (102), n represents an integer greater than 1, and m represents an integer greater than 0. In formula (Y1-3), R101 is preferably a group obtained by removing n hydrogen atoms from an aliphatic hydrocarbon, an aromatic hydrocarbon, or a structure formed by such a bond, and more preferably a group obtained by removing n hydrogen atoms from a saturated aliphatic hydrocarbon having 2 to 30 carbon atoms, benzene, or naphthalene. In formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1. In formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.

作為亞胺鹽的具體例，可以舉出以下化合物，但是本發明並不限定於此。 [化學式41] As specific examples of imine salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 41]

[鋶鹽] 在本發明中，鋶鹽表示鋶陽離子與陰離子的鹽。作為陰離子，可以例示與上述銨鹽中之陰離子相同者，較佳態樣亦相同。[Sirconium salt] In the present invention, the term "sirconium salt" refers to a salt of a cation and an anion of a iron. Examples of the anion include the same anions as those in the above-mentioned ammonium salt, and the preferred embodiment is also the same.

-鋶陽離子- 作為鋶陽離子，三級鋶陽離子為較佳，三芳基鋶陽離子為更佳。 又，作為鋶陽離子，下述式（103）所表示之陽離子為較佳。 [化學式42] - Copper cation - As the copper cation, a tertiary copper cation is preferred, and a triaryl copper cation is more preferred. In addition, as the copper cation, a cation represented by the following formula (103) is preferred. [Chemical Formula 42]

式（103）中，R8 ～R10 分別獨立地表示烴基。 R8 ～R10 分別獨立地為烷基或芳基為較佳，碳數1～10的烷基或碳數6～12的芳基為更佳，碳數6～12的芳基為進一步較佳，苯基為進一步較佳。 R8 ～R10 可以具有取代基，作為取代基的例子，可以舉出羥基、芳基、烷氧基、芳氧基、芳基羰基、烷基羰基、烷氧基羰基、芳氧基羰基、醯氧基等。其中，作為取代基，具有烷基或烷氧基為較佳，具有支鏈烷基或烷氧基為更佳，具有碳數3～10的支鏈烷基或碳數1～10的烷氧基為進一步較佳。 R8 ～R10 可以為相同的基團，亦可以為不同之基團，但是從合成適性的觀點考慮，相同的基團為較佳。In formula (103), R 8 to R 10 each independently represents a alkyl group. R 8 to R 10 each independently represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R 8 to R 10 may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among them, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R 8 to R 10 may be the same group or different groups, but from the viewpoint of synthetic suitability, it is preferred that they are the same group.

[錪鹽] 在本發明中，錪鹽表示錪陽離子與陰離子的鹽。作為陰離子，可以例示與上述銨鹽中之陰離子相同者，較佳態樣亦相同。[Iodine salt] In the present invention, an iodine salt refers to a salt of an iodine cation and an anion. Examples of anions include the same anions as those in the above-mentioned ammonium salts, and the preferred embodiments are also the same.

-錪陽離子- 作為錪陽離子，二芳基錪陽離子為較佳。 又，作為錪陽離子，下述式（104）所表示之陽離子為較佳。 [化學式43] -Ion cation- As the iodine cation, a diaryl iodine cation is preferred. Also, as the iodine cation, a cation represented by the following formula (104) is preferred. [Chemical Formula 43]

式（104）中，R11 及R12 分別獨立地表示烴基。 R11 及R12 分別獨立地為烷基或芳基為較佳，碳數1～10的烷基或碳數6～12的芳基為更佳，碳數6～12的芳基為進一步較佳，苯基為進一步較佳。 R11 及R12 可以具有取代基，作為取代基的例子，可以舉出羥基、芳基、烷氧基、芳氧基、芳基羰基、烷基羰基、烷氧基羰基、芳氧基羰基、醯氧基等。其中，作為取代基，具有烷基或烷氧基為較佳，具有支鏈烷基或烷氧基為更佳，具有碳數3～10的支鏈烷基或碳數1～10的烷氧基為進一步較佳。 R11 及R12 可以為相同的基團，亦可以為不同之基團，但是從合成適性的觀點考慮，相同的基團為較佳。In formula (104), R 11 and R 12 each independently represent a alkyl group. R 11 and R 12 each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among them, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R 11 and R 12 may be the same group or different groups, but from the viewpoint of synthetic suitability, it is preferred that they are the same group.

[鏻鹽] 在本發明中，鏻鹽表示鏻陽離子與陰離子的鹽。作為陰離子，可以例示與上述銨鹽中之陰離子相同者，較佳態樣亦相同。[Phosphonium salt] In the present invention, phosphonium salt means a salt of a phosphonium cation and an anion. Examples of anions include the same anions as those in the above-mentioned ammonium salts, and the preferred embodiments are also the same.

-鏻陽離子- 作為鏻陽離子，四級鏻陽離子為較佳，可以舉出四烷基鏻陽離子、三芳基單烷基鏻陽離子等。 又，作為鏻陽離子，下述式（105）所表示之陽離子為較佳。 [化學式44] -Phosphonium cation- As the phosphonium cation, a quaternary phosphonium cation is preferred, and examples thereof include tetraalkylphosphonium cations and triarylmonoalkylphosphonium cations. Furthermore, as the phosphonium cation, a cation represented by the following formula (105) is preferred. [Chemical formula 44]

式（105）中，R13 ～R16 分別獨立地表示氫原子或烴基。 R13 ～R16 分別獨立地為烷基或芳基為較佳，碳數1～10的烷基或碳數6～12的芳基為更佳，碳數6～12的芳基為進一步較佳，苯基為進一步較佳。 R13 ～R16 可以具有取代基，作為取代基的例子，可以舉出羥基、芳基、烷氧基、芳氧基、芳基羰基、烷基羰基、烷氧基羰基、芳氧基羰基、醯氧基等。其中，作為取代基，具有烷基或烷氧基為較佳，具有支鏈烷基或烷氧基為更佳，具有碳數3～10的支鏈烷基或碳數1～10的烷氧基為進一步較佳。 R13 ～R16 可以為相同的基團，亦可以為不同之基團，但是從合成適性的觀點考慮，相同的基團為較佳。In formula (105), R 13 to R 16 each independently represent a hydrogen atom or a alkyl group. R 13 to R 16 each independently represent an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. R 13 to R 16 may have a substituent, and examples of the substituent include a hydroxyl group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among them, as a substituent, an alkyl group or an alkoxy group is preferred, a branched alkyl group or an alkoxy group is more preferred, and a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms is further preferred. R 13 to R 16 may be the same group or different groups, but from the viewpoint of synthetic suitability, the same group is preferred.

在本發明的硬化性樹脂組成物包含鎓鹽之情況下，鎓鹽的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1～50質量%為較佳。下限為0.5質量%以上為更佳，0.85質量%以上為進一步較佳，1質量%以上為更進一步較佳。上限為30質量%以下為更佳，20質量%以下為進一步較佳，10質量%以下為更進一步較佳，可以為5質量%以下，亦可以為4質量%以下。 鎓鹽能夠使用一種或兩種以上。在使用兩種以上之情況下，合計量在上述範圍內為較佳。When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50 mass % relative to the total solid content of the curable resin composition of the present invention. The lower limit is preferably 0.5 mass % or more, 0.85 mass % or more is further preferred, and 1 mass % or more is further preferred. The upper limit is preferably 30 mass % or less, 20 mass % or less is further preferred, 10 mass % or less is further preferred, and can be 5 mass % or less, or 4 mass % or less. One or more onium salts can be used. When two or more are used, the total amount is preferably within the above range.

＜熱鹼產生劑＞ 本發明的硬化性樹脂組成物可以包含熱鹼產生劑。 尤其，在硬化性樹脂組成物包括包含式（2-1）所表示之重複單元或式（2-4）所表示之重複單元之樹脂作為特定樹脂之情況下，硬化性樹脂組成物包含熱鹼產生劑為較佳。 熱鹼產生劑可以為與上述鎓鹽對應之化合物，亦可以為除了上述鎓鹽以外的其他熱鹼產生劑。 作為其他熱鹼產生劑，可以舉出非離子系熱鹼產生劑。 作為非離子系熱鹼產生劑，可以舉出式（B1）或式（B2）所表示之化合物。 [化學式45] <Thermoalkali generator> The curable resin composition of the present invention may contain a thermoalkali generator. In particular, when the curable resin composition includes a resin containing a repeating unit represented by formula (2-1) or a repeating unit represented by formula (2-4) as a specific resin, it is preferred that the curable resin composition contains a thermoalkali generator. The thermoalkali generator may be a compound corresponding to the above-mentioned onium salt, or may be another thermoalkali generator other than the above-mentioned onium salt. As another thermoalkali generator, a non-ionic thermoalkali generator may be mentioned. As a non-ionic thermoalkali generator, a compound represented by formula (B1) or formula (B2) may be mentioned. [Chemical formula 45]

式（B1）及式（B2）中，Rb1 、Rb2 及Rb3 分別獨立地為不具有三級胺結構的有機基、鹵素原子或氫原子。其中，Rb1 及Rb2 不會同時成為氫原子。又，Rb1 、Rb2 及Rb3 均不具有羧基。另外，在本說明書中，三級胺結構是指3價氮原子的三個鍵結鍵均與烴系碳原子進行共價鍵結之結構。因此，在所鍵結之碳原子為形成羰基之碳原子之情況亦即在與氮原子一同形成醯胺基之情況下，並不限於此。In formula (B1) and formula (B2), Rb1 , Rb2 and Rb3 are independently an organic group, a halogen atom or a hydrogen atom that does not have a tertiary amine structure. However, Rb1 and Rb2 will not be hydrogen atoms at the same time. Moreover, Rb1 , Rb2 and Rb3 do not have a carboxyl group. In the present specification, a tertiary amine structure refers to a structure in which the three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon carbon atom. Therefore, when the carbon atom to which the bond is formed is a carbon atom that forms a carbonyl group, that is, when an amide group is formed together with a nitrogen atom, it is not limited to this.

式（B1）、式（B2）中，Rb1 、Rb2 及Rb3 中的至少一個包含環狀結構為較佳，至少兩個包含環狀結構為更佳。作為環狀結構，可以為單環及縮合環中的任一個，單環或兩個單環縮合而成之縮合環為較佳。單環為5員環或6員環為較佳，6員環為較佳。單環為環己烷環及苯環為較佳，環己烷環為更佳。In formula (B1) and formula (B2), at least one of Rb1 , Rb2 and Rb3 preferably has a cyclic structure, and at least two of them more preferably have a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferred. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is preferred. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and a cyclohexane ring is more preferred.

更具體而言，Rb1 及Rb2 為氫原子、烷基（碳數1～24為較佳，2～18為更佳，3～12為進一步較佳）、烯基（碳數2～24為較佳，2～18為更佳，3～12為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）或芳烷基（碳數7～25為較佳，7～19為更佳，7～12為進一步較佳）為較佳。該等基團可以在發揮本發明的效果之範圍內具有取代基。Rb1 與Rb2 可以相互鍵結而形成環。作為所形成之環，4～7員的含氮雜環為較佳。尤其，Rb1 及Rb2 為可以具有取代基之直鏈、支鏈或環狀的烷基（碳數1～24為較佳，2～18為更佳，3～12為進一步較佳）為較佳，可以具有取代基之環烷基（碳數3～24為較佳，3～18為更佳，3～12為進一步較佳）為更佳，可以具有取代基之環己基為進一步較佳。More specifically, Rb1 and Rb2 are preferably hydrogen atoms, alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), or aralkyl groups (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms). These groups may have substituents within the range in which the effects of the present invention are exerted. Rb1 and Rb2 may be bonded to each other to form a ring. As the ring formed, a 4-7-membered nitrogen-containing heterocyclic ring is preferred. In particular, Rb1 and Rb2 are preferably linear, branched or cyclic alkyl groups which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), more preferably cycloalkyl groups which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), and further preferably cyclohexyl groups which may have a substituent.

作為Rb3 ，可以舉出烷基（碳數1～24為較佳，2～18為更佳，3～12為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、烯基（碳數2～24為較佳，2～12為更佳，2～6為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳）、芳烯基（碳數8～24為較佳，8～20為更佳，8～16為進一步較佳）、烷氧基（碳數1～24為較佳，2～18為更佳，3～12為進一步較佳）、芳氧基（碳數6～22為較佳，6～18為更佳，6～12為進一步較佳）或芳烷氧基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳）。其中，環烷基（碳數3～24為較佳，3～18為更佳，3～12為進一步較佳）、芳烯基、芳烷氧基為較佳。Rb3 在發揮本發明的效果之範圍內還可以具有取代基。Examples of Rb 3 include alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), alkenyl (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), aralkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), Aralkenyl (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), alkoxy (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryloxy (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or aralkyloxy (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). Among them, cycloalkyl (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aralkenyl, and aralkyloxy are preferred. Rb3 may further have a substituent within the range in which the effect of the present invention is exerted.

式（B1）所表示之化合物為下述式（B1-1）或下述式（B1-2）所表示之化合物為較佳。 [化學式46] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical Formula 46]

式中，Rb11 及Rb12 和Rb31 及Rb32 分別與式（B1）中之Rb1 及Rb2 的含義相同。 Rb13 為烷基（碳數1～24為較佳，2～18為更佳，3～12為進一步較佳）、烯基（碳數2～24為較佳，2～18為更佳，3～12為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～12為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳），在發揮本發明的效果之範圍內可以具有取代基。其中，Rb13 為芳烷基為較佳。In the formula, Rb11 and Rb12 and Rb31 and Rb32 have the same meanings as Rb1 and Rb2 in formula (B1), respectively. Rb13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), and may have a substituent within a range in which the effects of the present invention are exerted. Among them, Rb13 is preferably an aralkyl group.

Rb33 及Rb34 分別獨立地為氫原子、烷基（碳數1～12為較佳，1～8為更佳，1～3為進一步較佳）、烯基（碳數2～12為較佳，2～8為更佳，2～3為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳），氫原子為較佳。 Rb33 and Rb34 are independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), preferably a hydrogen atom.

Rb35 為烷基（碳數1～24為較佳，1～12為更佳，3～8為進一步較佳）、烯基（碳數2～12為較佳，2～10為更佳，3～8為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～12為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳），芳基為較佳。Rb 35 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), and an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), and an aryl group is preferred.

又，式（B1-1）所表示之化合物為式（B1-1a）所表示之化合物亦較佳。 [化學式47] Furthermore, the compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a). [Chemical Formula 47]

Rb11 及Rb12 與式（B1-1）中之Rb11 及Rb12 的含義相同。 Rb15 及Rb16 為氫原子、烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、烯基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳），氫原子或甲基為較佳。 Rb17 為烷基（碳數1～24為較佳，1～12為更佳，3～8為進一步較佳）、烯基（碳數2～12為較佳，2～10為更佳，3～8為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～12為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳），其中，芳基為較佳。 Rb11 and Rb12 have the same meanings as Rb11 and Rb12 in formula (B1-1). Rb15 and Rb16 are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), preferably hydrogen atoms or methyl groups. Rb 17 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), wherein the aryl group is preferred.

非離子系熱鹼產生劑的分子量為800以下為較佳，600以下為更佳，500以下為進一步較佳。作為下限，100以上為較佳，200以上為更佳，300以上為進一步較佳。The molecular weight of the non-ionic thermal alkali generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. As the lower limit, it is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

在上述鎓鹽中，關於作為熱鹼產生劑的化合物的具體例或其他熱鹼產生劑的具體例，可以舉出以下化合物。 [化學式48] [化學式49] Among the above-mentioned onium salts, the following compounds can be cited as specific examples of compounds serving as thermal alkali generators or other specific examples of thermal alkali generators. [Chemical Formula 48] [Chemical formula 49]

[化學式50] [Chemical formula 50]

熱鹼產生劑的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1～50質量%為較佳。下限為0.5質量%以上為更佳，1質量%以上為進一步較佳。上限為30質量%以下為更佳，20質量%以下為進一步較佳。熱鹼產生劑能夠使用一種或兩種以上。在使用兩種以上之情況下，合計量在上述範圍內為較佳。The content of the alkali generator is preferably 0.1 to 50% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. The alkali generator can be used alone or in combination. When two or more types are used, the total amount is preferably within the above range.

＜具有磺醯胺結構之化合物、具有硫脲結構之化合物＞ 從提高所獲得之圖案（硬化膜）對基材的密接性之觀點考慮，本發明的感光性樹脂組成物還包含選自包括具有磺醯胺結構之化合物及具有硫脲結構之化合物之群組中的至少一種化合物為較佳。 尤其，在硬化性樹脂組成物包括包含選自包括式（2-2）所表示之重複單元及式（2-3）所表示之重複單元之群組中的至少一者重複單元之特定樹脂作為特定樹脂之情況下，還包含選自包括具有磺醯胺結構之化合物及具有硫脲結構之化合物之群組中的至少一種化合物為較佳。<Compounds having a sulfonamide structure, compounds having a thiourea structure> From the viewpoint of improving the adhesion of the obtained pattern (cured film) to the substrate, the photosensitive resin composition of the present invention preferably further comprises at least one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure. In particular, when the curable resin composition comprises a specific resin comprising at least one repeating unit selected from the group consisting of repeating units represented by formula (2-2) and repeating units represented by formula (2-3) as the specific resin, it is preferred that the photosensitive resin composition further comprises at least one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure.

[具有磺醯胺結構之化合物] 磺醯胺結構為下述式（S-1）所表示之結構。 [化學式51] 式（S-1）中，R表示氫原子或有機基，R可以與其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。 上述R為與下述式（S-2）中之R2 相同的基團為較佳。 具有磺醯胺結構之化合物可以為具有兩個以上的磺醯胺結構之化合物，但是具有一個磺醯胺結構之化合物為較佳。[Compounds having a sulfonamide structure] The sulfonamide structure is represented by the following formula (S-1). [Chemical formula 51] In formula (S-1), R represents a hydrogen atom or an organic group, and R may form a ring structure by bonding with other structures, and * independently represents the bonding site with other structures. It is preferred that the above R is the same group as R2 in the following formula (S-2). The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but a compound having one sulfonamide structure is preferred.

具有磺醯胺結構之化合物為下述式（S-2）所表示之化合物為較佳。 [化學式52] 式（S-2）中，R1 、R2 及R3 分別獨立地表示氫原子或1價有機基，R1 、R2 及R3 中的兩個以上可以相互鍵結而形成環結構。 R1 、R2 及R3 分別獨立地為1價有機基為較佳。 作為R1 、R2 及R3 的例子，可以舉出氫原子或烷基、環烷基、烷氧基、烷基醚基、烷基甲矽烷基、烷氧基甲矽烷基、芳基、芳基醚基、羧基、羰基、烯丙基、乙烯基、雜環基或該等組合兩個以上而獲得之基團等。 作為上述烷基，碳數1～10的烷基為較佳，碳數1～6的烷基為更佳。作為上述烷基，例如可以舉出甲基、乙基、丙基、丁基、戊基、己基、異丙基、2-乙基己基等。 作為上述環烷基，碳數5～10的環烷基為較佳，碳數6～10的環烷基為更佳。作為上述環烷基，例如可以舉出環丙基、環丁基、環戊基及環己基等。 作為上述烷氧基，碳數1～10的烷氧基為較佳，碳數1～5的烷氧基為更佳。作為上述烷氧基，可以舉出甲氧基、乙氧基、丙氧基、丁氧基及戊氧基等。 作為上述烷氧基甲矽烷基，碳數1～10的烷氧基甲矽烷基為較佳，碳數1～4的烷氧基甲矽烷基為更佳。作為上述烷氧基甲矽烷基，可以舉出甲氧基甲矽烷基、乙氧基甲矽烷基、丙氧基甲矽烷基及丁氧基甲矽烷基等。 作為上述芳基，碳數6～20的芳基為較佳，碳數6～12的芳基為更佳。上述芳基可以具有烷基等取代基。作為上述芳基，可以舉出苯基、甲苯基、二甲苯基及萘基等。 作為上述雜環基，可以舉出從三唑環、吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡唑環、異㗁唑環、異噻唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、嗎啉環、二氫哌喃環、四氫吡喃基、三𠯤環等雜環結構去除一個氫原子而獲得之基團等。The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical Formula 52] In formula (S-2), R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group, and two or more of R 1 , R 2 and R 3 may be bonded to each other to form a ring structure. It is preferred that R 1 , R 2 and R 3 each independently represent a monovalent organic group. Examples of R 1 , R 2 and R 3 include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group obtained by combining two or more of these groups. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl. Examples of the cycloalkyl group include cycloalkyl groups having 5 to 10 carbon atoms, and cycloalkyl groups having 6 to 10 carbon atoms are more preferred. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are more preferred. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Examples of the alkoxysilyl group include alkoxysilyl groups having 1 to 10 carbon atoms, and alkoxysilyl groups having 1 to 4 carbon atoms are more preferred. Examples of the alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of the aryl group include 6 to 20 carbon atoms, and 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include groups obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxadiazole ring, a thiazole ring, a pyrazole ring, an isoxadiazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a piperidine ring, a piperidine ring, a morpholine ring, a dihydropyranyl ring, a tetrahydropyranyl ring, and a trihydropyranyl ring.

其中，R1 為芳基且R2 及R3 分別獨立地為氫原子或烷基之化合物為較佳。Among them, the compound in which R 1 is an aryl group and R 2 and R 3 are independently a hydrogen atom or an alkyl group is preferred.

作為具有磺醯胺結構之化合物的例子，可以舉出苯磺醯胺、二甲基苯磺醯胺、N-丁基苯磺醯胺、磺胺、鄰甲苯磺醯胺、對甲苯磺醯胺、羥基萘磺醯胺、萘-1-磺醯胺、萘-2-磺醯胺、間硝基苯磺醯胺、對氯苯磺醯胺、甲磺醯胺、N,N-二甲基甲磺醯胺、N,N-二甲基乙磺醯胺、N,N-二乙基甲磺醯胺、N-甲氧基甲磺醯胺、N-十二基甲磺醯胺、N-環己基-1-丁烷磺醯胺、2-胺基乙磺醯胺等。Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1-sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethylsulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

[具有硫脲結構之化合物] 硫脲結構為下述式（T-1）所表示之結構。 [化學式53] 式（T-1）中，R4 及R5 分別獨立地表示氫原子或1價有機基，R4 及R5 可以鍵結而形成環結構，R4 可以與*所鍵結之其他結構鍵結而形成環結構，R5 可以與*所鍵結之其他結構鍵結而形成環結構，*分別獨立地表示與其他結構的鍵結部位。[Compounds having a thiourea structure] The thiourea structure is represented by the following formula (T-1). [Chemical formula 53] In formula (T-1), R4 and R5 each independently represent a hydrogen atom or a monovalent organic group, R4 and R5 may be bonded to form a ring structure, R4 may be bonded to another structure to which * is bonded to form a ring structure, R5 may be bonded to another structure to which * is bonded to form a ring structure, and * each independently represents a bonding site to another structure.

R4 及R5 分別獨立地為氫原子為較佳。 作為R4 及R5 的例子，可以舉出氫原子或烷基、環烷基、烷氧基、烷基醚基、烷基甲矽烷基、烷氧基甲矽烷基、芳基、芳基醚基、羧基、羰基、烯丙基、乙烯基、雜環基或該等組合兩個以上而獲得之基團等。 作為上述烷基，碳數1～10的烷基為較佳，碳數1～6的烷基為更佳。作為上述烷基，例如可以舉出甲基、乙基、丙基、丁基、戊基、己基、異丙基、2-乙基己基等。 作為上述環烷基，碳數5～10的環烷基為較佳，碳數6～10的環烷基為更佳。作為上述環烷基，例如可以舉出環丙基、環丁基、環戊基及環己基等。 作為上述烷氧基，碳數1～10的烷氧基為較佳，碳數1～5的烷氧基為更佳。作為上述烷氧基，可以舉出甲氧基、乙氧基、丙氧基、丁氧基及戊氧基等。 作為上述烷氧基甲矽烷基，碳數1～10的烷氧基甲矽烷基為較佳，碳數1～4的烷氧基甲矽烷基為更佳。作為上述烷氧基甲矽烷基，可以舉出甲氧基甲矽烷基、乙氧基甲矽烷基、丙氧基甲矽烷基及丁氧基甲矽烷基等。 作為上述芳基，碳數6～20的芳基為較佳，碳數6～12的芳基為更佳。上述芳基可以具有烷基等取代基。作為上述芳基，可以舉出苯基、甲苯基、二甲苯基及萘基等。 作為上述雜環基，可以舉出從三唑環、吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡唑環、異㗁唑環、異噻唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、嗎啉環、二氫哌喃環、四氫吡喃基、三𠯤環等雜環結構去除一個氫原子而獲得之基團等。 具有硫脲結構之化合物可以為具有兩個以上的硫脲結構之化合物，但是具有一個硫脲結構之化合物為較佳。 R4 and R5 are preferably independently a hydrogen atom. Examples of R4 and R5 include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group obtained by combining two or more of these groups. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. As the above-mentioned alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group, etc. are cited. As the above-mentioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are more preferred. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Examples of the alkoxysilyl group include alkoxysilyl groups having 1 to 10 carbon atoms, and alkoxysilyl groups having 1 to 4 carbon atoms are more preferred. Examples of the alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, and aryl groups having 6 to 12 carbon atoms are more preferred. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include groups obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, a thiazole ring, a pyrazole ring, an iso-pyrazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyrimidine ring, a piperidine ring, a piperidine ring, a morpholine ring, a dihydropyranyl ring, a tetrahydropyranyl, and a trihydropyranyl ring. The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferred.

具有硫脲結構之化合物為下述式（T-2）所表示之化合物為較佳。 [化學式54] 式（T-2）中，R4 ～R7 分別獨立地表示氫原子或1價有機基，R4 ～R7 中的至少兩個可以相互鍵結而形成環結構。The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical Formula 54] In formula (T-2), R 4 to R 7 each independently represent a hydrogen atom or a monovalent organic group, and at least two of R 4 to R 7 may be bonded to each other to form a ring structure.

式（T-2）中，R4 及R5 與式（T-1）中的R4 及R5 的含義相同，較佳態樣亦相同。 式（T-2）中，R6 及R7 分別獨立地為1價有機基為較佳。 式（T-2）中，R6 及R7 中之1價有機基的較佳態樣與式（T-1）中的R4 及R5 中之1價有機基的較佳態樣相同。In formula (T-2), R4 and R5 have the same meanings as R4 and R5 in formula (T-1), and the preferred embodiments are also the same. In formula (T-2), R6 and R7 are each independently a monovalent organic group, which is preferred. In formula (T-2), the preferred monovalent organic group of R6 and R7 is the same as the preferred monovalent organic group of R4 and R5 in formula (T-1).

作為具有硫脲結構之化合物的例子，可以舉出N-乙醯基硫脲、N-烯丙基硫脲、N-烯丙基-N’-（2-羥基乙基）硫脲、1-金剛烷基硫脲、N-苯甲醯基硫脲、N,N’-二苯基硫脲、1-苄基-苯基硫脲、1,3-二丁基硫脲、1,3-二異丙基硫脲、1,3-二環己基硫脲、1-（3-（三甲氧基甲矽烷基）丙基）-3-甲基硫脲、三甲基硫脲、四甲基硫脲、N,N-二苯基硫脲、乙烯硫脲（2-咪唑啉硫酮）、卡比嗎唑（Carbimazole）、1,3-二甲基-2-硫乙內醯脲等。Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantylthiourea, N-benzoylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylenethiourea (2-imidazolinethione), carbimazole, and 1,3-dimethyl-2-thiohydantoin.

具有磺醯胺結構之化合物及具有硫脲結構之化合物的合計含量相對於本發明的感光性樹脂組成物的總質量為0.05～10質量%為較佳，0.1～5質量%為更佳，0.2～3質量%為進一步較佳。 本發明的感光性樹脂組成物可以僅包含一種選自包括具有磺醯胺結構之化合物及具有硫脲結構之化合物之群組中的化合物，亦可以包含兩種以上。在僅包含一種之情況下，該化合物的含量在上述範圍內，並且在包含兩種以上之情況下，其合計量在上述範圍內為較佳。The total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10 mass %, more preferably 0.1 to 5 mass %, and further preferably 0.2 to 3 mass % relative to the total mass of the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention may contain only one compound selected from the group including compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more. When only one compound is contained, the content of the compound is within the above range, and when two or more compounds are contained, the total amount is preferably within the above range.

＜遷移抑制劑＞ 本發明的硬化性樹脂組成物還包含遷移抑制劑為較佳。藉由包含遷移抑制劑，能夠有效地抑制源自金屬層（金屬配線）的金屬離子轉移至硬化性樹脂組成物層內。<Migration inhibitor> The curable resin composition of the present invention preferably further comprises a migration inhibitor. By comprising the migration inhibitor, it is possible to effectively inhibit the migration of metal ions originating from the metal layer (metal wiring) into the curable resin composition layer.

作為遷移抑制劑，並無特別限制，可以舉出具有雜環（吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡唑環、異㗁唑環、異噻唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、嗎啉環、2H-吡喃環及6H-吡喃環、三𠯤環）之化合物、具有硫脲類及氫硫基之化合物、受阻酚系化合物、水楊酸衍生物系化合物、醯肼衍生物系化合物。尤其，能夠較佳地使用1,2,4-三唑、苯并三唑、5-甲基苯并三唑、4-甲基苯并三唑等三唑系化合物、1H-四唑、5-苯基四唑等四唑系化合物。The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxadiazole ring, thiazole ring, pyrazole ring, isoxadiazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazole ring), compounds having thiourea and thiohydrin, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, and 4-methylbenzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

或者，亦能夠使用捕捉鹵素離子等陰離子之離子捕捉劑。Alternatively, an ion scavenger that captures anions such as halogen ions may be used.

作為其他遷移抑制劑，能夠使用日本特開2013-015701號公報的0094段中所記載的防鏽劑、日本特開2009-283711號公報的0073～0076段中所記載的化合物、日本特開2011-059656號公報的0052段中所記載的化合物、日本特開2012-194520號公報的0114段、0116段及0118段中所記載的化合物、國際公開第2015/199219號的0166段中所記載的化合物等。As other migration inhibitors, the rustproofing agent described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used.

作為遷移抑制劑的具體例，可以舉出下述化合物。As specific examples of the migration inhibitor, the following compounds can be cited.

[化學式55] [Chemical formula 55]

在硬化性樹脂組成物具有遷移抑制劑之情況下，遷移抑制劑的含量相對於硬化性樹脂組成物的總固體成分為0.01～5.0質量%為較佳，0.05～2.0質量%為更佳，0.1～1.0質量%為進一步較佳。When the curable resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass % relative to the total solid content of the curable resin composition.

遷移抑制劑可以為僅一種，亦可以為兩種以上。在遷移抑制劑為兩種以上之情況下，合計量在上述範圍內為較佳。The migration inhibitor may be one or more than one. When there are two or more migration inhibitors, the total amount is preferably within the above range.

＜聚合抑制劑＞ 本發明的硬化性樹脂組成物包含聚合抑制劑為較佳。<Polymerization inhibitor> The curable resin composition of the present invention preferably contains a polymerization inhibitor.

作為聚合抑制劑，例如較佳地使用氫醌、鄰甲氧基酚、對甲氧基酚、二-第三丁基-對甲酚、五倍子酚、對-第三丁基鄰苯二酚、1,4-苯醌、二苯基-對苯醌、4,4’-硫代雙（3-甲基-6-第三丁基酚）、2,2’-亞甲基雙（4-甲基-6-第三丁基酚）、N-亞硝基-N-苯基羥基胺鋁鹽、啡噻𠯤、N-亞硝基二苯胺、N-苯基萘胺、伸乙基二胺四乙酸、1,2-環己二胺四乙酸、乙二醇醚二胺四乙酸、2,6-二-第三丁基-4-甲基酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-（N-乙基-N-磺基丙基胺）酚、N-亞硝基苯基羥基胺第一鈰鹽、N-亞硝基-N-（1-萘基）羥胺銨鹽、雙（4-羥基-3,5-第三丁基）苯基甲烷、1,3,5-三（4-第三丁基-3-羥基）-2,6-二甲基芐基）-1,3,5-三𠯤-2,4,6-（1H，3H，5H）-三酮、4-羥基-2,2,6,6-四甲基哌啶1-氧基自由基、吩噻𠯤、1,1-二苯基-2-吡咯肼、二丁基二硫代碳酸銅（II）、硝基苯、N-亞硝基-N-苯基羥胺鋁鹽、N-亞硝基-N-苯基羥基胺銨鹽等。又，亦能夠使用日本特開2015-127817號公報的0060段中所記載的聚合抑制劑及國際公開第2015/125469號的0031～0046段中所記載的化合物。As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, p-tert-butyl-o-catechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenathiophene, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, etc. are preferably used. Phenol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitrosophenylhydroxylamine first barium salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5 -trioxathione-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinium 1-oxyl radical, phenothiazine, 1,1-diphenyl-2-pyrrolohydrazide, dibutylcopper(II)dithiocarbonate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

又，能夠使用下述化合物（Me為甲基）。Furthermore, the following compounds (Me is methyl group) can be used.

[化學式56] [Chemical formula 56]

在本發明的硬化性樹脂組成物具有聚合抑制劑之情況下，可以舉出聚合抑制劑的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.01～20.0質量%，0.01～5質量%為較佳，0.02～3質量%為更佳，0.05～2.5質量%為進一步較佳。When the curable resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 20.0 mass %, preferably 0.01 to 5 mass %, more preferably 0.02 to 3 mass %, and even more preferably 0.05 to 2.5 mass % relative to the total solid content of the curable resin composition of the present invention.

聚合抑制劑可以為僅一種，亦可以為兩種以上。在聚合抑制劑為兩種以上之情況下，合計量在上述範圍內為較佳。The polymerization inhibitor may be one or more than one. When there are two or more polymerization inhibitors, the total amount is preferably within the above range.

＜金屬接著性改良劑＞ 本發明的硬化性樹脂組成物包含用於提高與電極或配線等中所使用之金屬材料的接著性之金屬接著性改良劑為較佳。作為金屬接著性改良劑，可以舉出矽烷偶合劑、鋁系接著助劑、鈦系接著助劑、具有磺醯胺結構之化合物及具有硫脲之化合物、磷酸衍生物化合物、β酮酸酯化合物、胺基化合物等。<Metal Adhesion Improver> The curable resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes or wiring. Examples of metal adhesion improvers include silane coupling agents, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds having a sulfonamide structure and compounds having thiourea, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

作為矽烷偶合劑的例子，可以舉出國際公開第2015/199219號的0167段中所記載的化合物、日本特開2014-191002號公報的0062～0073段中所記載的化合物、國際公開第2011/080992號的0063～0071段中所記載的化合物、日本特開2014-191252號公報的0060～0061段中所記載的化合物、日本特開2014-041264號公報的0045～0052段中所記載的化合物、國際公開第2014/097594號的0055段中所記載的化合物。又，如日本特開2011-128358號公報的0050～0058段中所記載，使用不同的兩種以上的矽烷偶合劑亦較佳。又，矽烷偶合劑使用下述化合物亦較佳。以下式中，Et表示乙基。Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014/097594. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. Furthermore, it is also preferable to use the following compounds as silane coupling agents. In the following formula, Et represents an ethyl group.

[化學式57] [Chemical formula 57]

又，作為金屬接著性改良劑，亦能夠使用日本特開2014-186186號公報的0046～0049段中所記載的化合物、日本特開2013-072935號公報的0032～0043段中所記載的硫化物系化合物。作為其他矽烷偶合劑，例如可以舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-（3,4-環氧環己基）乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、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三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、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-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基甲矽烷基-N-（1,3-二甲基-亞丁基）丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、三-（三甲氧基甲矽烷基丙基）異氰脲酸酯、3-脲基丙基三烷氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、3-三甲氧基甲矽烷基丙基琥珀酸酐。該等能夠單獨使用一種或組合使用兩種以上。Furthermore, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used. Examples of other silane coupling agents include vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxyhexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-butylenepropylmethyldimethoxysilane, 3-butylenepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

作為鋁系接著助劑，例如可以舉出鋁三（乙醯乙酸乙酯）鋁、三（乙醯丙酮）鋁、乙醯乙酸乙酯二異丙醇鋁等。Examples of the aluminum-based bonding agent include aluminum tri(ethyl acetylacetate), aluminum tri(acetylacetone), and aluminum diisopropyl acetylacetate.

金屬接著性改良劑的含量相對於特定樹脂100質量份較佳為0.1～30質量份，更佳為0.5～15質量份的範圍，進一步較佳為0.5～5質量份的範圍。藉由設為上述下限值以上，硬化步驟後的硬化膜與金屬層的接著性變得良好，藉由設為上述上限值以下，硬化步驟後的硬化膜的耐熱性、機械特性變得良好。金屬接著性改良劑可以為僅一種，亦可以為兩種以上。在使用兩種以上之情況下，合計量在上述範圍內為較佳。The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the specific resin. By setting it to be above the above lower limit, the adhesion between the cured film and the metal layer after the curing step becomes good, and by setting it to be below the above upper limit, the heat resistance and mechanical properties of the cured film after the curing step become good. The metal adhesion improver may be only one kind or may be two or more kinds. When two or more kinds are used, it is preferred that the total amount is within the above range.

＜其他添加劑＞ 本發明的硬化性樹脂組成物能夠依據需要配合各種添加物，例如N-苯基二乙醇胺等敏化劑、光鹼產生劑、鏈轉移劑、界面活性劑、高級脂肪酸衍生物、無機粒子、硬化劑、硬化觸媒、填充劑、抗氧化劑、紫外線吸收劑、凝聚抑制劑等。在配合該等添加劑之情況下，將合計配合量設為硬化性樹脂組成物的固體成分的3質量%以下為較佳。<Other additives> The curable resin composition of the present invention can be formulated with various additives as needed, such as sensitizers such as N-phenyldiethanolamine, photobase generators, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When such additives are formulated, it is preferred that the total amount is set to less than 3% by weight of the solid content of the curable resin composition.

[敏化劑] 本發明的硬化性樹脂組成物可以具有敏化劑。敏化劑吸收特定的活性放射線而成為電子激勵狀態。成為電子激勵狀態之敏化劑與熱硬化促進劑、熱自由基聚合起始劑、光自由基聚合起始劑等接觸，從而產生電子轉移、能量轉移、發熱等作用。藉此，熱硬化促進劑、熱自由基聚合起始劑、光自由基聚合起始劑引起化學變化而分解，並生成自由基、酸或鹼。 作為敏化劑，可以舉出N-苯基二乙醇胺等敏化劑。 又，作為敏化劑，亦可以使用敏化色素。 關於敏化色素的詳細內容，能夠參閱日本特開2016-027357號公報的0161～0163段的記載，且該內容被編入本說明書中。[Sensitizer] The curable resin composition of the present invention may have a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., thereby generating electron transfer, energy transfer, heat, etc. Thereby, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator cause chemical changes and decompose, and generate free radicals, acids, or bases. As a sensitizer, a sensitizer such as N-phenyldiethanolamine can be cited. In addition, a sensitizing pigment can also be used as a sensitizer. For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, and the contents are incorporated into this specification.

在本發明的硬化性樹脂組成物包含敏化劑之情況下，敏化劑的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.01～20質量%為較佳，0.1～15質量%為更佳，0.5～10質量%為進一步較佳。敏化劑可以單獨使用一種，亦可以同時使用兩種以上。When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass % relative to the total solid content of the curable resin composition of the present invention. The sensitizer may be used alone or in combination of two or more.

[鏈轉移劑] 本發明的硬化性樹脂組成物可以具有鏈轉移劑。關於鏈轉移劑，例如在高分子詞典第三版（高分子學會（The Society of Polymer Science,Japan）編，2005年）683-684頁中被定義。作為鏈轉移劑，例如使用在分子內具有SH、PH、SiH及GeH之化合物群組。該等對低活性自由基供給氫而生成自由基或者在被氧化之後可以藉由去質子來生成自由基。尤其，能夠較佳地使用硫醇化合物。[Chain transfer agent] The curable resin composition of the present invention may have a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As chain transfer agents, for example, a compound group having SH, PH, SiH and GeH in the molecule is used. These compounds generate free radicals by donating hydrogen to low-activity free radicals or can generate free radicals by deprotonation after being oxidized. In particular, thiol compounds can be preferably used.

又，鏈轉移劑亦能夠使用國際公開第2015/199219號的0152～0153段中所記載的化合物。Furthermore, the chain transfer agent may also include compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219.

在本發明的硬化性樹脂組成物具有鏈轉移劑之情況下，鏈轉移劑的含量相對於本發明的硬化性樹脂組成物的總固體成分100質量份為0.01～20質量份為較佳，1～10質量份為更佳，1～5質量份為進一步較佳。鏈轉移劑可以為僅一種，亦可以為兩種以上。在鏈轉移劑為兩種以上之情況下，合計量在上述範圍內為較佳。When the curable resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the curable resin composition of the present invention. The chain transfer agent may be only one kind or two or more kinds. When there are two or more kinds of chain transfer agents, the total amount is preferably within the above range.

[界面活性劑] 從進一步提高塗佈性的觀點考慮，在本發明的硬化性樹脂組成物中可以添加各種界面活性劑。作為界面活性劑，能夠使用氟系界面活性劑、非離子系界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑、聚矽氧系界面活性劑等各種界面活性劑。又，下述界面活性劑亦較佳。下述式中，表示主鏈的重複單元之括號表示各重複單元的含量（莫耳%），表示側鏈的重複單元之括號表示各重複單元的重複數。 [化學式58] 又，界面活性劑亦能夠使用國際公開第2015/199219號的0159～0165段中所記載的化合物。[Surfactant] From the viewpoint of further improving the coating properties, various surfactants can be added to the curable resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, non-ionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. In addition, the following surfactants are also preferred. In the following formula, the parentheses representing the repeating units of the main chain represent the content (molar %) of each repeating unit, and the parentheses representing the repeating units of the side chain represent the number of repetitions of each repeating unit. [Chemical Formula 58] Furthermore, the compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used as the surfactant.

作為氟系界面活性劑，例如可以舉出MEGAFACE F171、MEGAFACE F172、MEGAFACE F173、MEGAFACE F176、MEGAFACE F177、MEGAFACE F141、MEGAFACE F142、MEGAFACE F143、MEGAFACE F144、MEGAFACE R30、MEGAFACE F437、MEGAFACE F475、MEGAFACE F479、MEGAFACE F482、MEGAFACE F554、MEGAFACE F780、RS-72-K（以上為DIC CORPORATION製）、Fluorad FC430、Fluorad FC431、Fluorad FC171、Novell FC4430、Novell FC4432（以上為3M Japan Limited製）、Surflon S-382、Surflon SC-101、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC1068、Surflon SC-381、Surflon SC-383、Surflon S393、Surflon KH-40（以上為ASAHI GLASS CO.,LTD.製）、PF636、PF656、PF6320、PF6520、PF7002（OMNOVA Solutions Inc.製）等。氟系界面活性劑亦能夠使用日本特開2015-117327號公報的0015～0158段中所記載的化合物、日本特開2011-132503號公報的0117～0132段中所記載的化合物。亦能夠使用嵌段聚合物作為氟系界面活性劑，作為具體例，例如可以舉出日本特開2011-089090號公報中所記載之化合物。 氟系界面活性劑亦能夠較佳地使用含氟高分子化合物，該含氟高分子化合物包含來自具有氟原子之（甲基）丙烯酸酯化合物之重複單元和來自具有2個以上（較佳為5個以上）伸烷氧基（較佳為乙烯氧基、丙烯氧基）之（甲基）丙烯酸酯化合物之重複單元。 氟系界面活性劑亦能夠將在側鏈上具有乙烯性不飽和基之含氟聚合物用作氟系界面活性劑。作為具體例，可以舉出日本特開2010-164965號公報的0050～0090段及0289～0295段中所記載之化合物、例如DIC CORPORATION製的MEGAFACE RS-101、RS-102、RS-718K等。Examples of the fluorine-based surfactant include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. The fluorine-based surfactant may also include compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503. Block polymers can also be used as fluorine-based surfactants. As specific examples, compounds described in Japanese Patent Publication No. 2011-089090 can be cited. Fluorine-based surfactants can also preferably use fluorine-containing polymer compounds, which contain repeating units from (meth)acrylate compounds having fluorine atoms and repeating units from (meth)acrylate compounds having 2 or more (preferably 5 or more) alkoxy groups (preferably ethyleneoxy and propyleneoxy groups). Fluorine-based surfactants can also use fluorine-containing polymers having ethylenically unsaturated groups on the side chains as fluorine-based surfactants. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC CORPORATION.

氟系界面活性劑中的氟含有率為3～40質量%為較佳，更佳為5～30質量%，特佳為7～25質量%。在塗佈膜的厚度的均勻性或省液性的方面而言，氟含有率在該範圍內的氟系界面活性劑為有效，在組成物中之溶解性亦良好。The fluorine content in the fluorine-based surfactant is preferably 3 to 40 mass %, more preferably 5 to 30 mass %, and particularly preferably 7 to 25 mass %. In terms of uniformity of the thickness of the coating film or liquid saving, the fluorine-based surfactant having a fluorine content within this range is effective and has good solubility in the composition.

作為聚矽氧系界面活性劑，例如可以舉出Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH8400（以上為Dow Corning Toray Co.,Ltd.製）、TSF-4440、TSF-4300、TSF-4445、TSF-4460、TSF-4452（以上為Momentive performance Materials Inc.製）、KP341、KF6001、KF6002（以上為Shin-Etsu Chemical Co., Ltd.製）、BYK307、BYK323、BYK330（以上為BYK Chemie GmbH製）等。Examples of the polysilicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

作為烴系界面活性劑，例如可以舉出PIONIN A-76、Newkalgen FS-3PG、PIONIN B-709、PIONIN B-811-N、PIONIN D-1004、PIONIN D-3104、PIONIN D-3605、PIONIN D-6112、PIONIN D-2104-D、PIONIN D-212、PIONIN D-931、PIONIN D-941、PIONIN D-951、PIONIN E-5310、PIONIN P-1050-B、PIONIN P-1028-P、PIONIN P-4050-T等（以上為TAKEMOTO OIL&FAT CO.,LTD.製）等。Examples of hydrocarbon-based surfactants include PIONIN A-76, Newkalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by TAKEMOTO OIL & FAT CO., LTD.).

作為非離子型界面活性劑，可以舉出甘油、三羥甲基丙烷、三羥甲基乙烷以及該等乙氧基化物及丙氧基化物（例如，甘油丙氧基化物、甘油乙氧基化物等）、聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、脫水山梨糖醇脂肪酸酯、Pluronic L10、L31、L61、L62、10R5、17R2、25R2（BASF公司製）、Tetronic 304、701、704、901、904、150R1（BASF公司製）、Solsperse 20000（Lubrizol Japan Limited.製）、NCW-101、NCW-1001、NCW-1002（Wako Pure Chemical Industries, Ltd.製）、PIONIN D-6112、D-6112-W、D-6315（Takemoto Oil&Fat Co.,Ltd.製）、Olfine E1010、Surfynol 104、400、440（Nissin Chemical Co.,Ltd.製）等。Examples of the nonionic surfactant include glycerin, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (Nissin Chemical Co., Ltd.) Wait.

作為陽離子系界面活性劑，具體而言，可以舉出有機矽氧烷聚合物KP341（Shin-Etsu Chemical Co., Ltd.製）、（甲基）丙烯酸系（共）聚合物Polyflow No.75、No.77、No.90、No.95（KYOEISHA CHEMICAL Co.,LTD.製）、W001（Yusho Co.,Ltd.製）等。Specific examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No.75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co., LTD.), and W001 (manufactured by Yusho Co., Ltd.).

作為陰離子系界面活性劑，具體而言，可以舉出W004、W005、W017（Yusho Co.,Ltd.製）、SANDET BL（SANYO KASEI Co.Ltd.製）等。Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by Sanyo Kasei Co., Ltd.).

本發明的硬化性樹脂組成物具有界面活性劑時，界面活性劑的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.001～2.0質量%為較佳，更佳為0.005～1.0質量%。界面活性劑可以為僅一種，亦可以為兩種以上。在界面活性劑為兩種以上之情況下，合計量在上述範圍內為較佳。When the curable resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % relative to the total solid content of the curable resin composition of the present invention, and more preferably 0.005 to 1.0 mass %. The surfactant may be only one kind or two or more kinds. When there are two or more kinds of surfactants, the total amount is preferably within the above range.

[高級脂肪酸衍生物] 為了防止因氧引起的聚合阻礙，可以在本發明的硬化性樹脂組成物中添加如二十二酸或二十二酸醯胺的高級脂肪酸衍生物，從而使其在塗佈後的乾燥過程中不均勻地存在於硬化性樹脂組成物的表面上。[Higher fatty acid derivatives] In order to prevent polymerization hindrance caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the curable resin composition of the present invention so that it is unevenly present on the surface of the curable resin composition during the drying process after coating.

又，高級脂肪酸衍生物亦能夠使用國際公開第2015/199219號的0155段中所記載的化合物。Furthermore, as the higher fatty acid derivatives, the compounds described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

在本發明的硬化性樹脂組成物具有高級脂肪酸衍生物之情況下，高級脂肪酸衍生物的含量相對於本發明的硬化性樹脂組成物的總固體成分為0.1～10質量%為較佳。高級脂肪酸衍生物可以為僅一種，亦可以為兩種以上。在高級脂肪酸衍生物為兩種以上之情況下，合計量在上述範圍內為較佳。When the curable resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more kinds of higher fatty acid derivatives, the total amount is preferably within the above range.

[無機粒子] 本發明的樹脂組成物可以包含無機粒子。作為無機粒子，具體而言，能夠包含碳酸鈣、磷酸鈣、二氧化矽、高嶺土、滑石、二氧化鈦、氧化鋁、硫酸鋇、氟化鈣、氟化鋰、沸石、硫化鉬、玻璃等。[Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

作為上述無機粒子的平均粒徑，0.01～2.0μm為較佳，0.02～1.5μm為更佳，0.03～1.0μm為進一步較佳，0.04～0.5μm為特佳。 藉由大量含有上述無機粒子的平均粒徑，上述硬化膜的機械特性可能劣化。又，若上述無機粒子的平均粒徑超過2.0μm，則因曝光光源的散射而解析度可能下降。The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The mechanical properties of the cured film may be deteriorated by the large amount of the average particle size of the inorganic particles. In addition, if the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to the scattering of the exposure light source.

[紫外線吸收劑] 本發明的組成物可以包含紫外線吸收劑。作為紫外線吸收劑，能夠使用水楊酸酯系、二苯甲酮系、苯并三唑系、取代丙烯腈系、三𠯤系等紫外線吸收劑。 作為水楊酸酯系紫外線吸收劑的例子，可以舉出水楊酸苯酯、水楊酸對辛基苯酯、水楊酸對第三丁基苯酯等，作為二苯甲酮系紫外線吸收劑的例子，可以舉出2,2’-二羥基-4-甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2,4-二羥基二苯甲酮、2-羥基-4-辛氧基二苯甲酮等。又，作為苯并三唑系紫外線吸收劑的例子，可以舉出2-（2’-羥基-3’,5’-二-第三丁基苯基）-5-氯苯并三唑、2-（2’-羥基-3’-第三丁基-5’-甲基苯基）-5-氯苯并三唑、2-（2’-羥基-3’-第三戊基-5’-異丁基苯基）-5-氯苯并三唑、2-（2’-羥基-3’-異丁基-5’-甲基苯基）-5-氯苯并三唑、2-（2’-羥基-3’-異丁基-5’-丙基苯基）-5-氯苯并三唑、2-（2’-羥基-3’,5’-二-第三丁基苯基）苯并三唑、2-（2’-羥基-5’-甲基苯基）苯并三唑、2-[2’-羥基-5’-（1,1,3,3-四甲基）苯基]苯并三唑等。[Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylic acid ester-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, tris(III)-based ultraviolet absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole. 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

作為取代丙烯腈系紫外線吸收劑的例子，可以舉出2-氰基-3,3-二苯基丙烯酸乙酯、2-氰基-3,3-二苯基丙烯酸2-乙基己酯等。進而，作為三𠯤系紫外線吸收劑的例子，可以舉出2-[4-[（2-羥基-3-十二烷氧基丙基）氧基]-2-羥基苯基]-4,6-雙（2,4-二甲基苯基）-1,3,5-三𠯤、2-[4-[（2-羥基-3-十三烷氧基丙基）氧基]-2-羥基苯基]-4,6-雙（2,4-二甲基苯基）-1,3,5-三𠯤、2-（2,4-二羥基苯基）-4,6-雙（2,4-二甲基苯基）-1,3,5-三𠯤等的單（羥基苯基）三𠯤化合物；2,4-雙（2-羥基-4-丙氧基苯基）-6-（2,4-二甲基苯基）-1,3,5-三𠯤、2,4-雙（2-羥基-3-甲基-4-丙氧基苯基）-6-（4-甲基苯基）-1,3,5-三𠯤、2,4-雙（2-羥基-3-甲基-4-己氧基苯基）-6-（2,4-二甲基苯基）-1,3,5-三𠯤等的雙（羥基苯基）三𠯤化合物；2,4-雙（2-羥基-4-丁氧基苯基）-6-（2,4-二丁氧基苯基）-1,3,5-三𠯤、2,4,6-三（2-羥基-4-辛氧基苯基）-1,3,5-三𠯤、2,4,6-三[2-羥基-4-（3-丁氧基-2-羥基丙氧基）苯基]-1,3,5-三𠯤等的三（羥基苯基）三𠯤化合物等。Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Examples of tris(iodine-based ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris(iodine-based ultraviolet absorbers), 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -bis(2,4-dimethylphenyl)-1,3,5-trisinium, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trisinium, etc.; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-trisinium, Bis(hydroxyphenyl)trisinium compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-trisinium and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-trisinium; 2,4-bis(2-hydroxy-4- tris(hydroxyphenyl)tris(iota) compounds such as 2,4-dibutoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris(iota), 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris(iota), and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris(iota).

在本發明中，上述各種紫外線吸收劑可以單獨使用一種，亦可以組合使用兩種以上。 本發明的組成物可以包含紫外線吸收劑，亦可以不包含紫外線吸收劑，但是在包含之情況下，紫外線吸收劑的含量相對於本發明的組成物的總固體成分質量為0.001質量%以上且1質量%以下為較佳，0.01質量%以上且0.1質量%以下為更佳。In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may contain ultraviolet absorbers or may not contain ultraviolet absorbers, but when contained, the content of ultraviolet absorbers is preferably 0.001 mass % or more and 1 mass % or less, and more preferably 0.01 mass % or more and 0.1 mass % or less relative to the total solid content of the composition of the present invention.

[有機鈦化合物] 本實施形態的樹脂組成物可以含有有機鈦化合物。由於樹脂組成物含有有機鈦化合物，因此即使在低溫下硬化時，亦能夠形成耐藥品性優異之樹脂層。[Organic titanium compound] The resin composition of this embodiment may contain an organic titanium compound. Since the resin composition contains the organic titanium compound, a resin layer with excellent chemical resistance can be formed even when hardening at a low temperature.

作為能夠使用的有機鈦化合物，可以舉出有機基經由共價鍵或離子鍵與鈦原子鍵結者。 將有機鈦化合物的具體例示於以下的I）～VII）中： I）鈦螯合化合物：其中，負型感光性樹脂組成物的保存穩定性優異，並且可以獲得良好的硬化圖案，從而具有兩個以上烷氧基之鈦螯合化合物為更佳。具體的例子為二異丙醇雙（三乙醇胺）鈦、二（正丁醇）雙（2,4-戊二酮）鈦、二異丙醇雙（2,4-戊二酮）鈦、二異丙醇雙（四甲基庚二酮）鈦、二異丙醇雙（乙醯乙酸乙酯）鈦等。 II）四烷氧基鈦化合物：例如為四（正丁醇）鈦、四乙醇鈦、四（2-乙基己醇）鈦、四異丁醇鈦、四異丙醇鈦、四甲醇鈦、四甲氧基丙醇鈦、四甲基苯氧化鈦、四（正壬醇）鈦、四（正丙醇）鈦、四硬脂醇鈦、四[雙｛2,2-（烯丙氧基甲基）丁醇｝]鈦等。 III）二茂鈦化合物：例如為五甲基環戊二烯基三甲醇鈦、雙（η5-2,4-環戊二烯-1-基）雙（2,6-二氟苯基）鈦、雙（η5-2,4-環戊二烯-1-基）雙（2,6-二氟-3-（1H-吡咯-1-基）苯基）鈦等。 IV）單烷氧基鈦化合物：例如為三（二辛基磷酸酯）異丙醇鈦、三（十二烷苯基磺酸酯）異丙醇鈦等。 V）氧化鈦化合物：例如為氧化鈦雙（戊二酮）、氧化鈦雙（四甲基庚二酮）、酞菁氧化鈦等。 VI）四乙醯丙酮鈦化合物：例如為四乙醯丙酮鈦等。 VII）鈦酸酯偶合劑：例如為異丙基三十二烷基苯磺醯鈦酸鹽等。As the organic titanium compound that can be used, there can be cited those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organic titanium compound are shown in the following I) to VII): I) Titanium chelate compound: Among them, the storage stability of the negative photosensitive resin composition is excellent, and a good curing pattern can be obtained, so a titanium chelate compound having two or more alkoxy groups is more preferred. Specific examples include titanium diisopropyl alcohol bis(triethanolamine), titanium di(n-butyl alcohol) bis(2,4-pentanedione), titanium diisopropyl alcohol bis(2,4-pentanedione), titanium diisopropyl alcohol bis(tetramethylheptanedione), titanium diisopropyl alcohol bis(ethyl acetylacetate), etc. II) Tetraalkoxy titanium compounds: for example, titanium tetra(n-butanol), titanium tetraethanol, titanium tetra(2-ethylhexanol), titanium tetraisobutanol, titanium tetraisopropanol, titanium tetramethanol, titanium tetramethoxypropanol, titanium tetramethylphenoxide, titanium tetra(n-nonanol), titanium tetra(n-propanol), titanium tetrastearyl alcohol, titanium tetra[bis{2,2-(allyloxymethyl)butanol}], etc. III) Titanium bis(cyclopentadienyl)trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Titanium monoalkoxy compounds: for example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylphenyl sulfonate) isopropoxide, etc. V) Titanium oxide compounds: for example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), titanium phthalocyanine oxide, etc. VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanium ester coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanium salt, etc.

其中，作為有機鈦化合物，從發揮更良好的耐藥品性之觀點考慮，選自包括上述I）鈦螯合化合物、II）四烷氧基鈦化合物及III）二茂鈦化合物之群組中的至少一種化合物為較佳。尤其，二異丙醇雙（乙醯乙酸乙酯）鈦、四（正丁醇）鈦及雙（η5-2,4-環戊二烯-1-基）雙（2,6-二氟-3-（1H-吡咯-1-基）苯基）鈦為較佳。Among them, as an organic titanium compound, from the viewpoint of exerting better drug resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dioctenyl titanium compounds is preferred. In particular, titanium diisopropylate bis(ethyl acetate), titanium tetra(n-butoxide) and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) are preferred.

在配合有機鈦化合物之情況下，其配合量相對於環化樹脂的前驅物100質量份為0.05～10質量份為較佳，更較佳為0.1～2質量份。在配合量為0.05質量份以上之情況下，所獲得之硬化圖案顯現出良好的耐熱性及耐藥品性，另一方面，在配合量為10質量份以下之情況下，組成物的保存穩定性優異。When an organic titanium compound is added, the amount thereof is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the precursor of the cyclized resin. When the amount is 0.05 parts by mass or more, the obtained hardened pattern exhibits good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the storage stability of the composition is excellent.

[抗氧化劑] 本發明的組成物可以包含抗氧化劑。藉由含有抗氧化劑作為添加劑，能夠提高硬化後的膜的伸長特性和與金屬材料的密接性。作為抗氧化劑，可以舉出酚化合物、亞磷酸酯化合物及硫醚化合物等。作為酚化合物，能夠使用作為酚系抗氧化劑已知之任意的酚化合物。作為較佳的酚化合物，可以舉出受阻酚化合物。在與酚性羥基相鄰之部位（鄰位）上具有取代基之化合物為較佳。作為前述取代基，碳數1～22的經取代或未經取代的烷基為較佳。又，抗氧化劑為在同一分子內具有酚基及亞磷酸酯基之化合物亦較佳。又，抗氧化劑亦能夠較佳地使用磷系抗氧化劑。作為磷系抗氧化劑，可以舉出三[2-[[2,4,8,10-四（1,1-二甲基乙基）二苯并[d,f][1,3,2]二氧雜膦雜環庚二烯-6-基]氧基]乙基]胺、三[2-[（4,6,9,11-四-第三丁基二苯并[d,f][1,3,2]二氧雜膦雜環庚二烯-2-基）氧基]乙基]胺及亞磷酸乙基雙（2,4-二-第三丁基-6-甲基苯基）等。作為抗氧化劑的市售品，例如可以舉出Adekastab AO-20、Adekastab AO-30、Adekastab AO-40、Adekastab AO-50、Adekastab AO-50F、Adekastab AO-60、Adekastab AO-60G、Adekastab AO-80及Adekastab AO-330（以上為ADEKA CORPORATION製）等。又，抗氧化劑亦能夠使用日本專利第6268967號公報的0023～0048段中所記載之化合物。又，本發明的組成物依據據需要可以含有潛在的抗氧化劑。作為潛在的抗氧化劑，可以舉出發揮抗氧化劑作用之部位被保護基保護之化合物，且為藉由在100～250℃下進行加熱或在酸/鹼觸媒存在下在80～200℃下進行加熱以使保護基脫離而發揮抗氧化劑作用之化合物。作為潛在的抗氧化劑，可以舉出國際公開第2014/021023號、國際公開第2017/030005號及日本特開2017-008219號公報中所記載之化合物。作為潛在的抗氧化劑的市售品，可以舉出ADEKA ARKLSGPA-5001（ADEKA CORPORATION製）等。作為較佳的抗氧化劑的例子，可以舉出2,2-硫代雙（4-甲基-6-第三丁基酚）、2,6-二-第三丁基酚及通式（3）所表示之化合物。[Antioxidant] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the elongation characteristics of the cured film and the adhesion to the metal material can be improved. As the antioxidant, phenol compounds, phosphite compounds and thioether compounds can be cited. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. As a preferred phenol compound, a hindered phenol compound can be cited. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (adjacent position) are preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Moreover, the antioxidant can also preferably use a phosphorus antioxidant. Examples of the phosphorus antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphinylcycloheptadien-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-t-butyldibenzo[d,f][1,3,2]dioxaphosphinylcycloheptadien-2-yl)oxy]ethyl]amine, and phosphite ethylbis(2,4-di-t-butyl-6-methylphenyl). As commercially available antioxidants, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80 and Adekastab AO-330 (all manufactured by ADEKA CORPORATION) can be cited. In addition, the antioxidant can also use the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967. In addition, the composition of the present invention can contain a potential antioxidant as needed. As potential antioxidants, compounds in which the site that exerts antioxidant action is protected by a protecting group and the protective group is removed by heating at 100 to 250°C or heating at 80 to 200°C in the presence of an acid/base catalyst to exert antioxidant action can be cited. As potential antioxidants, compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Publication No. 2017-008219 can be cited. As commercially available products of potential antioxidants, ADEKA ARKLSGPA-5001 (manufactured by ADEKA CORPORATION) and the like can be cited. Preferred examples of antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and compounds represented by the general formula (3).

[化學式59] [Chemical formula 59]

通式（3）中，R5表示氫原子或碳數2以上的烷基，R6表示碳數2以上的伸烷基。R7表示包含碳數2以上的伸烷基、O原子及N原子中的至少任一個之1～4價有機基。k表示1～4的整數。In the general formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, R6 represents an alkylene group having 2 or more carbon atoms, R7 represents a monovalent to tetravalent organic group including at least one of an alkylene group having 2 or more carbon atoms, an O atom, and a N atom, and k represents an integer of 1 to 4.

通式（3）所表示之化合物抑制樹脂的脂肪族基和酚性羥基的氧化劣化。又，能夠藉由對金屬材料的防鏽作用來抑制金屬氧化。The compound represented by the general formula (3) inhibits the oxidative degradation of the aliphatic group and the phenolic hydroxyl group of the resin. In addition, it can inhibit metal oxidation by its rust-proofing effect on metal materials.

能夠同時作用於樹脂和金屬材料，因此k為2～4的整數為更佳。作為R7，可以舉出烷基、環烷基、烷氧基、烷基醚基、烷基甲矽烷基、烷氧基甲矽烷基、芳基、芳基醚基、羧基、羰基、烯丙基、乙烯基、雜環基、-O-、-NH-、-NHNH-、組合了該等者等，還可以具有取代基。其中，從在顯影液中的溶解性和金屬密接性的觀點考慮，具有烷基醚、-NH-為較佳，從與樹脂的相互作用和金屬錯合物形成時之金屬密接性的觀點考慮，-NH-為更佳。It can act on the resin and the metal material at the same time, so k is preferably an integer of 2 to 4. As R7, alkyl, cycloalkyl, alkoxy, alkyl ether, alkyl silyl, alkoxy silyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, combinations thereof, etc. can be cited, and it may further have a substituent. Among them, from the viewpoint of solubility in the developer and metal adhesion, alkyl ether and -NH- are preferred, and from the viewpoint of interaction with the resin and metal adhesion when a metal complex is formed, -NH- is more preferred.

關於下述通式（3）所表示之化合物，作為例子，可以舉出以下者，但是並不限於下述結構。The compounds represented by the following general formula (3) can be exemplified as follows, but are not limited to the following structures.

[化學式60] [Chemical formula 60]

[化學式61] [Chemical formula 61]

[化學式62] [Chemical formula 62]

[化學式63] [Chemical formula 63]

抗氧化劑的添加量相對於樹脂為0.1～10質量份為較佳，0.5～5質量份為更佳。在添加量少於0.1質量份的情況下，不易獲得提高硬化後的膜的伸長特性和對金屬材料之密接性的效果，並且在添加量多於10質量份的情況下，存在由於與光敏劑的相互作用而引起樹脂組成物的靈敏度下降之慮。抗氧化劑可以僅使用一種，亦可以使用兩種以上。在使用兩種以上之情況下，該等的合計量在上述範圍內為較佳。The amount of the antioxidant added is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, relative to the resin. When the amount added is less than 0.1 parts by weight, it is difficult to obtain the effect of improving the elongation characteristics of the cured film and the adhesion to the metal material, and when the amount added is more than 10 parts by weight, there is a concern that the sensitivity of the resin composition will decrease due to the interaction with the photosensitizer. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount thereof is preferably within the above range.

＜關於其他含有物質的限制＞ 從塗佈面性狀的觀點考慮，本發明的硬化性樹脂組成物的水分含量小於5質量%為較佳，小於1質量%為更佳，小於0.6質量%為進一步較佳。作為維持水分的含量之方法，可以舉出調整保管條件中之濕度及降低收容容器的孔隙率等。<Restrictions on other contained substances> From the perspective of coating surface properties, the water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass. Methods for maintaining the water content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container.

從絕緣性的觀點考慮，本發明的硬化性樹脂組成物的金屬含量小於5質量ppm（parts per million（百萬分率））為較佳，小於1質量ppm為更佳，小於0.5質量ppm為進一步較佳。作為金屬，可以舉出鈉、鉀、鎂、鈣、鐵、鉻、鎳等。在包含複數個金屬之情況下，該等金屬的合計在上述範圍內為較佳。From the viewpoint of insulation, the metal content of the hardening resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total of the metals is preferably within the above range.

又，作為減少意外包含於本發明的硬化性樹脂組成物中之金屬雜質之方法，可以舉出如下方法：選擇金屬含量少的原料作為構成本發明的硬化性樹脂組成物之原料；對構成本發明的硬化性樹脂組成物之原料進行過濾器過濾；將聚四氟乙烯等內襯於裝置內以在盡可能抑制污染之條件下進行蒸餾。Furthermore, as a method for reducing the metal impurities accidentally contained in the hardening resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as a raw material constituting the hardening resin composition of the present invention; filtering the raw material constituting the hardening resin composition of the present invention with a filter; lining polytetrafluoroethylene or the like in an apparatus to perform distillation under conditions that suppress contamination as much as possible.

若考慮本發明的硬化性樹脂組成物作為半導體材料的用途，則從配線腐蝕性的觀點考慮，鹵素原子的含量小於500質量ppm為較佳，小於300質量ppm為更佳，小於200質量ppm為進一步較佳。其中，以鹵素離子的狀態存在者小於5質量ppm為較佳，小於1質量ppm為更佳，小於0.5質量ppm為進一步較佳。作為鹵素原子，可以舉出氯原子及溴原子。氯原子及溴原子或氯離子及溴離子的合計分別在上述範圍內為較佳。作為調節鹵素原子的含量之方法，可以較佳地舉出離子交換處理等。When the curable resin composition of the present invention is used as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion. Among them, the content of halogen atoms in the form of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. It is preferred that the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions are respectively within the above ranges. As a method for adjusting the content of halogen atoms, ion exchange treatment can be preferably cited.

作為本發明的硬化性樹脂組成物的收容容器，能夠使用先前公知的收容容器。又，作為收容容器，為了抑制雜質混入原材料或硬化性樹脂組成物中，使用由6種6層樹脂構成容器內壁之多層瓶、將6種樹脂形成為7層結構之瓶亦較佳。作為該種容器，例如可以舉出日本特開2015-123351號公報中所記載的容器。As a container for storing the curable resin composition of the present invention, a previously known container can be used. In addition, as a container, in order to suppress the mixing of impurities into the raw materials or the curable resin composition, it is also preferable to use a multi-layer bottle in which the inner wall of the container is composed of six types of six layers of resins, or a bottle in which six types of resins are formed into a seven-layer structure. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

＜硬化性樹脂組成物的製備＞ 關於本發明的硬化性樹脂組成物，能夠藉由混合上述各成分來製備。混合方法並無特別限定，能夠藉由先前公知的方法來進行。<Preparation of hardening resin composition> The hardening resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be performed by a conventionally known method.

又，為了去除硬化性樹脂組成物中的灰塵或微粒等異物，進行使用過濾器之過濾為較佳。過濾器孔徑為1μm以下為較佳，0.5μm以下為更佳，0.1μm以下為進一步較佳。另一方面，從生產率的觀點考慮，5μm以下為較佳，3μm以下為更佳，1μm以下為進一步較佳。過濾器的材質為聚四氟乙烯、聚乙烯或尼龍為較佳。過濾器可以使用藉由有機溶劑預先清洗者。在過濾器的過濾步驟中，亦可以串聯或並聯連接複數種過濾器而使用。在使用複數種過濾器之情況下，可以組合使用孔徑或材質不同之過濾器。又，可以將各種材料過濾複數次。在過濾複數次之情況下，可以為循環過濾。又，亦可以在加壓之後進行過濾。在加壓之後進行過濾之情況下，進行加壓之壓力為0.05MPa以上且0.3MPa以下為較佳。另一方面，從生產率的觀點考慮，0.01MPa以上且1.0MPa以下為較佳，0.03MPa以上且0.9MPa以下為更佳，0.05MPa以上且0.7MPa以下為進一步較佳。 除了使用過濾器之過濾以外，還可以進行使用吸附材料之雜質去除處理。亦可以組合過濾器過濾與使用吸附材料之雜質去除處理。作為吸附材料，能夠使用公知的吸附材料。例如，可列舉矽膠、沸石等無機系吸附材料、活性碳等有機系吸附材料。Furthermore, in order to remove foreign matter such as dust or particles in the curable resin composition, it is preferred to perform filtering using a filter. The pore size of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.1 μm or less. On the other hand, from the perspective of productivity, 5 μm or less is preferred, 3 μm or less is more preferred, and 1 μm or less is further preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be pre-cleaned with an organic solvent. In the filtering step of the filter, multiple filters may be connected in series or in parallel for use. When using multiple filters, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cycle filtering. In addition, filtering can also be performed after pressurization. When filtering is performed after pressurization, the pressure of pressurization is preferably 0.05MPa or more and 0.3MPa or less. On the other hand, from the perspective of productivity, 0.01MPa or more and 1.0MPa or less is preferred, 0.03MPa or more and 0.9MPa or less is more preferred, and 0.05MPa or more and 0.7MPa or less is even more preferred. In addition to filtering using a filter, impurity removal using an adsorbent can also be performed. Filtering using a filter and impurity removal using an adsorbent can also be combined. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be listed.

＜硬化性樹脂組成物的用途＞ 本發明的硬化性樹脂組成物用於形成再配線層用層間絕緣膜為較佳。 又，此外，亦能夠用於半導體器件的絕緣膜的形成或應力緩衝膜的形成等。<Application of the curable resin composition> The curable resin composition of the present invention is preferably used to form an interlayer insulating film for a redistribution layer. In addition, it can also be used to form an insulating film of a semiconductor device or a stress buffer film.

（硬化膜、積層體、半導體器件及該等的製造方法） 接著，對硬化膜、積層體、半導體器件及該等的製造方法進行說明。(Curing film, laminate, semiconductor device, and method for manufacturing the same) Next, the curing film, laminate, semiconductor device, and method for manufacturing the same are described.

本發明的硬化膜為將本發明的硬化性樹脂組成物硬化而成。本發明的硬化膜的膜厚例如能夠設為0.5μm以上，亦能夠設為1μm以上。又，作為上限值，能夠設為100μm以下，亦能夠設為30μm以下。The cured film of the present invention is formed by curing the curable resin composition of the present invention. The film thickness of the cured film of the present invention can be set to 0.5 μm or more, or 1 μm or more, and the upper limit can be set to 100 μm or less, or 30 μm or less.

可以將本發明的硬化膜積層兩層以上、進而積層3～7層來作為積層體。本發明的積層體為具有兩層以上的硬化膜且在硬化膜之間具有金屬層之積層體為較佳。又，本發明的積層體包含兩層以上的硬化膜，在任意上述硬化膜彼此之間包含金屬層之態樣為較佳。例如，可以較佳地舉出至少包含依序積層有第一硬化膜、金屬層、第二硬化膜這三個層之層結構之積層體。上述第一硬化膜及上述第二硬化膜均為本發明的硬化膜，例如可以較佳地舉出上述第一硬化膜及上述第二硬化膜均為將本發明的硬化性樹脂組成物硬化而成之膜之態樣。用於形成上述第一硬化膜之本發明的硬化性樹脂組成物與用於形成上述第二硬化膜之本發明的硬化性樹脂組成物可以為組成相同的組成物，亦可以為組成不同的組成物，但是從製造適性的觀點考慮，組成相同的組成物為較佳。該種金屬層可以較佳地用作再配線層等金屬配線。The cured film of the present invention may be laminated in two or more layers, and further laminated in 3 to 7 layers to form a laminate. The laminate of the present invention is preferably a laminate having two or more cured films and a metal layer between the cured films. Furthermore, the laminate of the present invention is preferably a laminate having two or more cured films and a metal layer between any of the cured films. For example, a laminate having a layered structure including at least three layers of a first cured film, a metal layer, and a second cured film laminated in sequence can be preferably cited. The first cured film and the second cured film are both cured films of the present invention. For example, the first cured film and the second cured film are both films formed by curing the curable resin composition of the present invention. The curable resin composition of the present invention used to form the first cured film and the curable resin composition of the present invention used to form the second cured film may be the same composition or different compositions, but from the perspective of manufacturing suitability, the same composition is preferred. Such a metal layer can be preferably used as a metal wiring such as a redistribution layer.

作為能夠適用本發明的硬化膜的領域，可以舉出半導體器件的絕緣膜、再配線層用層間絕緣膜、應力緩衝膜等。除此以外，亦可以舉出密封膜、基板材料（柔性印刷電路板的基底膜或覆蓋膜、層間絕緣膜）或藉由對如上述實際安裝用途的絕緣膜進行蝕刻而形成圖案之情況等。關於該等用途，例如能夠參閱Science&Technology Co.,Ltd.“聚醯亞胺的高功能化和應用技術”2008年4月、柿本雅明/監修、CMC技術圖書館“聚醯亞胺材料的基礎和開發”2011年11月發行、日本聚醯亞胺/芳香族系高分子研究會/編“最新聚醯亞胺 基礎和應用”NTS,2010年8月等。Examples of fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, and stress buffer films. In addition, examples include sealing films, substrate materials (base films or cover films, interlayer insulating films for flexible printed circuit boards), and situations in which patterns are formed by etching insulating films for actual mounting purposes such as those described above. For such applications, for example, see Science & Technology Co., Ltd., "Advanced Functionality and Application Technology of Polyimide," April 2008, Kakimoto Masaaki, CMC Technical Library, "Basics and Development of Polyimide Materials," November 2011, Japan Polyimide/Aromatic Polymer Research Society, "Latest Polyimide: Fundamentals and Applications," NTS, August 2010, etc.

又，本發明中之硬化膜亦能夠用於膠印版面或網版版面等版面的製造、蝕刻成形組件的用途、電子尤其微電子中之保護漆及介電層的製造等中。Furthermore, the cured film of the present invention can also be used in the manufacture of offset printing plates or screen plates, the use of etching forming components, the manufacture of protective varnishes and dielectric layers in electronics, especially microelectronics, etc.

本發明的硬化膜的製造方法（以下，亦簡稱為“本發明的製造方法”。）包括將本發明的硬化性樹脂組成物適用於基材而形成膜之膜形成步驟為較佳。 進而，本發明的硬化膜的製造方法包括上述膜形成步驟，並且還包括對上述膜進行曝光之曝光步驟及對上述膜進行顯影之（對上述膜進行顯影處理）顯影步驟為更佳。 進而，本發明的硬化膜的製造方法包括上述膜形成步驟（及依據需要包括上述顯影步驟），並且還包括在50～450℃下對上述膜進行加熱之加熱步驟為更佳。 具體而言，包括以下（a）～（d）的步驟亦較佳。 （a）將硬化性樹脂組成物適用於基材而形成膜（硬化性樹脂組成物層）之膜形成步驟 （b）在膜形成步驟之後，對膜進行曝光之曝光步驟 （c）對經曝光之上述膜進行顯影處理之顯影步驟 （d）在50～450℃下對經顯影之上述膜進行加熱之加熱步驟 藉由在上述加熱步驟中進行加熱，能夠使顯影後的硬化性樹脂組成物層進一步硬化。在該加熱步驟中，例如上述熱鹼產生劑分解，從而可以獲得充分的硬化性。The method for producing a cured film of the present invention (hereinafter, also referred to as "the method for producing the present invention") preferably includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film. Furthermore, the method for producing a cured film of the present invention preferably includes the film forming step, and further includes an exposure step of exposing the film and a development step of developing the film (developing the film). Furthermore, the method for producing a cured film of the present invention preferably includes the film forming step (and the development step as required), and further includes a heating step of heating the film at 50 to 450°C. Specifically, it is also preferred to include the following steps (a) to (d). (a) a film forming step of applying a curable resin composition to a substrate to form a film (curable resin composition layer) (b) an exposure step of exposing the film after the film forming step (c) a developing step of developing the exposed film (d) a heating step of heating the developed film at 50 to 450°C By heating in the heating step, the developed curable resin composition layer can be further cured. In the heating step, for example, the hot alkali generator is decomposed, thereby obtaining sufficient curability.

本發明的較佳的實施形態之積層體的製造方法包括本發明的硬化膜的製造方法。關於本實施形態的積層體的製造方法，按照上述硬化膜的製造方法形成硬化膜之後，進而再次進行（a）的步驟或（a）～（c）的步驟或（a）～（d）的步驟。尤其，將上述各步驟依序進行複數次，例如進行2～5次（亦即，總計3～6次）為較佳。藉由如此積層硬化膜，能夠形成積層體。在本發明中，尤其在設置有硬化膜之部分上或硬化膜之間或在該兩個位置設置金屬層為較佳。另外，在積層體的製造中，無需重複（a）～（d）的所有步驟，能夠如上述藉由進行複數次至少（a）、較佳為（a）～（c）或（a）～（d）的步驟而獲得硬化膜的積層體。The method for manufacturing a laminated body of a preferred embodiment of the present invention includes the method for manufacturing a cured film of the present invention. Regarding the method for manufacturing a laminated body of the present embodiment, after forming a cured film according to the above-mentioned method for manufacturing a cured film, step (a) or steps (a) to (c) or steps (a) to (d) are performed again. In particular, it is preferred to perform the above-mentioned steps in sequence a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this way, a laminated body can be formed. In the present invention, it is preferred to provide a metal layer on a portion where a cured film is provided or between the cured films or at these two locations. In addition, in the manufacture of the laminate, it is not necessary to repeat all steps (a) to (d), and the laminate of the cured film can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) multiple times as described above.

＜膜形成步驟（層形成步驟）＞ 本發明的較佳的實施形態之製造方法包括將硬化性樹脂組成物適用於基材而形成膜（層狀）之膜形成步驟（層形成步驟）。<Film-forming step (layer-forming step)> The manufacturing method of a preferred embodiment of the present invention includes a film-forming step (layer-forming step) of applying a curable resin composition to a substrate to form a film (layer).

基材的種類能夠依據用途適當設定，但是並無特別限制，可以舉出矽、氮化矽、多晶矽、氧化矽、非晶矽等半導體製作基材、石英、玻璃、光學膜、陶瓷材料、蒸鍍膜、磁性膜、反射膜、Ni、Cu、Cr、Fe等金屬基材、紙、SOG（Spin On Glass：旋塗式玻璃）、TFT（薄膜晶體管）陣列基材、電漿顯示面板（PDP）的電極板等。又，在該等基材的表面上可以設置有密接層或氧化層等層。在本發明中，尤其半導體製作基材為較佳，矽基材、Cu基材及模具基材為更佳。 又，作為基材，例如使用板狀的基材（基板）。 基材的形狀並無特別限定，可以為圓形，亦可以為矩形，但是矩形為較佳。 在該等基材的表面上可以設置有由六甲基二矽氮烷（HMDS）等製成之密接層和氧化層等層。 作為基材的尺寸，若為圓形，則例如直徑為100～450mm，較佳為200～450mm。若為矩形，則例如短邊的長度為100～1000mm，較佳為200～700mm。The type of substrate can be appropriately set according to the purpose, but there is no particular limitation. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, evaporated films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, and electrode plates of plasma display panels (PDP). In addition, a bonding layer or an oxide layer may be provided on the surface of the substrate. In the present invention, a semiconductor substrate is particularly preferred, and a silicon substrate, a Cu substrate, and a mold substrate are more preferred. In addition, as a substrate, for example, a plate-shaped substrate (substrate) is used. The shape of the substrate is not particularly limited, and may be circular or rectangular, but a rectangular shape is preferred. On the surface of the substrate, a bonding layer and an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided. As for the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm.

又，在硬化性樹脂組成物層等樹脂層的表面或金屬層的表面上形成硬化性樹脂組成物層之情況下，樹脂層或金屬層成為基材。Furthermore, when a hardening resin composition layer is formed on the surface of a resin layer such as a hardening resin composition layer or on the surface of a metal layer, the resin layer or the metal layer becomes a base material.

作為將硬化性樹脂組成物適用於基材之方法，塗佈為較佳。As a method of applying the curable resin composition to the base material, coating is preferred.

具體而言，作為所適用之方法，可以例示浸塗法、氣刀塗佈法、簾式塗佈法、線棒塗佈法、凹版塗佈法、擠壓塗佈法、噴塗法、旋塗法、狹縫塗佈法及噴墨法等。從硬化性樹脂組成物層的厚度均勻性的觀點考慮，更佳為旋塗法、狹縫塗佈法、噴塗法、噴墨法。依據方法調整適當的固體成分濃度或塗佈條件，從而能夠獲得所期望的厚度的樹脂層。又，亦能夠依據基材的形狀適當選擇塗佈方法，若為晶圓等圓形基材，則旋塗法或噴塗法、噴墨法等為較佳，若為矩形基材，則狹縫塗佈法或噴塗法、噴墨法等為較佳。在使用旋塗法的情況下，例如能夠以500～2,000rpm（revolutions per minute：每分鐘轉數）的轉速適用10秒鐘～1分鐘左右。依據樹脂組成物的黏度和要設定之膜厚，以300～3,500rpm的轉速適用10～180秒鐘亦較佳。又，為了獲得膜厚的均勻性，亦能夠組合複數個轉速來進行塗佈。 又，亦能夠適用將藉由上述賦予方法預先賦予至偽支撐體上而形成之塗膜轉印到基材上之方法。 關於轉印方法，本發明中亦能夠較佳地採用日本特開2006-023696號公報的0023段、0036～0051段或日本特開2006-047592號公報的0096～0108段中所記載的製作方法。 又，可以進行在基材的端部中去除多餘的膜的步驟。在該種步驟的例子中，可以舉出邊珠沖洗（EBR）、氣刀、背面沖洗（Back rinse）等。亦可以採用預濕步驟，該預濕步驟在將樹脂組成物塗佈於基材上之前，對基材塗佈各種溶劑以提高基材的潤濕性之後，塗佈樹脂組成物。Specifically, as the applicable method, there can be exemplified dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the perspective of thickness uniformity of the curable resin composition layer, spin coating, slit coating, spray coating, and inkjet coating are more preferred. By adjusting the appropriate solid component concentration or coating conditions according to the method, a resin layer of desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, spin coating, spray coating, inkjet coating, etc. are preferred. If it is a rectangular substrate, slit coating, spray coating, inkjet coating, etc. are preferred. When using the spin coating method, for example, it can be applied at a speed of 500 to 2,000 rpm (revolutions per minute) for about 10 seconds to 1 minute. Depending on the viscosity of the resin composition and the film thickness to be set, it is also preferred to apply at a speed of 300 to 3,500 rpm for 10 to 180 seconds. Furthermore, in order to obtain uniform film thickness, multiple rotation speeds can be combined for coating. Furthermore, a method of transferring the coating formed by pre-applying the coating to the pseudo support by the above-mentioned applying method to the substrate can also be applied. Regarding the transfer method, the present invention can also preferably adopt the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Publication No. 2006-047592. Furthermore, a step of removing excess film at the end of the substrate can be performed. Examples of such steps include edge bead rinsing (EBR), air knife, back rinse, etc. A pre-wetting step may also be used, in which various solvents are applied to the substrate to improve the wettability of the substrate before the resin composition is applied on the substrate, and then the resin composition is applied.

＜乾燥步驟＞ 本發明的製造方法亦可以在形成上述膜（硬化性樹脂組成物層）之後包括膜形成步驟（層形成步驟）之後，為了去除溶劑進行乾燥之步驟。較佳的乾燥溫度為50～150℃，70～130℃為更佳，90～110℃為進一步較佳。作為乾燥時間，可以例示30秒鐘～20分鐘，1分鐘～10分鐘為較佳，3分鐘～7分鐘為更佳。<Drying step> The manufacturing method of the present invention may also include a drying step for removing the solvent after the film forming step (layer forming step) after forming the above-mentioned film (hardening resin composition layer). The preferred drying temperature is 50 to 150°C, 70 to 130°C is more preferred, and 90 to 110°C is further preferred. As the drying time, 30 seconds to 20 minutes can be exemplified, 1 minute to 10 minutes is preferred, and 3 minutes to 7 minutes is more preferred.

＜曝光步驟＞ 本發明的製造方法亦可以包括對上述膜（硬化性樹脂組成物層）進行曝光之曝光步驟。關於曝光量，只要能夠將硬化性樹脂組成物硬化，則並無特別限定，例如以在波長365nm下的曝光能量換算計照射100～10,000mJ/cm2 為較佳，照射200～8,000mJ/cm2 為更佳。<Exposure step> The manufacturing method of the present invention may also include an exposure step of exposing the above-mentioned film (hardening resin composition layer). There is no particular limitation on the exposure amount as long as the hardening resin composition can be hardened. For example, it is preferably 100 to 10,000 mJ/ cm2 , and more preferably 200 to 8,000 mJ/ cm2 , calculated as the exposure energy at a wavelength of 365 nm.

曝光波長能夠在190～1,000nm的範圍內適當設定，240～550nm為較佳。The exposure wavelength can be appropriately set within the range of 190 to 1,000 nm, with 240 to 550 nm being the best.

關於曝光波長，若以與光源的關係進行說明，則可以舉出（1）半導體雷射（波長830nm、532nm、488nm、405nm etc.）、（2）金屬鹵化物燈、（3）高壓水銀燈、g射線（波長436nm）、h射線（波長405nm）、i射線（波長365nm）、寬（g、h、i射線的3波長）、（4）準分子雷射、KrF準分子雷射（波長248nm）、ArF準分子雷射（波長193nm）、F2準分子雷射（波長157nm）、（5）極紫外線；EUV（波長13.6nm）、（6）電子束、（7）YAG雷射的第二諧波532nm、第三諧波355nm等。關於本發明的硬化性樹脂組成物，尤其基於高壓水銀燈之曝光為較佳，其中，基於i射線之曝光為較佳。藉此，可以獲得尤其高的曝光靈敏度。從處理和生產率的觀點考慮，高壓水銀燈的寬（g、h、i射線的三個波長）光源或半導體雷射405nm亦較佳。Regarding the exposure wavelength, if we explain it in relation to the light source, we can cite (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide (3 wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm. The curable resin composition of the present invention is preferably exposed by a high-pressure mercury lamp, and preferably by i-rays. This can achieve particularly high exposure sensitivity. From the perspective of handling and productivity, a wide (three wavelengths of g, h, and i-rays) light source of a high-pressure mercury lamp or a semiconductor laser 405nm is also preferred.

＜顯影步驟＞ 本發明的製造方法亦可以包括對經曝光之膜（硬化性樹脂組成物層）進行顯影處理之顯影步驟。藉由進行顯影，未曝光之部分（非曝光部）被去除。只要能夠形成所期望的圖案，則顯影方法並無特別限制，例如可以舉出從噴嘴吐出顯影液、噴霧器噴霧及將基材浸漬於顯影液中等，較佳地利用從噴嘴的吐出。在顯影步驟中，能夠採用將顯影液連續地供給至基材上之步驟、在基材上使顯影液保持大致靜止狀態之步驟、利用超聲波等使顯影液振動之步驟及組合了該等之步驟等。<Developing step> The manufacturing method of the present invention may also include a developing step of developing the exposed film (hardening resin component layer). By developing, the unexposed portion (non-exposed portion) is removed. As long as the desired pattern can be formed, there is no particular limitation on the developing method, and examples include spitting developer from a nozzle, spraying with a sprayer, and immersing the substrate in the developer, and preferably using spitting from a nozzle. In the developing step, there can be a step of continuously supplying the developer to the substrate, a step of keeping the developer in a substantially stationary state on the substrate, a step of vibrating the developer using ultrasound, etc., and a step combining these.

顯影使用顯影液來進行。若硬化性樹脂組成物為負型硬化性樹脂組成物，則能夠不受特別限制地使用硬化性樹脂組成物層的未曝光部分（非曝光部）被去除之顯影液，若本發明的硬化性樹脂組成物為正型硬化性樹脂組成物，則能夠不受特別限制地使用曝光部分（曝光部）被去除之顯影液。 在本發明中，將使用鹼顯影液作為顯影液之情況稱為鹼性顯影，將使用含有50質量%以上的有機溶劑之顯影液作為顯影液之情況稱為溶劑顯影。Development is performed using a developer. If the curable resin composition is a negative curable resin composition, a developer in which the unexposed portion (non-exposed portion) of the curable resin composition layer is removed can be used without particular restrictions, and if the curable resin composition of the present invention is a positive curable resin composition, a developer in which the exposed portion (exposed portion) is removed can be used without particular restrictions. In the present invention, the use of an alkaline developer as a developer is referred to as alkaline development, and the use of a developer containing 50% by mass or more of an organic solvent as a developer is referred to as solvent development.

在鹼性顯影中，顯影液中的有機溶劑的含量相對於顯影液的總質量為10質量%以下為較佳，5質量%以下為更佳，1質量%以下為進一步較佳，不含有有機溶劑為特佳。 鹼性顯影中之顯影液為pH為9～14之水溶液為更佳。 作為鹼性顯影中之顯影液中所包含之鹼性化合物，例如可以舉出氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、矽酸鈉、矽酸鉀、偏矽酸鈉、偏矽酸鉀、氨或胺等。作為胺，例如可以舉出乙胺、正丙胺、二乙胺、二正丙胺、三乙胺、甲基二乙胺、烷醇胺、二甲基乙醇胺、三乙醇胺、四級銨氫氧化物、氫氧化四甲基銨（TMAH）或氫氧化四乙基銨、氫氧化四丁基銨等。其中，不含有金屬的鹼性化合物為較佳，銨化合物為更佳。 鹼性化合物可以為僅一種，亦可以為兩種以上。例如在使用TMAH之情況下，顯影液中之鹼性化合物的含量在顯影液總質量中為0.01～10質量%為較佳，0.1～5質量%為更佳，0.3～3質量%為進一步較佳。In alkaline development, the content of the organic solvent in the developer is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less relative to the total mass of the developer. It is particularly preferred that the developer contains no organic solvent. The developer in alkaline development is preferably an aqueous solution having a pH of 9 to 14. As the alkaline compound contained in the developer in alkaline development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, ammonia or amine can be cited. As amines, for example, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. can be cited. Among them, alkaline compounds that do not contain metal are preferred, and ammonium compounds are more preferred. The alkaline compound may be only one or more than two. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, and further preferably 0.3 to 3 mass % in the total mass of the developer.

在溶劑顯影中，顯影液包含90%以上的有機溶劑為更佳。在本發明中，顯影液包含ClogP值為-1～5的有機溶劑為較佳，包含ClogP值為0～3的有機溶劑為更佳。關於ClogP值，能夠藉由ChemBioDraw（化學生物圖）輸入結構式以作為計算值來求出。In solvent development, the developer preferably contains 90% or more of an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained by inputting a structural formula as a calculated value in ChemBioDraw.

關於有機溶劑，作為酯類，例如可以較佳地舉出乙酸乙酯、乙酸正丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯、ε-己內酯、δ-戊內酯、烷氧基乙酸烷基酯（例：烷氧基乙酸甲酯、烷氧基乙酸乙酯、烷氧基乙酸丁酯（例如，甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等））、3-烷氧基丙酸烷基酯類（例：3-烷氧基丙酸甲酯、3-烷氧基丙酸乙酯等（例如，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-乙氧基丙酸乙酯等））、2-烷氧基丙酸烷基酯類（例：2-烷氧基丙酸甲酯、2-烷氧基丙酸乙酯、2-烷氧基丙酸丙酯等（例如，2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯））、2-烷氧基-2-甲基丙酸甲酯及2-烷氧基-2-甲基丙酸乙酯（例如，2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等）、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯等，以及作為醚類，例如可以較佳地舉出二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯等，以及作為酮類，例如可以較佳地舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、N-甲基-2-吡咯啶酮等，以及作為芳香族烴類，例如可以較佳地舉出甲苯、二甲苯、苯甲醚、檸檬烯等，作為亞碸類，可以較佳地舉出二甲基亞碸。As for the organic solvent, examples of the esters include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.), )), 3-alkoxy alkyl propionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy alkyl propionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.) ethyl propionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl Examples of the base solvent include cellulose acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene, etc., and examples of sulfoxides include dimethyl sulfoxide.

在本發明中，尤其環戊酮、γ-丁內酯為較佳，環戊酮為更佳。在顯影液包含有機溶劑之情況下，有機溶劑亦能夠使用一種或混合使用兩種以上。 顯影液還可以包含其他成分。作為其他成分，例如可以舉出公知的界面活性劑和公知的消泡劑等。In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. When the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more. The developer may also contain other components. As other components, for example, well-known surfactants and well-known defoaming agents can be cited.

顯影液的50質量%以上為有機溶劑為較佳，70質量%以上為有機溶劑為更佳，90質量%以上為有機溶劑為進一步較佳。又，亦可以為顯影液的100質量%為有機溶劑。Preferably, 50% by mass or more of the developer is an organic solvent, more preferably 70% by mass or more of the developer is an organic solvent, and even more preferably 90% by mass or more of the developer is an organic solvent. Alternatively, 100% by mass of the developer may be an organic solvent.

[顯影液的供給方法] 關於顯影液的供給方法，只要能夠形成所期望的圖案，則並無特別限制，存在將基材浸漬於顯影液中之方法、使用噴嘴向基材上供給顯影液以進行旋覆浸沒顯影或連續供給顯影液之方法。噴嘴的種類並無特別限制，可以舉出直式噴嘴、噴淋噴嘴、噴霧噴嘴等。 從顯影液的滲透性、非圖像部的去除性、製造上的效率的觀點考慮，使用直式噴嘴供給顯影液之方法或使用噴霧噴嘴連續供給之方法為較佳，從顯影液向圖像部的滲透性的觀點考慮，使用噴霧噴嘴進行供給之方法為更佳。 又，可以採用在使用直式噴嘴連續供給顯影液之後，旋轉基材以從基材上去除顯影液，在旋轉乾燥之後再次使用直式噴嘴連續供給之後，旋轉基材以從基材上去除顯影液之步驟，亦可以反覆進行複數次該步驟。 又，作為顯影步驟中之顯影液的供給方法，能夠採用將顯影液連續地供給至基材上之步驟、在基材上使顯影液保持大致靜止狀態之步驟、在基材上利用超聲波等使顯影液振動之步驟及組合了該等之步驟等。[Developer supply method] Regarding the developer supply method, there is no particular limitation as long as the desired pattern can be formed. There are methods of immersing the substrate in the developer, using a nozzle to supply the developer to the substrate for rotary immersion development, or continuously supplying the developer. There is no particular limitation on the type of nozzle, and examples include vertical nozzles, shower nozzles, and mist nozzles. From the perspective of developer permeability, non-image removal, and manufacturing efficiency, a method of supplying developer using a vertical nozzle or a method of continuously supplying developer using a spray nozzle is preferred. From the perspective of developer permeability to the image portion, a method of supplying developer using a spray nozzle is more preferred. In addition, after continuously supplying developer using a vertical nozzle, the substrate is rotated to remove the developer from the substrate, and after rotating and drying, the substrate is continuously supplied using a vertical nozzle again, and then the substrate is rotated to remove the developer from the substrate. This step may also be repeated multiple times. In addition, as a method for supplying the developer in the developing step, there can be adopted a step of continuously supplying the developer to the substrate, a step of keeping the developer in a substantially static state on the substrate, a step of vibrating the developer on the substrate using ultrasound or the like, and a step combining these.

作為顯影時間，5秒鐘～10分鐘為較佳，10秒鐘～5分鐘為更佳。顯影時的顯影液的溫度並無特別限定，通常能夠在10～45℃下進行，較佳為在20～40℃下進行。The developing time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developer during the development is not particularly limited, but can usually be carried out at 10 to 45°C, preferably 20 to 40°C.

亦可以在使用顯影液之處理之後，進一步進行沖洗。又，可以採用與圖案接觸之顯影液沒有完全乾燥之前供給沖洗液等的方法。 在進行溶劑顯影之情況下，使用與顯影液不同之有機溶劑進行沖洗為較佳。作為溶劑顯影時的沖洗液，可以舉出PGMEA（丙二醇單甲醚乙酸酯）、IPA（異丙醇）等，較佳為PGMEA。 在進行鹼性顯影之情況下，使用純水進行沖洗為較佳。 沖洗時間為10秒鐘～10分鐘為較佳，20秒鐘～5分鐘為更佳，5秒鐘～1分鐘為進一步較佳。沖洗時的沖洗液的溫度並無特別限定，能夠較佳為在10～45℃下進行，更較佳為在18℃～30℃下進行。After the developer is treated, further rinsing may be performed. Alternatively, a method may be adopted in which a rinsing solution is supplied before the developer in contact with the pattern is completely dried. In the case of solvent development, it is preferred to use an organic solvent different from the developer for rinsing. As rinsing solutions for solvent development, PGMEA (propylene glycol monomethyl ether acetate), IPA (isopropyl alcohol), etc. may be cited, and PGMEA is preferred. In the case of alkaline development, it is preferred to use pure water for rinsing. The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid during rinsing is not particularly limited, but can be preferably performed at 10 to 45°C, more preferably 18 to 30°C.

作為沖洗液包含有機溶劑時的有機溶劑，作為酯類，例如可以較佳地舉出乙酸乙酯、乙酸正丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯、ε-己內酯、δ-戊內酯、烷氧基乙酸烷基酯（例：烷氧基乙酸甲酯、烷氧基乙酸乙酯、烷氧基乙酸丁酯（例如，甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等））、3-烷氧基丙酸烷基酯類（例：3-烷氧基丙酸甲酯、3-烷氧基丙酸乙酯等（例如，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-乙氧基丙酸乙酯等））、2-烷氧基丙酸烷基酯類（例：2-烷氧基丙酸甲酯、2-烷氧基丙酸乙酯、2-烷氧基丙酸丙酯等（例如，2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯））、2-烷氧基-2-甲基丙酸甲酯及2-烷氧基-2-甲基丙酸乙酯（例如，2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等）、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯等，以及作為醚類，例如可以較佳地舉出二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚（PGME）、丙二醇單甲醚乙酸酯（PGMEA）、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯等，以及作為酮類，例如可以較佳地舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、N-甲基-2-吡咯啶酮等，以及作為芳香族烴類，例如可以較佳地舉出甲苯、二甲苯、苯甲醚、檸檬烯等、作為亞碸類，可以較佳地舉出二甲基亞碸以及作為醇類，可以較佳地舉出甲醇、乙醇、丙醇、異丙醇、丁醇、戊醇、辛醇、二乙二醇、丙二醇、甲基異丁基甲醇、三乙二醇等以及作為醯胺類，可以較佳地舉出N-甲基吡咯啶酮、N-乙基吡咯啶酮、二甲基甲醯胺等。When the rinsing liquid contains an organic solvent, the organic solvent may be preferably esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.)), alkyl 3-alkoxy propionates (e.g., 3-alkoxy propionates, etc.), and alkyl 3-alkoxy propionates. 2-alkoxypropionic acid methyl esters, 3-alkoxypropionic acid ethyl esters, etc. (for example, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, etc.)), 2-alkoxypropionic acid alkyl esters (for example, 2-alkoxypropionic acid methyl ester, 2-alkoxypropionic acid ethyl ester, 2-alkoxypropionic acid propyl ester, etc. (for example, 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and 2-alkoxy-2-methylpropionic acid ethyl ester (for example, 2-methoxy-2-methyl The ethers include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate. etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and as sulfoxides, dimethyl sulfoxide, and as alcohols, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc., can be preferably exemplified.

在沖洗液包含有機溶劑之情況下，有機溶劑能夠使用一種或混合使用兩種以上。在本發明中，尤其環戊酮、γ-丁內酯、二甲基亞碸、N-甲基吡咯啶酮、環己酮、PGMEA、PGME為較佳，環戊酮、γ-丁內酯、二甲基亞碸、PGMEA、PGME為更佳，環己酮、PGMEA為進一步較佳。When the rinsing liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are further preferred.

在沖洗液包含有機溶劑之情況下，沖洗液的50質量%以上為有機溶劑為較佳，70質量%以上為有機溶劑為更佳，90質量%以上為有機溶劑為進一步較佳。又，亦可以為沖洗液的100質量%為有機溶劑。When the rinse liquid contains an organic solvent, preferably 50 mass % or more of the rinse liquid is the organic solvent, more preferably 70 mass % or more of the rinse liquid is the organic solvent, and even more preferably 90 mass % or more of the rinse liquid is the organic solvent. Alternatively, 100 mass % of the rinse liquid may be the organic solvent.

沖洗液還可以包含其他成分。 作為其他成分，例如可以舉出公知的界面活性劑和公知的消泡劑等。The rinse solution may also contain other components. As other components, for example, well-known surfactants and well-known defoaming agents can be cited.

[沖洗液的供給方法] 關於沖洗液的供給方法，只要能夠形成所期望的圖案，則並無特別限制，存在將基材浸漬於沖洗液中之方法、在基材上的旋覆浸沒顯影、以噴淋形式向基材供給沖洗液之方法、藉由直式噴嘴等機構將顯影液連續供給至基材上之方法。 從沖洗液的滲透性、非圖像部的去除性、製造上的效率的觀點考慮，存在使用噴淋噴嘴、直式噴嘴、噴霧噴嘴等供給沖洗液之方法，使用噴霧噴嘴連續供給之方法為較佳，從沖洗液向圖像部的滲透性的觀點考慮，使用噴霧噴嘴進行供給之方法為更佳。噴嘴的種類並無特別限制，可以舉出直式噴嘴、噴淋噴嘴、噴霧噴嘴等。 亦即，沖洗步驟為藉由直式噴嘴將沖洗液供給或連續供給至上述曝光後的膜中之步驟為較佳，藉由噴霧噴嘴供給沖洗液之步驟為更佳。 又，作為沖洗步驟中之沖洗液的供給方法，能夠採用將沖洗液連續地供給至基材上之步驟、在基材上使沖洗液保持大致靜止狀態之步驟、在基材上利用超聲波等使沖洗液振動之步驟及組合了該等之步驟等。[Method for supplying rinse liquid] There are no particular restrictions on the method for supplying rinse liquid as long as the desired pattern can be formed. There are methods of immersing the substrate in the rinse liquid, performing rotary immersion development on the substrate, supplying the rinse liquid to the substrate in a spraying manner, and continuously supplying the developer to the substrate by a mechanism such as a vertical nozzle. From the perspective of the permeability of the rinse liquid, the removability of the non-image area, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a vertical nozzle, a spray nozzle, etc. The method of continuous supply using a spray nozzle is preferred. From the perspective of the permeability of the rinse liquid to the image area, the method of supplying using a spray nozzle is more preferred. There is no particular limitation on the type of nozzle, and vertical nozzles, shower nozzles, spray nozzles, etc. can be cited. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the film after exposure by a vertical nozzle, and it is more preferably a step of supplying the rinsing liquid by a spray nozzle. In addition, as a method of supplying the rinsing liquid in the rinsing step, it is possible to adopt a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially static state on the substrate, a step of vibrating the rinsing liquid on the substrate using ultrasound or the like, and a step combining these.

＜加熱步驟＞ 本發明的製造方法包括在50～450℃下對經顯影之上述膜進行加熱之步驟（加熱步驟）為較佳。 在膜形成步驟（層形成步驟）、乾燥步驟及顯影步驟之後包括加熱步驟為較佳。 本發明的硬化性樹脂組成物包含除了特定樹脂以外的聚合性化合物，但是能夠在該步驟中使除了特定樹脂以外的未反應的聚合性化合物進行硬化反應及使特定樹脂中之未反應的聚合性基進行硬化反應等。 又，在特定樹脂為聚醯亞胺前驅物且硬化性樹脂組成物包含熱鹼產生劑之情況下，在加熱步驟中，例如藉由熱鹼產生劑進行分解而產生鹼，從而使聚醯亞胺前驅物進行環化反應。 作為加熱步驟中之層的加熱溫度（最高加熱溫度），50℃以上為較佳，80℃以上為更佳，140℃以上為進一步較佳，150℃以上為特佳，160℃以上為更進一步較佳，170℃以上為最佳。作為上限，450℃以下為較佳，350℃以下為更佳，250℃以下為進一步較佳，220℃以下為特佳。<Heating step> The manufacturing method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450°C. It is preferred to include a heating step after the film formation step (layer formation step), the drying step, and the development step. The curable resin composition of the present invention contains polymerizable compounds other than the specific resin, but in this step, unreacted polymerizable compounds other than the specific resin can be cured and unreacted polymerizable groups in the specific resin can be cured. Furthermore, when the specific resin is a polyimide precursor and the curable resin composition contains a thermal alkali generator, in the heating step, for example, the thermal alkali generator is decomposed to generate a base, thereby causing the polyimide precursor to undergo a cyclization reaction. As the heating temperature (maximum heating temperature) of the layer in the heating step, 50°C or more is preferred, 80°C or more is more preferred, 140°C or more is further preferred, 150°C or more is particularly preferred, 160°C or more is further preferred, and 170°C or more is optimal. As the upper limit, 450°C or less is preferred, 350°C or less is more preferred, 250°C or less is further preferred, and 220°C or less is particularly preferred.

關於加熱，從加熱開始時的溫度至最高加熱溫度以1～12℃/分鐘的升溫速度進行為較佳，2～10℃/分鐘為更佳，3～10℃/分鐘為進一步較佳。藉由將升溫速度設為1℃/分鐘以上，能夠確保生產性，並且防止胺的過度揮發，藉由將升溫速度設為12℃/分鐘以下，能夠緩和硬化膜的殘存應力。另外，在為能夠急速加熱的烘箱的情況下，從加熱開始時的溫度至最高加熱溫度以1～8℃/秒鐘的升溫速度進行為較佳，2～7℃/秒鐘為更佳，3～6℃/秒鐘為進一步較佳。Regarding heating, it is preferred that the heating rate be 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the heating rate to 1°C/min or more, productivity can be ensured and excessive volatilization of amine can be prevented, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be relaxed. In addition, in the case of an oven capable of rapid heating, it is preferred that the heating rate be 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec.

加熱開始時的溫度為20℃～150℃為較佳，20℃～130℃為更佳，25℃～120℃為進一步較佳。加熱開始時的溫度是指，開始加熱至最高加熱溫度之步驟時的溫度。例如，在將硬化性樹脂組成物適用於基材上之後使其乾燥之情況下，為該乾燥後的膜（層）的溫度，例如從比硬化性樹脂組成物中所包含之溶劑的沸點低30～200℃的溫度開始逐漸升溫為較佳。The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when a curable resin composition is applied to a substrate and then dried, it is the temperature of the dried film (layer), and it is preferably to gradually increase the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the curable resin composition.

加熱時間（在最高加熱溫度下的加熱時間）為10～360分鐘為較佳，20～300分鐘為更佳，30～240分鐘為進一步較佳。The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.

尤其，在形成多層積層體之情況下，從硬化膜的層間的密接性的觀點考慮，在180℃～320℃的加熱溫度下進行加熱為較佳，在180℃～260℃下進行加熱為更佳。其理由尚不明確，但是認為其原因在於藉由設為該溫度，層間的特定樹脂中之聚合性基彼此進行交聯反應。In particular, when forming a multi-layer laminate, from the viewpoint of the adhesion between the layers of the cured film, heating is preferably performed at a heating temperature of 180°C to 320°C, and more preferably at 180°C to 260°C. The reason for this is not clear, but it is believed that the reason is that the polymerizable groups in the specific resin between the layers undergo cross-linking reactions by setting the temperature to this level.

加熱可以分階段進行。作為例子，可以進行如下預處理步驟，亦即，從25℃以3℃/分鐘升溫至180℃且在180℃下保持60分鐘，並且從180℃以2℃/分鐘升溫至200℃且在200℃下保持120分鐘。作為預處理步驟的加熱溫度為100～200℃為較佳，110～190℃為更佳，120～185℃為進一步較佳。在該預處理步驟中，如美國專利9159547號說明書中所記載，一邊照射紫外線一邊進行處理亦較佳。藉由該等預處理步驟，能夠提高膜的特性。預處理步驟在10秒鐘～2小時左右的短時間內進行即可，15秒鐘～30分鐘為更佳。預處理可以為兩階段以上的步驟，例如可以在100～150℃的範圍內進行預處理步驟1，之後在150～200℃的範圍內進行預處理步驟2。Heating can be performed in stages. As an example, the following pretreatment step can be performed, that is, the temperature is raised from 25°C to 180°C at 3°C/min and maintained at 180°C for 60 minutes, and the temperature is raised from 180°C to 200°C at 2°C/min and maintained at 200°C for 120 minutes. The heating temperature of the pretreatment step is preferably 100-200°C, more preferably 110-190°C, and further preferably 120-185°C. In the pretreatment step, as described in the specification of U.S. Patent No. 9159547, it is also preferred to perform the treatment while irradiating ultraviolet rays. By means of such pretreatment steps, the properties of the membrane can be improved. The pretreatment step can be carried out in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can be a step of more than two stages, for example, pretreatment step 1 can be carried out in the range of 100 to 150°C, and then pretreatment step 2 can be carried out in the range of 150 to 200°C.

進而，可以在加熱之後進行冷卻，作為此時的冷卻速度，1～5℃/分鐘為較佳。Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5°C/minute.

在防止特定樹脂分解的方面而言，藉由在加熱步驟中使氮氣、氦氣、氬氣等非活性氣體流過等而在低氧濃度的環境下進行為較佳。氧濃度為50ppm（體積比）以下為較佳，20ppm（體積比）以下為更佳。 作為加熱機構，並無特別限定，例如可以舉出加熱板、紅外線爐、電烘箱、熱風式烘箱等。In terms of preventing the decomposition of specific resins, it is better to conduct the heating process in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium, or argon during the heating step. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. The heating mechanism is not particularly limited, and examples thereof include a heating plate, an infrared furnace, an electric oven, a hot air oven, and the like.

＜金屬層形成步驟＞ 本發明的製造方法包括在顯影處理後的膜（硬化性樹脂組成物層）的表面上形成金屬層之金屬層形成步驟為較佳。<Metal layer forming step> The manufacturing method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (hardening resin composition layer) after the development process.

作為金屬層，並無特別限定，能夠使用現有的金屬種類，可以例示銅、鋁、鎳、釩、鈦、鉻、鈷、金、鎢及包含該等金屬之合金，銅及鋁為更佳，銅為進一步較佳。The metal layer is not particularly limited, and existing metals can be used. Examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, and alloys containing these metals. Copper and aluminum are more preferred, and copper is further preferred.

金屬層的形成方法並無特別限定，能夠適用現有的方法。例如，能夠使用日本特開2007-157879號公報、日本特表2001-521288號公報、日本特開2004-214501號公報、日本特開2004-101850號公報中所記載之方法。例如，可以考慮光微影、剝離、電解電鍍、無電解電鍍、蝕刻、印刷及組合該等之方法等。更具體而言，可以舉出組合了濺射、光微影及蝕刻之圖案化方法、組合了光微影和電解電鍍之圖案化方法。The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, and Japanese Patent Publication No. 2004-101850 can be used. For example, photolithography, stripping, electrolytic plating, electroless plating, etching, printing, and a combination of these methods can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited.

作為金屬層的厚度，可以舉出最厚的部分為0.01～100μm作為例子，0.1～50μm為較佳，1～10μm為更佳。As an example of the thickness of the metal layer, the thickest part may be 0.01 to 100 μm, preferably 0.1 to 50 μm, and more preferably 1 to 10 μm.

＜積層步驟＞ 本發明的製造方法還包括積層步驟為較佳。<Lamination step> The manufacturing method of the present invention preferably also includes a layering step.

積層步驟為包括在硬化膜（樹脂層）或金屬層的表面上再次依序進行（a）膜形成步驟（層形成步驟）、（b）曝光步驟、（c）顯影步驟、（d）加熱步驟之一系列步驟。其中，可以為僅重複（a）膜形成步驟之態樣。又，亦可以設為（d）加熱步驟在積層的最後或中間統括進行之態樣。亦即，亦可以設為如下態樣，亦即，重複進行既定次數的（a）～（c）的步驟，之後進行（d）的加熱，從而將所積層之硬化性樹脂組成物層統括硬化。又，亦可以在（c）顯影步驟之後包括（e）金屬層形成步驟，此時亦可以每次進行（d）的加熱，亦可以在積層既定次數之後統括進行（d）的加熱。在積層步驟中可以進一步適當包括上述乾燥步驟和加熱步驟等，這係毋庸置疑的。The lamination step includes a series of steps including (a) film formation step (layer formation step), (b) exposure step, (c) development step, and (d) heating step, which are sequentially performed again on the surface of the hardened film (resin layer) or metal layer. Among them, only (a) film formation step may be repeated. Alternatively, (d) heating step may be performed at the end or in the middle of the lamination. That is, (a) to (c) steps may be repeated a predetermined number of times, and then (d) heating may be performed to cure the hardened resin composition layer that has been laminated. Furthermore, the step (e) of forming a metal layer may be included after the step (c) of developing, and the step (d) of heating may be performed each time, or the step (d) of heating may be performed all at once after a predetermined number of times of lamination. It is beyond doubt that the step of lamination may further include the above-mentioned drying step and heating step, etc.

在積層步驟之後進一步進行積層步驟之情況下，可以在上述加熱步驟之後，上述曝光步驟之後或上述金屬層形成步驟之後，進一步進行表面活化處理步驟。作為表面活化處理，可以例示電漿處理。When a further layering step is performed after the layering step, a surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer forming step. As the surface activation treatment, plasma treatment may be exemplified.

上述積層步驟進行2～5次為較佳，進行3～5次為更佳。又，積層步驟中之各層可以為組成、形狀、膜厚等相同的層，亦可以為不同之層。The above-mentioned lamination step is preferably performed 2 to 5 times, and more preferably performed 3 to 5 times. In addition, the layers in the lamination step can be the same in composition, shape, film thickness, etc., or different in composition, shape, film thickness, etc.

例如，可以舉出如樹脂層/金屬層/樹脂層/金屬層/樹脂層/金屬層的樹脂層為2層以上且20層以下之結構作為例子，樹脂層為3層以上且7層以下的結構為較佳，3層以上且5層以下為進一步較佳。For example, a structure such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer in which the number of resin layers is 2 or more and 20 or less can be cited as an example, a structure in which the number of resin layers is 3 or more and 7 or less is preferred, and a structure in which the number of resin layers is 3 or more and 5 or less is further preferred.

＜表面活性化處理步驟＞ 本發明的硬化膜的製造方法可以包括對上述金屬層及感光性樹脂組成物層的至少一部分進行表面活性化處理之表面活性化處理步驟。 表面活性化處理步驟通常在金屬層形成步驟之後進行，但是亦可以在上述曝光顯影步驟之後，對感光性樹脂組成物層進行表面活性化處理步驟之後進行金屬層形成步驟。 關於表面活性化處理，可以僅對金屬層的至少一部分進行，亦可以僅對曝光後的感光性樹脂組成物層的至少一部分進行，亦可以分別對金屬層及曝光後的感光性樹脂組成物層這兩者的至少一部分進行。對金屬層的至少一部分進行表面活性化處理為較佳，對金屬層中在表面上形成感光性樹脂組成物層之區域的一部分或全部進行表面活性化處理為較佳。如此，藉由對金屬層的表面進行表面活性化處理，能夠提高與設置於其表面上之樹脂層的密接性。 又，對曝光後的感光性樹脂組成物層（樹脂層）的一部分或全部亦進行表面活性化處理為較佳。如此，藉由對感光性樹脂組成物層的表面進行表面活性化處理，能夠提高與設置於經表面活性化處理之表面上之金屬層和樹脂層的密接性。 作為表面活性化處理，具體而言，選自各種原料氣體（氧氣、氫氣、氬氣、氮氣、氮氣/氫氣混合氣體、氬氣/氧氣混合氣體等）的電漿處理、電暈放電處理、基於CF4 /O2 、NF3 /O2 、SF6 、NF3 、NF3 /O2 之蝕刻處理、基於紫外線（UV）臭氧法之表面處理、浸漬於鹽酸水溶液中以去除氧化皮膜之後浸漬於包含具有至少一種胺基和硫醇基之化合物之有機表面處理劑中的浸漬處理、使用了刷子之機械粗面化處理，電漿處理為較佳，尤其使用氧氣作為原料氣體之氧氣電漿處理為較佳。在進行電暈放電處理之情況下，能量為500～200,000J/m2 為較佳，1000～100,000J/m2 為更佳，10,000～50,000J/m2 為最佳。<Surface activation treatment step> The method for producing a cured film of the present invention may include a surface activation treatment step of performing surface activation treatment on at least a portion of the metal layer and the photosensitive resin composition layer. The surface activation treatment step is usually performed after the metal layer forming step, but the metal layer forming step may be performed after the exposure and development step and then after the photosensitive resin composition layer is subjected to the surface activation treatment step. The surface activation treatment may be performed only on at least a portion of the metal layer, only on at least a portion of the exposed photosensitive resin composition layer, or on at least a portion of both the metal layer and the exposed photosensitive resin composition layer. It is preferred to perform surface activation treatment on at least a portion of the metal layer, and it is preferred to perform surface activation treatment on a portion or all of the region of the metal layer where the photosensitive resin composition layer is formed on the surface. In this way, by performing surface activation treatment on the surface of the metal layer, the adhesion with the resin layer disposed on the surface can be improved. In addition, it is preferred to perform surface activation treatment on a portion or all of the photosensitive resin composition layer (resin layer) after exposure. In this way, by performing surface activation treatment on the surface of the photosensitive resin composition layer, the adhesion with the metal layer and the resin layer disposed on the surface subjected to surface activation treatment can be improved. Specifically, the surface activation treatment includes plasma treatment using various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on CF4 / O2 , NF3 / O2 , SF6 , NF3 , NF3 / O2 , surface treatment based on ultraviolet (UV) ozone method, immersion treatment in an organic surface treatment agent containing a compound having at least one amino group and thiol group after immersion in an aqueous hydrochloric acid solution to remove an oxide film, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. When performing corona discharge treatment, the energy is preferably 500-200,000 J/ m2 , more preferably 1000-100,000 J/ m2 , and most preferably 10,000-50,000 J/ m2 .

在本發明中，尤其以在設置金屬層之後進一步覆蓋上述金屬層之方式形成上述硬化性樹脂組成物的硬化膜（樹脂層）之態樣為較佳。具體而言，可以舉出依序重複（a）膜形成步驟、（b）曝光步驟、（c）顯影步驟、（e）金屬層形成步驟、（d）加熱步驟之態樣或依序重複（a）膜形成步驟、（b）曝光步驟、（c）顯影步驟、（e）金屬層形成步驟，最後或中間統括設置（d）加熱步驟之態樣。藉由交替進行積層硬化性樹脂組成物層（樹脂層）之積層步驟和金屬層形成步驟，能夠交替積層硬化性樹脂組成物層（樹脂層）和金屬層。In the present invention, it is particularly preferred that the hardened film (resin layer) of the hardening resin composition is formed by further covering the metal layer after the metal layer is provided. Specifically, there can be cited an embodiment in which (a) the film forming step, (b) the exposure step, (c) the development step, (e) the metal layer forming step, and (d) the heating step are repeated in sequence, or an embodiment in which (a) the film forming step, (b) the exposure step, (c) the development step, and (e) the metal layer forming step are repeated in sequence, and (d) the heating step is provided at the end or in the middle. By alternately performing the step of laminating the hardening resin composition layer (resin layer) and the step of forming the metal layer, the hardening resin composition layer (resin layer) and the metal layer can be alternately laminated.

本發明中亦揭示包含本發明的硬化膜或積層體之半導體器件。作為將本發明的硬化性樹脂組成物用於再配線層用層間絕緣膜的形成中之半導體器件的具體例，能夠參閱日本特開2016-027357號公報的0213～0218段的記載及圖1的記載，且該等內容被編入本說明書中。The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As a specific example of a semiconductor device using the curable resin composition of the present invention in forming an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Application Publication No. 2016-027357, and the contents are incorporated into this specification.

（樹脂） 本發明的樹脂包含上述式（1-1）所表示之重複單元且包含選自包括上述式（3-1）所表示之重複單元、上述式（3-2）所表示之重複單元、上述式（3-3）所表示之重複單元及上述式（3-4）所表示之重複單元之群組中的至少一種重複單元為較佳。 本發明的樹脂包含選自包括上述式（3-1）所表示之重複單元及上述式（3-2）所表示之重複單元、上述式（3-3）所表示之重複單元及上述式（3-4）所表示之重複單元之群組中的至少一種重複單元，除此以外，與上述特定樹脂的含義相同，較佳態樣亦相同。(Resin) The resin of the present invention preferably contains the repeating unit represented by the above formula (1-1) and contains at least one repeating unit selected from the group including the repeating unit represented by the above formula (3-1), the repeating unit represented by the above formula (3-2), the repeating unit represented by the above formula (3-3) and the repeating unit represented by the above formula (3-4). The resin of the present invention contains at least one repeating unit selected from the group including the repeating unit represented by the above formula (3-1) and the repeating unit represented by the above formula (3-2), the repeating unit represented by the above formula (3-3) and the repeating unit represented by the above formula (3-4). Except for this, the resin has the same meaning as the above specific resin and the preferred embodiment is also the same.

＜用途＞ 本發明的樹脂用作硬化性樹脂組成物中所包含之樹脂為較佳。 又，例如在層間絕緣膜用組成物等使用先前之聚醯亞胺之組成物中，並無特別限制，能夠將先前的聚醯亞胺的一部分或全部替換成本發明的樹脂來使用。 認為由於本發明的樹脂的耐藥品性優異，因此本發明的樹脂例如較佳地用於如下組成物中，該組成物為用於形成絕緣膜的組成物、用於形成積層體的組成物等用於需要耐藥品性之用途中之組成物。 [實施例]<Application> The resin of the present invention is preferably used as a resin included in a curable resin composition. In addition, in a composition using a conventional polyimide, such as an interlayer insulating film composition, there is no particular limitation, and a part or all of the conventional polyimide can be replaced with the resin of the present invention. Since the resin of the present invention has excellent chemical resistance, the resin of the present invention is preferably used in a composition for forming an insulating film, a composition for forming a laminate, and other compositions for applications requiring chemical resistance. [Example]

以下，舉出實施例對本發明進行更詳細的說明。以下實施例所示之材料、使用量、比例、處理內容、處理步驟等只要不脫離本發明的宗旨，則能夠適當地進行變更。從而，本發明的範圍並不限定於以下所示之具體例。以下，除非另有說明，則“份”、“%”為質量基準。The present invention is described in more detail below by way of examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

（特定樹脂的合成） ＜二胺的合成＞ [二硝基體（A-1）的合成] 在安裝有冷凝器及攪拌機之燒瓶中，將甲基丙烯酸2-羥基乙酯（FFUJIFILM Wako Pure Chemical Corporation製）26.0g（0.2莫耳）、脫水吡啶（FFUJIFILM Wako Pure Chemical Corporation製）17.4g（0.22莫耳）溶解於78g的乙酸乙酯中，並冷卻至5℃以下。接著，將3,5-二硝基苯甲醯基氯（Tokyo Chemical Industry Co.,Ltd.製）48.4g（0.21莫耳）溶解於145g乙酸乙酯中，並使用滴加漏斗將該溶液經1小時滴加到燒瓶中。在滴加結束之後，在10℃以下的溫度下攪拌30分鐘，升溫至25℃並攪拌了3小時。接著，用乙酸乙酯（CH3 COOEt）600mL稀釋反應液，並轉移到分液漏斗中，用水300mL、飽和碳酸氫鈉水300mL、稀鹽酸300mL、飽和食鹽水依序進行了清洗。在分液清洗之後，用硫酸鎂30g進行乾燥，之後使用蒸餾器進行濃縮和真空乾燥，從而獲得了61.0g的二硝基體（A-1）。由NMR光譜確認為二硝基體（A-1）。藉由1 H-NMR對二硝基體（A-1）進行了分析。將其結果示於以下。1 H-NMR資料（氘代氯仿、400MHz、內部標準：四甲基矽烷）δ（ppm）=1.97（s、3H）、4.55-4.57（m、2H）、4.70-4.73（m、2H）、5.63（s、1H）、6.16（s、1H）、9.16-9.17（d、2H）、9.24-9.25（d、1H） 以相同的方式合成了後述結構的二硝基體（A-2）～（A-8）。(Synthesis of specific resin) <Synthesis of diamine> [Synthesis of dinitro compound (A-1)] In a flask equipped with a condenser and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by FFUJIFILM Wako Pure Chemical Corporation) and 17.4 g (0.22 mol) of dehydrated pyridine (manufactured by FFUJIFILM Wako Pure Chemical Corporation) were dissolved in 78 g of ethyl acetate, and the mixture was cooled to 5°C or less. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate, and the solution was added dropwise to the flask over 1 hour using a dropping funnel. After the addition was completed, the mixture was stirred at a temperature below 10°C for 30 minutes, and then the temperature was raised to 25°C and stirred for 3 hours. The reaction solution was then diluted with 600 mL of ethyl acetate (CH 3 COOEt), transferred to a separatory funnel, and washed with 300 mL of water, 300 mL of saturated sodium bicarbonate, 300 mL of dilute hydrochloric acid, and saturated saline in that order. After separation and washing, the mixture was dried with 30 g of magnesium sulfate, and then concentrated and vacuum dried using a distiller to obtain 61.0 g of a dinitro compound (A-1). The NMR spectrum confirmed that the compound was a dinitro compound (A-1). The dinitro compound (A-1) was analyzed by 1 H-NMR. The results are shown below. 1 H-NMR data (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 1.97 (s, 3H), 4.55-4.57 (m, 2H), 4.70-4.73 (m, 2H), 5.63 (s, 1H), 6.16 (s, 1H), 9.16-9.17 (d, 2H), 9.24-9.25 (d, 1H) The following dinitro compounds (A-2) to (A-8) were synthesized in the same manner.

[二胺（AA-1）的合成] 將還原鐵（FFUJIFILM Wako Pure Chemical Corporation製）27.9g（500毫莫耳）、氯化銨（FFUJIFILM Wako Pure Chemical Corporation製）5.9g（110毫莫耳）、乙酸（FFUJIFILM Wako Pure Chemical Corporation製）3.0g（50毫莫耳）、2,2,6,6-四甲基哌啶1-氧基自由基（Tokyo Chemical Industry Co.,Ltd.製）0.03g稱重到安裝有冷凝器及攪拌機之燒瓶中，並添加異丙醇（IPA）200mL、純水30mL進行了攪拌。 接著，將二硝基體（A-1）16.2g一點一點添加1小時，並攪拌了30分鐘。接著，將外部溫度升溫至85℃並攪拌2小時，在冷卻至25℃以下之後，使用CELITE（註冊商標）進行了過濾。用旋轉蒸發儀器將濾液進行濃縮，並溶解於乙酸乙酯800mL中。將其轉移到分液漏斗中，用飽和碳酸氫鈉水300mL清洗兩次，並用水300mL、飽和食鹽水300mL依序進行了清洗。在分液清洗之後，用硫酸鎂30g進行乾燥之後，使用蒸餾器進行濃縮和真空乾燥，從而獲得了11.0g的二胺（AA-1）。由NMR光譜確認為二胺（AA-1）。1 H-NMR資料（氘代氯仿、400MHz、內部標準：四甲基矽烷）δ（ppm）=1.95（s、3H）、3.68（s、4H）、4.45-4.47（m、2H）、4.50-4.53（m、2H）、5.58（s、1H）、6.14（s、1H）、6.19-6.20（t、1H）、6.77-6.78（d、2H） 以相同的方式，使用二硝基體（A-2）～（A-8）來代替二硝基體（A-1），從而合成了下述結構的二胺（AA-2）～（AA-8）。 [化學式64] [化學式65] [化學式66] [Synthesis of diamine (AA-1)] 27.9 g (500 mmol) of reduced iron (manufactured by FFUJIFILM Wako Pure Chemical Corporation), 5.9 g (110 mmol) of ammonium chloride (manufactured by FFUJIFILM Wako Pure Chemical Corporation), 3.0 g (50 mmol) of acetic acid (manufactured by FFUJIFILM Wako Pure Chemical Corporation), and 0.03 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were weighed into a flask equipped with a condenser and a stirrer, and 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred. Then, 16.2 g of the dinitro compound (A-1) was added little by little over 1 hour and stirred for 30 minutes. Next, the external temperature was raised to 85°C and stirred for 2 hours. After cooling to below 25°C, the mixture was filtered using CELITE (registered trademark). The filtrate was concentrated using a rotary evaporator and dissolved in 800 mL of ethyl acetate. The mixture was transferred to a separatory funnel and washed twice with 300 mL of saturated sodium bicarbonate water, and then washed with 300 mL of water and 300 mL of saturated saline water. After separation and washing, the mixture was dried with 30 g of magnesium sulfate, concentrated using a distiller, and vacuum dried to obtain 11.0 g of diamine (AA-1). The NMR spectrum confirmed that the mixture was diamine (AA-1). 1 H-NMR data (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 1.95 (s, 3H), 3.68 (s, 4H), 4.45-4.47 (m, 2H), 4.50-4.53 (m, 2H), 5.58 (s, 1H), 6.14 (s, 1H), 6.19-6.20 (t, 1H), 6.77-6.78 (d, 2H) In the same manner, using dinitro compounds (A-2) to (A-8) instead of dinitro compounds (A-1), diamines (AA-2) to (AA-8) of the following structures were synthesized. [Chemical formula 64] [Chemical formula 65] [Chemical formula 66]

＜酐（MA-1）的合成＞ 在安裝有冷凝器及攪拌機之燒瓶中，將偏苯三甲酸酐氯化物（Tokyo Chemical Industry Co.,Ltd.製）18.5g（0.88莫耳）溶解於乙酸乙酯200g中，並冷卻至-10℃以下。接著，將二胺（AA-1）10.6g（40毫莫耳）、吡啶7.12g（90毫莫耳）溶解於乙酸乙酯60g中，並將其滴加了1小時。滴加後，在-10℃以下的溫度下攪拌了1小時，並在25℃下攪拌了1小時。接著，添加乙酸乙酯500mL、水300mL並攪拌10分鐘之後，將其轉移到分液漏斗中，用300mL的水進行了清洗之後，用200mL的飽和碳酸氫鈉水溶液清洗兩次，並用200mL的稀鹽酸水溶液、飽和食鹽水依序進行了清洗。將其用硫酸鎂進行乾燥，用蒸餾器進行濃縮之後，將乙酸乙酯溶液結晶至己烷上。將其進行過濾和真空乾燥，從而獲得了酐（MA-1）20.0g。由1 H-NMR光譜確認為酐（MA-1）。藉由1 H-NMR對酐（MA-1）進行了分析。將其結果示於以下。1 H-NMR資料（重DMSO、400MHz、內部標準：四甲基矽烷） δ（ppm）=1.88（s、3H）、4.44-4.47（q、2H）、4.60-4.62（q、2H）、5.70（s、2H）、6.06（s、1H）、8.23-8.26（m、4H）、8.52-8.54（d、2H）、8.65（s、2H）、8.82-8.83（t、1H）、10.98（s、2H） [化學式67] <Synthesis of anhydride (MA-1)> In a flask equipped with a condenser and a stirrer, 18.5 g (0.88 mol) of trimellitic anhydride chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 200 g of ethyl acetate and cooled to below -10°C. Then, 10.6 g (40 mmol) of diamine (AA-1) and 7.12 g (90 mmol) of pyridine were dissolved in 60 g of ethyl acetate and added dropwise for 1 hour. After the addition, the mixture was stirred at a temperature below -10°C for 1 hour and at 25°C for 1 hour. Next, 500 mL of ethyl acetate and 300 mL of water were added and stirred for 10 minutes. The mixture was transferred to a separatory funnel and washed with 300 mL of water, then washed twice with 200 mL of saturated sodium bicarbonate aqueous solution, and washed with 200 mL of dilute hydrochloric acid aqueous solution and saturated saline water, respectively. The mixture was dried with magnesium sulfate, concentrated with a distiller, and the ethyl acetate solution was crystallized onto hexane. The mixture was filtered and vacuum dried to obtain 20.0 g of anhydride (MA-1). The anhydride (MA-1) was confirmed to be anhydride (MA-1) by 1 H-NMR spectrum. The anhydride (MA-1) was analyzed by 1 H-NMR. The results are shown below. 1 H-NMR data (heavy DMSO, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 1.88 (s, 3H), 4.44-4.47 (q, 2H), 4.60-4.62 (q, 2H), 5.70 (s, 2H), 6.06 (s, 1H), 8.23-8.26 (m, 4H), 8.52-8.54 (d, 2H), 8.65 (s, 2H), 8.82-8.83 (t, 1H), 10.98 (s, 2H) [Chemical formula 67]

＜聚醯亞胺前驅物樹脂（PZ-1）的合成例＞ 在安裝有冷凝器及攪拌機之燒瓶中，一邊去除水分一邊使氧代二鄰苯二甲酸二酐（Tokyo Chemical Industry Co.,Ltd.製）9.31g（30毫莫耳）懸浮於二甘二甲醚（Tokyo Chemical Industry Co.,Ltd.製）60g中。連續添加甲基丙烯酸2-羥基乙酯（Tokyo Chemical Industry Co.,Ltd.製）8.07g（62毫莫耳）、吡啶（Tokyo Chemical Industry Co.,Ltd.製）8.70g（110毫莫耳）、2,2,6,6-四甲基哌啶基1-氧基自由基（Tokyo Chemical Industry Co.,Ltd.製）0.04g，並在60℃的溫度下攪拌了4小時。接著，將混合物冷卻至-20℃之後，滴加了90分鐘亞硫醯氯8.68g（73毫莫耳）。可以獲得吡啶鹽酸鹽的白色沉澱物。接著，將混合物加溫至室溫並攪拌2小時之後，添加了下述式（BO-1）所表示之化合物6.40g（20毫莫耳）。接著，將4,4’-二胺基二苯醚（Tokyo Chemical Industry Co.,Ltd.製、二胺）9.01g（45毫莫耳）溶解於N-甲基吡咯啶酮（NMP）60mL中而獲得者經2小時滴加來進行了添加。添加上述二胺之期間，黏度增加。接著，添加甲醇6.0g（188毫莫耳）和2,2,6,6-四甲基哌啶1-氧基自由基（Tokyo Chemical Industry Co.,Ltd.製）0.05g，並將混合物攪拌了2小時。接著，使聚醯亞胺前驅物樹脂在3升水中沉澱，並將水-聚醯亞胺前驅物樹脂混合物以500rpm的速度攪拌了15分鐘。藉由過濾而獲取聚醯亞胺前驅物樹脂，並在3升水中再次攪拌30分鐘並再次進行了過濾。接著，在減壓狀態下，將所獲得之聚醯亞胺前驅物樹脂在45℃下乾燥了1天。關於該聚醯亞胺前驅物PZ-1的分子量，重量平均分子量（Mw）=21,600，數量平均分子量（Mn）=9,500。 推測PZ-1的結構為由下述式（PZ-1）表示之結構。 [化學式68] [化學式69] <Synthesis Example of Polyimide Procurator Resin (PZ-1)> In a flask equipped with a condenser and a stirrer, 9.31 g (30 mmol) of oxydiphthalic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was suspended in 60 g of diethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) while removing water. 8.07 g (62 mmol) of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.70 g (110 mmol) of pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.04 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added successively, and stirred at 60°C for 4 hours. Then, after the mixture was cooled to -20°C, 8.68 g (73 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Then, after the mixture was heated to room temperature and stirred for 2 hours, 6.40 g (20 mmol) of the compound represented by the following formula (BO-1) was added. Next, 9.01 g (45 mmol) of 4,4'-diaminodiphenyl ether (Tokyo Chemical Industry Co., Ltd., diamine) dissolved in 60 mL of N-methylpyrrolidone (NMP) was added dropwise over 2 hours. During the addition of the diamine, the viscosity increased. Next, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, the polyimide proto-driver resin was precipitated in 3 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 3 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 1 day under reduced pressure. The molecular weight of the polyimide precursor PZ-1 was a weight average molecular weight (Mw) = 21,600 and a number average molecular weight (Mn) = 9,500. The structure of PZ-1 is estimated to be a structure represented by the following formula (PZ-1). [Chemical formula 68] [Chemical formula 69]

＜聚醯亞胺前驅物樹脂（PZ-2）的合成例＞ 在安裝有冷凝器及攪拌機之燒瓶中，一邊去除水分一邊使氧代二鄰苯二甲酸二酐（Tokyo Chemical Industry Co.,Ltd.製）10.9g（35毫莫耳）懸浮於二甘二甲醚（Tokyo Chemical Industry Co.,Ltd.製）60.0g中。連續添加甲基丙烯酸2-羥基乙酯（Tokyo Chemical Industry Co.,Ltd.製）9.37g（50.4毫莫耳）、二乙二醇單乙醚（Tokyo Chemical Industry Co.,Ltd.製）2.90g（21.6毫莫耳）、吡啶（Tokyo Chemical Industry Co.,Ltd.製）8.70g（110毫莫耳）、氫醌（Tokyo Chemical Industry Co.,Ltd.製）0.03g，並在60℃的溫度下攪拌了4小時。接著，將混合物冷卻至-20℃之後，滴加了90分鐘亞硫醯氯（Tokyo Chemical Industry Co.,Ltd.製）8.68g（73毫莫耳）。可以獲得吡啶鹽酸鹽的白色沉澱物。接著，將混合物加溫至室溫並攪拌2小時之後，添加了上述式（BO-1）所表示之化合物4.78g（15毫莫耳）。接著，將4,4’-二胺基二苯醚（Tokyo Chemical Industry Co.,Ltd.製、二胺）9.01g（45毫莫耳）溶解於NMP60mL中而獲得者經2小時滴加來進行了添加。添加上述二胺之期間，黏度增加。接著，添加乙醇9.3g（200毫莫耳）和2,2,6,6-四甲基哌啶1-氧基自由基（Tokyo Chemical Industry Co.,Ltd.製）0.05g，並將混合物攪拌了2小時。接著，使聚醯亞胺前驅物樹脂在3升水中沉澱，並將水-聚醯亞胺前驅物樹脂混合物以500rpm的速度攪拌了15分鐘。藉由過濾而獲取聚醯亞胺前驅物樹脂，並在3升水中再次攪拌30分鐘並再次進行了過濾。接著，在減壓狀態下，將所獲得之聚醯亞胺前驅物樹脂在45℃下乾燥了1天。關於該聚醯亞胺前驅物PZ-2的分子量，Mw=23,100，Mn=10,900。 推測PZ-2的結構為由下述式（PZ-2）表示之結構。式中，*表示與R1所鍵結之氧原子的鍵結部位。 [化學式70] <Synthesis Example of Polyimide Procurator Resin (PZ-2)> In a flask equipped with a condenser and a stirrer, 10.9 g (35 mmol) of oxydiphthalic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was suspended in 60.0 g of diethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) while removing water. 9.37 g (50.4 mmol) of 2-hydroxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd.), 2.90 g (21.6 mmol) of diethylene glycol monoethyl ether (Tokyo Chemical Industry Co., Ltd.), 8.70 g (110 mmol) of pyridine (Tokyo Chemical Industry Co., Ltd.), and 0.03 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were added successively, and stirred at 60°C for 4 hours. Then, after the mixture was cooled to -20°C, 8.68 g (73 mmol) of thionyl chloride (Tokyo Chemical Industry Co., Ltd.) was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature and stirred for 2 hours, and then 4.78 g (15 mmol) of the compound represented by the above formula (BO-1) was added. Then, 9.01 g (45 mmol) of 4,4'-diaminodiphenyl ether (Tokyo Chemical Industry Co., Ltd., diamine) dissolved in 60 mL of NMP was added dropwise over 2 hours. During the addition of the diamine, the viscosity increased. Next, 9.3 g (200 mmol) of ethanol and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 3 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and was stirred again in 3 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 1 day under reduced pressure. Regarding the molecular weight of the polyimide precursor PZ-2, Mw=23,100, Mn=10,900. The structure of PZ-2 is estimated to be the structure represented by the following formula (PZ-2). In the formula, * represents the bonding site with the oxygen atom to which R1 is bonded. [Chemical Formula 70]

＜聚醯亞胺前驅物樹脂（PZ-3）的合成例＞ 在安裝有冷凝器及攪拌機之燒瓶中，一邊去除水分一邊使氧代二鄰苯二甲酸二酐（Tokyo Chemical Industry Co.,Ltd.製）10.9g（40毫莫耳）懸浮於二甘二甲醚（Tokyo Chemical Industry Co.,Ltd.製）60g中。連續添加二乙二醇單乙醚（Tokyo Chemical Industry Co.,Ltd.製）9.66g（72毫莫耳）、吡啶（Tokyo Chemical Industry Co.,Ltd.製）8.70g（110毫莫耳）、2,2,6,6-四甲基哌啶基1-氧基自由基（Tokyo Chemical Industry Co.,Ltd.製）0.03g，並在60℃的溫度下攪拌了4小時。接著，將混合物冷卻至-20℃之後，滴加了90分鐘亞硫醯氯（Tokyo Chemical Industry Co.,Ltd.製）8.68g（73毫莫耳）。可以獲得吡啶鹽酸鹽的白色沉澱物。接著，將混合物加溫至室溫並攪拌2小時之後，添加了上述式（BO-1）所表示之化合物4.78g（15毫莫耳）。接著，將二胺（AA-1）11.9g（45毫莫耳）溶解於NMP60mL中而獲得者經2小時滴加來進行了添加。添加上述二胺之期間，黏度增加。接著，添加甲醇6.0g（188毫莫耳）和2,2,6,6-四甲基哌啶1-氧基自由基（Tokyo Chemical Industry Co.,Ltd.製）0.05g，並將混合物攪拌了2小時。接著，使聚醯亞胺前驅物樹脂在3升水中沉澱，並將水-聚醯亞胺前驅物樹脂混合物以500rpm的速度攪拌了15分鐘。藉由過濾而獲取聚醯亞胺前驅物樹脂，並在3升水中再次攪拌30分鐘並再次進行了過濾。接著，在減壓狀態下，將所獲得之聚醯亞胺前驅物樹脂在45℃下乾燥了1天。關於該聚醯亞胺前驅物PZ-3的分子量，Mw=22,200，Mn=10,400。 推測PZ-3的結構為由下述式（PZ-3）表示之結構。 [化學式71] <Synthesis Example of Polyimide Procurator Resin (PZ-3)> In a flask equipped with a condenser and a stirrer, 10.9 g (40 mmol) of oxydiphthalic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was suspended in 60 g of diethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) while removing water. 9.66 g (72 mmol) of diethylene glycol monoethyl ether (Tokyo Chemical Industry Co., Ltd.), 8.70 g (110 mmol) of pyridine (Tokyo Chemical Industry Co., Ltd.), and 0.03 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were added successively, and stirred at 60°C for 4 hours. Then, after the mixture was cooled to -20°C, 8.68 g (73 mmol) of thionyl chloride (Tokyo Chemical Industry Co., Ltd.) was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, the mixture was heated to room temperature and stirred for 2 hours, and then 4.78 g (15 mmol) of the compound represented by the above formula (BO-1) was added. Then, 11.9 g (45 mmol) of diamine (AA-1) dissolved in 60 mL of NMP was added dropwise over 2 hours. During the addition of the above diamine, the viscosity increased. Next, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, the polyimide proto-driver resin was precipitated in 3 liters of water, and the water-polyimide proto-driver resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, stirred again in 3 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 1 day under reduced pressure. The molecular weight of the polyimide precursor PZ-3 was Mw=22,200 and Mn=10,400. The structure of PZ-3 is estimated to be represented by the following formula (PZ-3). [Chemical formula 71]

＜聚醯亞胺前驅物樹脂（PZ-4）的合成例＞ 在安裝有冷凝器及攪拌機之燒瓶中，一邊去除水分一邊使二苯基-3,3’,4,4’-四羧酸二酐（Tokyo Chemical Industry Co.,Ltd.製）14.7g（50毫莫耳）懸浮於二甘二甲醚（Tokyo Chemical Industry Co.,Ltd.製）60g中。連續添加甲基丙烯酸2-羥基乙酯（Tokyo Chemical Industry Co.,Ltd.製）5.21g（40毫莫耳）、3,3,3-三氟-1-丙醇（Tokyo Chemical Industry Co.,Ltd.製）7.07g（62毫莫耳）、吡啶（Tokyo Chemical Industry Co.,Ltd.製）10.3g（130毫莫耳）、2,2,6,6-四甲基哌啶基1-氧基自由基（Tokyo Chemical Industry Co.,Ltd.製）0.03g，並在60℃的溫度下攪拌了4小時。接著，將混合物冷卻至-20℃之後，滴加了90分鐘亞硫醯氯（Tokyo Chemical Industry Co.,Ltd.製）12.4g（104毫莫耳）。可以獲得吡啶鹽酸鹽的白色沉澱物。接著，攪拌2小時之後，將二胺（AA-1）7.29g（27.6毫莫耳）、5-胺基-2-（4-胺基苯基）苯并㗁唑（Tokyo Chemical Industry Co.,Ltd.製）5.05g（22.4毫莫耳）溶解於NMP70mL中而獲得者經2小時滴加來進行了添加。添加上述二胺之期間，黏度增加。接著，添加乙醇9.3g（200毫莫耳）和2,2,6,6-四甲基哌啶1-氧基自由基（Tokyo Chemical Industry Co.,Ltd.製）0.05g，並將混合物攪拌了2小時。接著，使聚醯亞胺前驅物樹脂在3升水中沉澱，並將水-聚醯亞胺前驅物樹脂混合物以500rpm的速度攪拌了15分鐘。藉由過濾而獲取聚醯亞胺前驅物樹脂，並在3升水中再次攪拌30分鐘並再次進行了過濾。接著，在減壓狀態下，將所獲得之聚醯亞胺前驅物樹脂在45℃下乾燥了1天。關於該聚醯亞胺前驅物PZ-4的分子量，Mw=22,000，Mn=10,400。 推測PZ-4的結構為由下述式（PZ-4）表示之結構。下述式（PZ-4）中，*表示與R1所鍵結之氧原子的鍵結部位。 [化學式72] <Synthesis Example of Polyimide Procurator Resin (PZ-4)> In a flask equipped with a condenser and a stirrer, 14.7 g (50 mmol) of diphenyl-3,3',4,4'-tetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was suspended in 60 g of diglycidyl dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) while removing water. 5.21 g (40 mmol) of 2-hydroxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd.), 7.07 g (62 mmol) of 3,3,3-trifluoro-1-propanol (Tokyo Chemical Industry Co., Ltd.), 10.3 g (130 mmol) of pyridine (Tokyo Chemical Industry Co., Ltd.), and 0.03 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were added successively, and stirred at 60°C for 4 hours. Then, after the mixture was cooled to -20°C, 12.4 g (104 mmol) of thionyl chloride (Tokyo Chemical Industry Co., Ltd.) was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Then, after stirring for 2 hours, 7.29 g (27.6 mmol) of diamine (AA-1) and 5.05 g (22.4 mmol) of 5-amino-2-(4-aminophenyl)benzoxazole (Tokyo Chemical Industry Co., Ltd.) dissolved in 70 mL of NMP were added dropwise over 2 hours. During the addition of the diamine, the viscosity increased. Then, 9.3 g (200 mmol) of ethanol and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 3 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and was stirred again in 3 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 1 day under reduced pressure. Regarding the molecular weight of the polyimide precursor PZ-4, Mw=22,000, Mn=10,400. The structure of PZ-4 is estimated to be the structure represented by the following formula (PZ-4). In the following formula (PZ-4), * represents the bonding site of the oxygen atom to which R1 is bonded. [Chemical formula 72]

＜聚醯亞胺前驅物樹脂（PZ-5）的合成例＞ 在安裝有冷凝器及攪拌機之燒瓶中，一邊去除水分一邊使氧代二鄰苯二甲酸二酐（Tokyo Chemical Industry Co.,Ltd.製）15.5g（50毫莫耳）懸浮於二甘二甲醚（Tokyo Chemical Industry Co.,Ltd.製）60g中。連續添加二乙二醇單乙醚（Tokyo Chemical Industry Co.,Ltd.製）9.66g（72毫莫耳）甲基丙烯酸2-羥基乙酯（Tokyo Chemical Industry Co.,Ltd.製）6.51g（50毫莫耳）、吡啶（Tokyo Chemical Industry Co.,Ltd.製）10.3g（130毫莫耳）、氫醌（Tokyo Chemical Industry Co.,Ltd.製）0.03g，並在60℃的溫度下攪拌了4小時。接著，將混合物冷卻至-20℃之後，滴加了90分鐘亞硫醯氯（Tokyo Chemical Industry Co.,Ltd.製）12.4g（104毫莫耳）。可以獲得吡啶鹽酸鹽的白色沉澱物。接著，攪拌2小時之後，將二胺（AA-4）8.91g（32毫莫耳）、5-胺基-2-（4-胺基苯基）苯并㗁唑（Tokyo Chemical Industry Co.,Ltd.製）3.15g（14毫莫耳）溶解於NMP70mL中而獲得者經2小時滴加來進行了添加。添加上述二胺之期間，黏度增加。接著，添加乙醇9.3g（200毫莫耳）和2,2,6,6-四甲基哌啶1-氧基自由基（Tokyo Chemical Industry Co.,Ltd.製）0.05g，並將混合物攪拌了2小時。接著，使聚醯亞胺前驅物樹脂在3升水中沉澱，並將水-聚醯亞胺前驅物樹脂混合物以500rpm的速度攪拌了15分鐘。藉由過濾而獲取聚醯亞胺前驅物樹脂，並在2升水中再次攪拌30分鐘並再次進行了過濾。接著，在減壓狀態下，將所獲得之聚醯亞胺前驅物樹脂在45℃下乾燥了1天。關於該聚醯亞胺前驅物PZ-5的分子量，Mw=25,200，Mn=12,000。 推測PZ-5的結構為由下述式（PZ-5）表示之結構。下述式（PZ-5）中，*表示與R1所鍵結之氧原子的鍵結部位。 [化學式73] <Synthesis Example of Polyimide Procurator Resin (PZ-5)> In a flask equipped with a condenser and a stirrer, 15.5 g (50 mmol) of oxydiphthalic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was suspended in 60 g of diethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) while removing water. 9.66 g (72 mmol) of diethylene glycol monoethyl ether (Tokyo Chemical Industry Co., Ltd.), 6.51 g (50 mmol) of 2-hydroxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd.), 10.3 g (130 mmol) of pyridine (Tokyo Chemical Industry Co., Ltd.), and 0.03 g of hydroquinone (Tokyo Chemical Industry Co., Ltd.) were added successively, and stirred at 60°C for 4 hours. Then, after the mixture was cooled to -20°C, 12.4 g (104 mmol) of thionyl chloride (Tokyo Chemical Industry Co., Ltd.) was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Next, after stirring for 2 hours, 8.91 g (32 mmol) of diamine (AA-4) and 3.15 g (14 mmol) of 5-amino-2-(4-aminophenyl)benzoxazole (Tokyo Chemical Industry Co., Ltd.) dissolved in 70 mL of NMP were added dropwise over 2 hours. During the addition of the diamine, the viscosity increased. Next, 9.3 g (200 mmol) of ethanol and 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 3 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and was stirred again in 2 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 1 day under reduced pressure. Regarding the molecular weight of the polyimide precursor PZ-5, Mw=25,200, Mn=12,000. The structure of PZ-5 is estimated to be the structure represented by the following formula (PZ-5). In the following formula (PZ-5), * represents the bonding site of the oxygen atom to which R1 is bonded. [Chemical formula 73]

＜聚醯亞胺樹脂（PI-1）的合成例＞ 在安裝有冷凝器及攪拌機之燒瓶中，一邊去除水分一邊連續添加氧代二鄰苯二甲酸二酐（Tokyo Chemical Industry Co.,Ltd.製）15.5g（50毫莫耳）、2,2,6,6-四甲基哌啶基1-氧基自由基（Tokyo Chemical Industry Co.,Ltd.製）0.05g、NMP（Tokyo Chemical Industry Co.,Ltd.製）81g，並在25℃的溫度下進行了攪拌。接著，添加二胺（AA-1）8.32g（31.5毫莫耳）、5-胺基-2-（4-胺基苯基）苯并㗁唑（Tokyo Chemical Industry Co.,Ltd.製）3.04g（13.5毫莫耳），並在25℃下攪拌了3小時。接著，添加NMP50g、吡啶（Tokyo Chemical Industry Co.,Ltd.製）15.8g（200毫莫耳）、乙酸酐（Tokyo Chemical Industry Co.,Ltd.製）12.76（125毫莫耳），並在80℃下攪拌了3小時。將其冷卻至25℃之後，使聚醯亞胺樹脂在3升甲醇中沉澱，並以1500rpm的速度攪拌了30分鐘。藉由過濾而獲取聚醯亞胺樹脂，並在2升甲醇水中再次攪拌30分鐘並再次進行了過濾。接著，在減壓狀態下，將所獲得之聚醯亞胺樹脂在45℃下乾燥了1天。關於該聚醯亞胺樹脂PI-1的分子量，Mw=20,800，Mn=8,500。 推測PI-1的結構為由下述式（PI-1）表示之結構。 [化學式74] <Synthesis Example of Polyimide Resin (PI-1)> In a flask equipped with a condenser and a stirrer, 15.5 g (50 mmol) of oxydiphthalic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.), and 81 g of NMP (manufactured by Tokyo Chemical Industry Co., Ltd.) were added continuously while removing water, and stirred at 25°C. Next, 8.32 g (31.5 mmol) of diamine (AA-1) and 3.04 g (13.5 mmol) of 5-amino-2-(4-aminophenyl)benzoxazole (Tokyo Chemical Industry Co., Ltd.) were added, and stirred at 25°C for 3 hours. Next, 50 g of NMP, 15.8 g (200 mmol) of pyridine (Tokyo Chemical Industry Co., Ltd.) and 12.76 g (125 mmol) of acetic anhydride (Tokyo Chemical Industry Co., Ltd.) were added, and stirred at 80°C for 3 hours. After cooling to 25°C, the polyimide resin was precipitated in 3 liters of methanol and stirred at 1500 rpm for 30 minutes. The polyimide resin was obtained by filtration, stirred again in 2 liters of methanol water for 30 minutes and filtered again. Then, the obtained polyimide resin was dried at 45°C for 1 day under reduced pressure. The molecular weight of the polyimide resin PI-1 was Mw=20,800 and Mn=8,500. The structure of PI-1 is estimated to be represented by the following formula (PI-1). [Chemical formula 74]

＜聚醯亞胺樹脂（PI-2）的合成例＞ 在安裝有冷凝器及攪拌機之燒瓶中，一邊去除水分一邊連續添加4,4’-（六氟亞異丙基）二鄰苯二甲酸酐（Tokyo Chemical Industry Co.,Ltd.製）22.2g（50毫莫耳）、2,2,6,6-四甲基哌啶基1-氧基自由基（Tokyo Chemical Industry Co.,Ltd.製）0.05g、NMP（Tokyo Chemical Industry Co.,Ltd.製）100g，並在25℃的溫度下進行了攪拌。接著，添加二胺（AA-1）6.08g（23毫莫耳）、5-胺基-2-（4-胺基苯基）苯并㗁唑（Tokyo Chemical Industry Co.,Ltd.製）5.18（23毫莫耳），並在25℃下攪拌了3小時。接著，添加NMP50g、吡啶（Tokyo Chemical Industry Co.,Ltd.製）15.8g（200毫莫耳）、乙酸酐（Tokyo Chemical Industry Co.,Ltd.製）12.76g（125毫莫耳），並在80℃下攪拌了3小時。將其冷卻至25℃之後，使聚醯亞胺樹脂在3升甲醇中沉澱，並以1500rpm的速度攪拌了30分鐘。藉由過濾而獲取聚醯亞胺樹脂，並在2升甲醇水中再次攪拌30分鐘並再次進行了過濾。接著，在減壓狀態下，將所獲得之聚醯亞胺樹脂在45℃下乾燥了1天。關於該聚醯亞胺前驅物PI-12的分子量，Mw=36,800，Mn=15,900。 推測PI-2的結構為由下述式（PI-2）表示之結構。 [化學式75] <Synthesis Example of Polyimide Resin (PI-2)> In a flask equipped with a condenser and a stirrer, 22.2 g (50 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.05 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.), and 100 g of NMP (manufactured by Tokyo Chemical Industry Co., Ltd.) were added continuously while removing water, and stirred at 25°C. Next, 6.08 g (23 mmol) of diamine (AA-1) and 5.18 g (23 mmol) of 5-amino-2-(4-aminophenyl)benzoxazole (Tokyo Chemical Industry Co., Ltd.) were added, and stirred at 25°C for 3 hours. Next, 50 g of NMP, 15.8 g (200 mmol) of pyridine (Tokyo Chemical Industry Co., Ltd.) and 12.76 g (125 mmol) of acetic anhydride (Tokyo Chemical Industry Co., Ltd.) were added, and stirred at 80°C for 3 hours. After cooling to 25°C, the polyimide resin was precipitated in 3 liters of methanol and stirred at 1500 rpm for 30 minutes. The polyimide resin was obtained by filtration, stirred again in 2 liters of methanol water for 30 minutes and filtered again. Then, the obtained polyimide resin was dried at 45°C for 1 day under reduced pressure. The molecular weight of the polyimide precursor PI-12 was Mw=36,800 and Mn=15,900. The structure of PI-2 is estimated to be represented by the following formula (PI-2). [Chemical formula 75]

＜聚醯亞胺樹脂（PI-3）的合成例＞ 在安裝有冷凝器及攪拌機之燒瓶中，一邊去除水分一邊將酐（MA-1）11.0g（18毫莫耳）、2,2,6,6-四甲基哌啶1-氧基自由基（Tokyo Chemical Industry Co.,Ltd.製）0.02g溶解於N-甲基吡咯啶酮（NMP）40.0g中。接著，添加5-胺基-2-（4-胺基苯基）苯并㗁唑（Tokyo Chemical Industry Co.,Ltd.製）2.43g（10.8毫莫耳）、二胺（AA-1）1.90g（7.2毫莫耳），在25℃下攪拌3小時，並在45℃下進一步攪拌了3小時。接著，添加吡啶5.69g（72毫莫耳）、乙酸酐4.59g（45毫莫耳）、N-甲基吡咯啶酮（NMP）37.7g，在80℃下攪拌3小時，並添加N-甲基吡咯啶酮（NMP）50g進行了稀釋。 使該反應液在1升甲醇中沉澱，並以3000rpm的速度攪拌了15分鐘。藉由過濾而獲取樹脂，並在1升甲醇中再次攪拌30分鐘並再次進行了過濾。在減壓狀態下，將所獲得之樹脂在40℃下乾燥了1天。關於PI-3的分子量，Mw=26,300，Mn=10,800。 推測PI-3的結構為由下述式（PI-3）表示之結構。 [化學式76] <Synthesis Example of Polyimide Resin (PI-3)> In a flask equipped with a condenser and a stirrer, 11.0 g (18 mmol) of anhydride (MA-1) and 0.02 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (Tokyo Chemical Industry Co., Ltd.) were dissolved in 40.0 g of N-methylpyrrolidone (NMP) while removing water. Then, 2.43 g (10.8 mmol) of 5-amino-2-(4-aminophenyl)benzoxazole (Tokyo Chemical Industry Co., Ltd.) and 1.90 g (7.2 mmol) of diamine (AA-1) were added, and stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Next, 5.69 g (72 mmol) of pyridine, 4.59 g (45 mmol) of acetic anhydride, and 37.7 g of N-methylpyrrolidone (NMP) were added, stirred at 80°C for 3 hours, and 50 g of N-methylpyrrolidone (NMP) was added for dilution. The reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was obtained by filtration, and stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried at 40°C for 1 day under reduced pressure. Regarding the molecular weight of PI-3, Mw=26,300, Mn=10,800. The structure of PI-3 is estimated to be the structure represented by the following formula (PI-3). [Chemical formula 76]

＜比較用聚醯亞胺樹脂（CP-1）的合成例＞ 在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中，一邊去除水分一邊使1,3-苯二胺20.0g（100毫莫耳）溶解於N-甲基吡咯啶酮（NMP）200.0g。接著，添加4,4’-（六氟亞異丙基）二鄰苯二甲酸酐44.4g（100毫莫耳），並在40℃的溫度下攪拌了2小時。接著，添加50mL的甲苯之後，一邊使200ml/min的流量的氮氣流動，一邊將溫度升溫至180℃並攪拌6小時之後，冷卻至室溫。接著，添加N-甲基吡咯啶酮130.0g並進行了稀釋之後，使聚醯亞胺在2升水中沉澱，並將水-聚醯亞胺混合物以2000rpm的速度攪拌了30分鐘。藉由過濾而獲取聚醯亞胺樹脂，並在1.5升甲醇中再次攪拌30分鐘並再次進行了過濾。接著，在減壓狀態下，所獲得之聚醯亞胺在40℃下乾燥1天，從而獲得了CP-1。CP-1的重量平均分子量（Mw）為32100，數量平均分子量（Mn）為15500。 推測CP-1的結構為由下述式（CP-1）表示之結構。 [化學式77] <Synthesis Example of Comparative Polyimide Resin (CP-1)> In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, 20.0 g (100 mmol) of 1,3-phenylenediamine was dissolved in 200.0 g of N-methylpyrrolidone (NMP) while removing water. Then, 44.4 g (100 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride was added and stirred at 40°C for 2 hours. Then, 50 mL of toluene was added, and the temperature was raised to 180°C while nitrogen gas was flowed at a flow rate of 200 ml/min, and stirred for 6 hours, and then cooled to room temperature. Next, after adding 130.0 g of N-methylpyrrolidone and diluting, the polyimide was precipitated in 2 liters of water, and the water-polyimide mixture was stirred at 2000 rpm for 30 minutes. The polyimide resin was obtained by filtration, and was stirred again in 1.5 liters of methanol for 30 minutes and filtered again. Then, the obtained polyimide was dried at 40°C for 1 day under reduced pressure to obtain CP-1. The weight average molecular weight (Mw) of CP-1 is 32100, and the number average molecular weight (Mn) is 15500. The structure of CP-1 is estimated to be the structure represented by the following formula (CP-1). [Chemical formula 77]

＜比較用聚醯亞胺前驅物CP-2的合成例＞ 在具備安裝有攪拌機、冷凝器及內部溫度計之平底接頭之乾燥反應器中，一邊去除水分一邊使二苯基-3,3’,4,4’-四羧酸二酐19.0g（64.5毫莫耳）懸浮於二甘二甲醚140mL中。連續添加甲基丙烯酸2-羥基乙酯16.8g（129毫莫耳）、氫醌0.05g及吡啶10.7g（135毫莫耳），並在60℃的溫度下攪拌了18小時。接著，將混合物冷卻至-20℃之後，滴加了90分鐘亞硫醯氯16.1g（135.5毫莫耳）。可以獲得吡啶鹽酸鹽的白色沉澱物。接著，將混合物加溫至室溫並攪拌2小時之後，添加吡啶9.7g（123毫莫耳）及N-甲基吡咯啶酮（NMP）25mL，從而獲得了透明溶液。接著，將4,4’-二胺基二苯醚11.8g（58.7毫莫耳）溶解於NMP 100mL中而獲得者向所獲得之透明溶液中經1小時滴加來進行了添加。在添加4,4’-二胺基二苯醚之期間，黏度增加。接著，添加甲醇5.6g（17.5毫莫耳）和3,5-二-第三丁基-4-羥甲苯0.05g，並將混合物攪拌了2小時。接著，使聚醯亞胺前驅物樹脂在4升水中沉澱，並將水-聚醯亞胺前驅物樹脂混合物以500rpm的速度攪拌了15分鐘。藉由過濾而獲取聚醯亞胺前驅物樹脂，並在4升水中再次攪拌30分鐘並再次進行了過濾。接著，在減壓狀態下，所獲得之聚醯亞胺前驅物樹脂在45℃下乾燥3天，從而獲得了CP-2。關於該聚醯亞胺前驅物CP-2的分子量，Mw=32,500，Mn=13,800。 推測CP-2的結構為由下述式（CP-2）表示之結構。 [化學式78] <Comparative Synthesis Example of Polyimide Precursor CP-2> In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, 19.0 g (64.5 mmol) of diphenyl-3,3',4,4'-tetracarboxylic dianhydride was suspended in 140 mL of diethylene glycol dimethyl ether while removing water. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 10.7 g (135 mmol) of pyridine were added successively, and stirred at 60°C for 18 hours. Then, after the mixture was cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Then, the mixture was heated to room temperature and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise to the obtained transparent solution over 1 hour. During the addition of 4,4'-diaminodiphenyl ether, the viscosity increased. Then, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and was stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45°C for 3 days under reduced pressure to obtain CP-2. Regarding the molecular weight of the polyimide precursor CP-2, Mw=32,500, Mn=13,800. The structure of CP-2 is estimated to be a structure represented by the following formula (CP-2). [Chemical Formula 78]

＜比較用聚醯亞胺前驅物CP-3的合成例＞ 在安裝有冷凝器及攪拌機之燒瓶中，一邊去除水分一邊連續添加氧代二鄰苯二甲酸二酐（Tokyo Chemical Industry Co.,Ltd.製）15.5g（50毫莫耳）、NMP（Tokyo Chemical Industry Co.,Ltd.製）78.9g，並在25℃的溫度下進行了攪拌。接著，添加5-胺基-2-（4-胺基苯基）苯并㗁唑（Tokyo Chemical Industry Co.,Ltd.製）10.1g（45毫莫耳），並在25℃下攪拌了3小時。接著，添加NMP30g，使聚醯亞胺前驅物樹脂在2升水中沉澱，並將水-聚醯亞胺前驅物樹脂混合物以500rpm的速度攪拌了15分鐘。藉由過濾而獲取聚醯亞胺前驅物樹脂，並在2升水中再次攪拌30分鐘並再次進行了過濾。接著，在減壓狀態下，所獲得之樹脂在45℃下乾燥1天，從而獲得了比較用聚醯亞胺前驅物CP-3。關於該含有苯并㗁唑基的聚醯胺酸之CP-3的分子量，Mw=25,800，Mn=10,400。 推測CP-3的結構為由下述式（CP-3）表示之結構。 [化學式79] <Comparative Synthesis Example of Polyimide Precursor CP-3> In a flask equipped with a condenser and a stirrer, 15.5 g (50 mmol) of oxydiphthalic dianhydride (Tokyo Chemical Industry Co., Ltd.) and 78.9 g of NMP (Tokyo Chemical Industry Co., Ltd.) were added successively while removing water, and stirred at 25°C. Then, 10.1 g (45 mmol) of 5-amino-2-(4-aminophenyl)benzoxazole (Tokyo Chemical Industry Co., Ltd.) was added, and stirred at 25°C for 3 hours. Next, 30 g of NMP was added to precipitate the polyimide precursor resin in 2 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and was stirred again in 2 liters of water for 30 minutes and filtered again. Then, the obtained resin was dried at 45°C for 1 day under reduced pressure to obtain a comparative polyimide precursor CP-3. Regarding the molecular weight of the benzoxazolyl-containing polyamide CP-3, Mw=25,800, Mn=10,400. The structure of CP-3 is estimated to be represented by the following formula (CP-3). [Chemical formula 79]

＜實施例及比較例＞ 在各實施例中，分別混合下述表1中所記載的成分，從而獲得了各硬化性樹脂組成物。又，在各比較例中，分別混合下述表1中所記載的成分，從而獲得了各比較用組成物。使所獲得之硬化性樹脂組成物及比較用組成物通過細孔寬度為0.8μm的聚四氟乙烯製過濾器來進行了加壓過濾。 在表1中，“質量份”一欄中的數值表示各成分的含量（質量份）。 在表1中，例如“種類”一欄中的“PZ-1/PZ-2”、“質量份”一欄中的“16/16”等記載表示分別使用了16質量份的PZ-1，使用了16質量份的PZ-2。 又，在表1中，“-”的記載表示不含有對應成分。<Examples and Comparative Examples> In each example, the components listed in Table 1 below were mixed to obtain each hardening resin composition. In each comparative example, the components listed in Table 1 below were mixed to obtain each comparative composition. The hardening resin composition and the comparative composition obtained were pressure filtered through a polytetrafluoroethylene filter having a pore width of 0.8 μm. In Table 1, the values in the "mass parts" column represent the content (mass parts) of each component. In Table 1, for example, "PZ-1/PZ-2" in the "Type" column and "16/16" in the "Parts by Mass" column indicate that 16 parts by mass of PZ-1 and 16 parts by mass of PZ-2 were used, respectively. In Table 1, "-" indicates that the corresponding component is not contained.

[表1] [Table 1]

表1中所記載之各成分的詳細內容如下。The details of each component listed in Table 1 are as follows.

[樹脂（特定樹脂或比較用樹脂）] ･PZ-1～PZ-5：在上述中合成之聚醯亞胺前驅物樹脂PZ-1～PZ-5 ･PI-1～PI-3：在上述中合成之聚醯亞胺樹脂PI-1～PI-3 ･CP-1～CP-3：在上述中合成之比較用聚醯亞胺CP-1、比較用聚醯亞胺前驅物CP-2～CP-3[Resin (specific resin or comparative resin)] ･PZ-1~PZ-5: Polyimide precursor resins PZ-1~PZ-5 synthesized in the above ･PI-1~PI-3: Polyimide resins PI-1~PI-3 synthesized in the above ･CP-1~CP-3: Comparative polyimide CP-1 and comparative polyimide precursors CP-2~CP-3 synthesized in the above

[溶劑] ･DMSO：二甲基亞碸 ･GBL：γ-丁內酯 ･EL：乳酸乙酯 ･NMP：N-甲基吡咯啶酮 在表1中，DMSO/GBL的記載表示將DMSO與GBL以DMSO:GBL=20:80（質量比）的比例進行混合而使用。 在表1中，NMP/EL的記載表示將NMP與EL以NMP:EL=80:20（質量比）的比例進行混合而使用。[Solvent] DMSO: dimethyl sulfoxide GBL: γ-butyrolactone EL: ethyl lactate NMP: N-methylpyrrolidone In Table 1, DMSO/GBL means that DMSO and GBL were mixed at a ratio of DMSO:GBL = 20:80 (mass ratio). In Table 1, NMP/EL means that NMP and EL were mixed at a ratio of NMP:EL = 80:20 (mass ratio).

[光聚合起始劑（光敏劑）] ･C-1：IRGACURE OXE 01（BASF公司製） ･C-2：IRGACURE OXE 02（BASF公司製）[Photopolymerization initiator (photosensitive agent)] ･C-1: IRGACURE OXE 01 (manufactured by BASF) ･C-2: IRGACURE OXE 02 (manufactured by BASF)

[聚合性化合物] ･SR-209：SR-209（Sartomer Company, Inc製） ･SR-231：SR-231（Sartomer Company, Inc製） ･SR-239：SR-239（Sartomer Company, Inc製） ･ADPH：二新戊四醇六丙烯酸酯（SHIN-NAKAMURA CHEMICAL CO, LTD.製） ･TG-G：TG-G（環氧交聯劑、SHIKOKU CHEMICALS CORPORATION.製） ･MX-270：NIKALAC MX-270（Sanwa Chemical Co.,Ltd.製）[Polymerizable compounds] ･SR-209: SR-209 (manufactured by Sartomer Company, Inc.) ･SR-231: SR-231 (manufactured by Sartomer Company, Inc.) ･SR-239: SR-239 (manufactured by Sartomer Company, Inc.) ･ADPH: Dipentatriol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD.) ･TG-G: TG-G (epoxy crosslinking agent, manufactured by SHIKOKU CHEMICALS CORPORATION.) ･MX-270: NIKALAC MX-270 (manufactured by Sanwa Chemical Co., Ltd.)

[聚合抑制劑] ･F-1：1,4-苯醌 ･F-2：4-甲氧基酚 ･F-3：1,4-二羥苯 ･F-4：2-亞硝基-1-萘酚（Tokyo Chemical Industry Co.,Ltd.製）[Polymerization inhibitor] ･F-1: 1,4-benzoquinone ･F-2: 4-methoxyphenol ･F-3: 1,4-dihydroxybenzene ･F-4: 2-nitroso-1-naphthol (Tokyo Chemical Industry Co., Ltd.)

[金屬接著性改良劑] ･G-1～G-4：下述結構的化合物。以下結構式中，Et表示乙基。 [化學式80] [Metal Adhesion Improver] ･G-1 to G-4: Compounds of the following structures. In the following structural formula, Et represents an ethyl group. [Chemical Formula 80]

[遷移抑制劑] ･H-1：1H-四唑 ･H-2：1,2,4-三唑 ･H-3：5-苯基四唑[Migration inhibitor] ･H-1: 1H-tetrazole ･H-2: 1,2,4-triazole ･H-3: 5-phenyltetrazole

[鎓鹽或熱鹼產生劑] ･I-1：下述結構的化合物 [化學式81] [Onium salt or thermal alkali generator] ･I-1: Compound having the following structure [Chemical formula 81]

[添加劑] ･J-1：N-苯基二乙醇胺（Tokyo Chemical Industry Co.,Ltd.製）[Additives] ･J-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

＜評價＞ [耐藥品性的評價] 將各實施例及比較例中所製備之各硬化性樹脂組成物或比較用組成物，分別藉由旋塗法適用於矽晶圓上，從而形成了硬化性樹脂組成物層。將適用了所獲得之硬化性樹脂組成物層之矽晶圓在加熱板上在100℃下乾燥5分鐘，從而在矽晶圓上形成了15μm的均勻厚度的硬化性樹脂組成物層。使用步進機（Nikon NSR 2005 i9C）以500mJ/cm2 的曝光能量對矽晶圓上的硬化性樹脂組成物層進行整面曝光，將所曝光之硬化性樹脂組成物層（樹脂層）在氮氣環境下以10℃/分鐘的升溫速度進行升溫，並在表1的“硬化條件”一欄中所記載的溫度下加熱180分鐘，從而獲得了硬化性樹脂組成物層的硬化層（樹脂層）。 將所獲得之樹脂層在下述條件下浸漬於下述藥液中，並算出溶解速度。 藥液：二甲基亞碸（DMSO）和25質量%的氫氧化四甲基銨（TMAH）水溶液的90:10（質量比）的混合物 評價條件：將樹脂層在75℃的藥液中浸漬15分鐘，比較浸漬前後的膜厚，並計算出溶解速度（nm/分鐘）。 按照下述評價基準進行評價，評價結果記載於表1的“耐藥品性”一欄中。可以說溶解速度越小，耐藥品性越優異。 -評價基準- A：溶解速度小於200nm/分鐘。 B：溶解速度為200nm/分鐘以上且小於300nm/分鐘。 C：溶解速度為300nm/分鐘以上且小於400nm/分鐘。 D：溶解速度為400nm/分鐘以上。＜Evaluation＞ [Evaluation of chemical resistance] Each hardening resin composition or comparative composition prepared in each embodiment and comparative example was applied to a silicon wafer by spin coating to form a hardening resin composition layer. The silicon wafer to which the hardening resin composition layer was applied was dried on a heating plate at 100°C for 5 minutes to form a hardening resin composition layer with a uniform thickness of 15 μm on the silicon wafer. The curable resin composition layer on the silicon wafer was exposed to light with an exposure energy of 500 mJ/cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed curable resin composition layer (resin layer) was heated at a heating rate of 10°C/min in a nitrogen atmosphere, and heated for 180 minutes at the temperature listed in the "Curing Conditions" column of Table 1, thereby obtaining a cured layer (resin layer) of the curable resin composition layer. The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated. Chemical solution: A mixture of 90:10 (mass ratio) of dimethyl sulfoxide (DMSO) and 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution Evaluation conditions: The resin layer was immersed in the chemical solution at 75°C for 15 minutes, the film thickness before and after immersion was compared, and the dissolution rate (nm/minute) was calculated. The evaluation was performed according to the following evaluation criteria, and the evaluation results are recorded in the "Chemical Resistance" column of Table 1. It can be said that the smaller the dissolution rate, the better the chemical resistance. -Evaluation Criteria- A: Dissolution rate is less than 200nm/minute. B: Dissolution rate is 200nm/minute or more and less than 300nm/minute. C: Dissolution rate is 300nm/minute or more and less than 400nm/minute. D: Dissolution rate is 400nm/minute or more.

[膜強度（斷裂伸長率）的評價] 藉由旋塗法，將各實施例及比較例中所製備之硬化性樹脂組成物或比較用組成物分別適用於矽晶圓上，從而形成了樹脂層。 將形成有所獲得之樹脂層之矽晶圓在加熱板上在100℃下乾燥5分鐘，從而在矽晶圓上獲得了約15μm的均勻厚度的硬化性樹脂組成物層。使用步進機（Nikon NSR 2005 i9C），並以500mJ/cm2 的曝光能量對矽晶圓上的硬化性樹脂組成物層的整面進行了i射線曝光。接著，將上述曝光後的硬化性樹脂組成物層在氮環境下以10℃/分鐘的升溫速度進行升溫，在達到表1中的“硬化條件”一欄中所記載的溫度之後，加熱了3小時。將硬化後的硬化性樹脂組成物層（硬化膜）浸漬於4.9質量%氫氟酸水溶液中，並從矽晶圓剝離了硬化膜。使用衝孔機對所剝離之硬化膜進行沖壓，從而製作出試樣寬度為3mm、試樣長度為30mm的試驗片。關於所獲得之試驗片的長邊方向的伸長率，使用拉伸試驗機（Tensilon）在十字頭速度300mm/分鐘、25℃、65%RH（相對濕度）的環境下依據JIS-K6251進行測定。分別實施5次測定，將5次測定中之試驗片斷裂時的伸長率（斷裂伸長率）的算術平均值用作指標值。 按照下述評價基準進行評價，評價結果記載於表1中。可以說指標值越大，硬化膜的膜強度越優異。 -評價基準- A：上述指標值為60%以上。 B：上述指標值為55%以上且小於60%。 C：上述指標值為50%以上且小於55%。 D：上述指標值小於50%。[Evaluation of film strength (elongation at break)] The hardening resin composition or the comparative composition prepared in each embodiment and comparative example was applied to a silicon wafer by spin coating to form a resin layer. The silicon wafer on which the resin layer was formed was dried on a heating plate at 100°C for 5 minutes to obtain a hardening resin composition layer with a uniform thickness of about 15 μm on the silicon wafer. The entire surface of the hardening resin composition layer on the silicon wafer was exposed to i-rays at an exposure energy of 500 mJ/ cm2 using a stepper (Nikon NSR 2005 i9C). Next, the exposed curable resin composition layer was heated at a rate of 10°C/min in a nitrogen environment, and after reaching the temperature listed in the "Curing Conditions" column in Table 1, it was heated for 3 hours. The cured curable resin composition layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer. The peeled cured film was punched using a punching machine to produce a test piece with a sample width of 3 mm and a sample length of 30 mm. The elongation in the long side direction of the obtained test piece was measured in accordance with JIS-K6251 using a tensile tester (Tensilon) at a crosshead speed of 300 mm/min, 25°C, and 65% RH (relative humidity). The measurement was carried out 5 times respectively, and the arithmetic mean of the elongation (fracture elongation) of the test piece when it broke in the 5 measurements was used as the index value. The evaluation was performed according to the following evaluation criteria, and the evaluation results are recorded in Table 1. It can be said that the larger the index value, the better the film strength of the cured film. -Evaluation Criteria- A: The above index value is 60% or more. B: The above index value is 55% or more and less than 60%. C: The above index value is 50% or more and less than 55%. D: The above index value is less than 50%.

[保存穩定性（膜變化率）的評價] -經時前膜厚的測定- 在各實施例及比較例中，藉由旋塗法分別將硬化性樹脂組成物或比較用組成物適用於矽晶圓上，從而形成了硬化性樹脂組成物層。將適用了所獲得之硬化性樹脂組成物層之矽晶圓在加熱板上在100℃下乾燥5分鐘，從而在矽晶圓上獲得了約15μm的均勻厚度的硬化性樹脂組成物層。測定上述矽晶圓上的硬化性樹脂組成物層的膜厚，並將該值設為經時前膜厚。關於膜厚，使用橢圓偏光計（Foothill公司製KT-22）在塗佈面上的10個點處實施膜厚測定，並作為其算術平均值而求出。 -經時後膜厚的測定- 在各實施例及比較例中，分別向玻璃容器中加入硬化性樹脂組成物或比較用組成物並密封，在25℃、遮光的環境下靜置14天之後，藉由旋塗法以與求出經時前膜厚時相同的轉速將其適用於矽晶圓上，從而形成了硬化性樹脂組成物層。將適用了所獲得之硬化性樹脂組成物層之矽晶圓在加熱板上在100℃下乾燥5分鐘，從而在矽晶圓上獲得了均勻厚度的硬化性樹脂組成物層。關於所獲得之硬化性樹脂組成物層的膜厚，藉由與上述經時前膜厚的測定方法中之膜厚的測定方法相同的方法進行測定，並將該值設為經時後膜厚。 -膜厚變化率- 藉由以下式，計算出膜厚變化率。 膜厚變化率（%）=|經時前膜厚-經時後膜厚|/經時前膜厚×100 按照下述評價基準對計算出的膜厚變化率進行評價，並將評價結果記載於表1的“保存穩定性”一欄中。可以說上述膜厚變化率越小，硬化性樹脂組成物的保存穩定性越優異。 -評價基準- A：上述膜厚變化率小於10%。 B：上述膜厚變化率為10%以上且小於15%。 C：上述膜厚變化率為15%以上且小於20%。 D：上述膜厚變化率為20%以上。[Evaluation of storage stability (film change rate)] -Measurement of film thickness before aging- In each embodiment and comparative example, a hardening resin composition or a comparative composition was applied to a silicon wafer by spin coating to form a hardening resin composition layer. The silicon wafer to which the hardening resin composition layer was applied was dried on a heating plate at 100°C for 5 minutes to obtain a hardening resin composition layer with a uniform thickness of about 15 μm on the silicon wafer. The film thickness of the hardening resin composition layer on the above silicon wafer was measured, and the value was set as the film thickness before aging. The film thickness was measured at 10 points on the coating surface using an elliptical polarimeter (KT-22 manufactured by Foothill Corporation) and the arithmetic mean value was obtained. -Measurement of film thickness after aging- In each embodiment and comparative example, a curable resin composition or a comparative composition was added to a glass container and sealed, and after standing for 14 days at 25°C in a light-shielded environment, it was applied to a silicon wafer by spin coating at the same rotation speed as when the film thickness before aging was obtained, thereby forming a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes, thereby obtaining a uniformly thick curable resin composition layer on the silicon wafer. The film thickness of the obtained curable resin composition layer was measured by the same method as the film thickness measurement method before aging, and the value was set as the film thickness after aging. -Film thickness change rate- The film thickness change rate was calculated by the following formula. Film thickness change rate (%) = |Film thickness before aging - Film thickness after aging|/Film thickness before aging × 100 The calculated film thickness change rate was evaluated according to the following evaluation criteria, and the evaluation results were recorded in the "Storage Stability" column of Table 1. It can be said that the smaller the above-mentioned film thickness variation rate is, the better the storage stability of the curable resin composition is. -Evaluation criteria- A: The above-mentioned film thickness variation rate is less than 10%. B: The above-mentioned film thickness variation rate is 10% or more and less than 15%. C: The above-mentioned film thickness variation rate is 15% or more and less than 20%. D: The above-mentioned film thickness variation rate is 20% or more.

從以上結果可知，本發明之包含特定樹脂之硬化性樹脂組成物的耐藥品性優異。 比較例1～比較例3之比較用組成物不含有特定樹脂。可知該比較例1～比較例3之比較用組成物的耐藥品性差。From the above results, it can be seen that the curable resin composition containing the specific resin of the present invention has excellent chemical resistance. The comparative compositions of Comparative Examples 1 to 3 do not contain the specific resin. It can be seen that the comparative compositions of Comparative Examples 1 to 3 have poor chemical resistance.

＜實施例101＞ 將實施例1中所記載的硬化性樹脂組成物旋轉塗佈於在表面形成有銅薄層之樹脂基材中之銅薄層的表面上，以使膜厚成為20μm。將塗佈於樹脂基材上之硬化性樹脂組成物在100℃下乾燥2分鐘之後，使用步進機（Nikon Corporation製、NSR1505 i6）進行了曝光。關於曝光，隔著正方形圖案（長寬各100μm的正方形圖案，重複數10）的遮罩，在波長365nm下以400mJ/cm2 的曝光量進行曝光，從而製作了殘留有正方形之圖案。曝光之後，用環戊酮顯影30秒鐘，用PGMEA沖洗20秒鐘，從而獲得了圖案。 接著，使其在氮氣環境下以10℃/分鐘的升溫速度進行升溫，達到表1的實施例1的“硬化條件”一欄中所記載的溫度之後，在該溫度下加熱3小時，從而形成了再配線層用層間絕緣膜。該再配線層用層間絕緣膜的絕緣性優異。又，使用該等再配線層用層間絕緣膜製造出半導體器件，其結果，確認到正常動作。<Example 101> The curable resin composition described in Example 1 was spin-coated on the surface of the copper thin layer in the resin substrate having the copper thin layer formed on the surface so that the film thickness was 20 μm. The curable resin composition coated on the resin substrate was dried at 100°C for 2 minutes and then exposed using a stepper (manufactured by Nikon Corporation, NSR1505 i6). The exposure was performed at a wavelength of 365 nm and an exposure amount of 400 mJ/ cm2 through a mask of a square pattern (a square pattern with a length and width of 100 μm each, repeated 10 times), thereby producing a pattern with a square remaining. After exposure, the pattern was obtained by developing with cyclopentanone for 30 seconds and rinsing with PGMEA for 20 seconds. Then, the temperature was raised at a rate of 10°C/min in a nitrogen environment until the temperature was reached as described in the "hardening conditions" column of Example 1 in Table 1. The temperature was then heated for 3 hours to form an interlayer insulating film for the redistribution layer. The interlayer insulating film for the redistribution layer had excellent insulation properties. In addition, semiconductor devices were manufactured using the interlayer insulating film for the redistribution layer, and normal operation was confirmed.

無。without.

無。without.

Claims (20)

一種硬化性樹脂組成物，其係包括包含下述式(1-1)所表示之重複單元且包含選自包括下述式(2-2)所表示之重複單元及下述式(2-3)所表示之重複單元之群組中的至少一種重複單元之樹脂及溶劑；前述樹脂係包含選自包括下述式(3-2)所表示之重複單元及下述式(3-3)所表示之重複單元之群組中的至少一種重複單元，
Figure 109142390-A0305-02-0191-1
 式(1-1)中，Y1表示2價連接基，Ar1表示可以具有縮合環結構之芳香族烴基，Y2表示單鍵或2價連接基；式(2-2)中，X2表示4價連接基；式(2-3)中，X3表示3價連接基；
Figure 109142390-A0305-02-0192-2
 式(3-2)中，X6表示4價連接基，Z2表示具有包含乙烯性不飽和鍵之基團之2價連接基；式(3-3)中，X7及X8分別獨立地表示3價連接基，Z3及Z4分別獨立地表示2價連接基，Z3及Z4中的至少一者表示具有包含乙烯性不飽和鍵之基團之2價連接基。 A curable resin composition comprising a resin including a repeating unit represented by the following formula (1-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (2-2) and a repeating unit represented by the following formula (2-3), and a solvent; the resin including at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-2) and a repeating unit represented by the following formula (3-3),
Figure 109142390-A0305-02-0191-1
 In formula (1-1), Y1 represents a divalent linking group, Ar1 represents an aromatic hydrocarbon group which may have a condensed ring structure, and Y2 represents a single bond or a divalent linking group; in formula (2-2), X2 represents a tetravalent linking group; in formula (2-3), X3 represents a trivalent linking group;
Figure 109142390-A0305-02-0192-2
 In formula (3-2), X6 represents a tetravalent connecting group, and Z2 represents a divalent connecting group having a group containing an ethylenic unsaturated bond; in formula (3-3), X7 and X8 each independently represent a trivalent connecting group, and Z3 and Z4 each independently represent a divalent connecting group, and at least one of Z3 and Z4 represents a divalent connecting group having a group containing an ethylenic unsaturated bond. 如請求項1所述之硬化性樹脂組成物，其中式(3-2)中的Z2為式(Z-1)所表示之基團，式(3-3)中的Z3及Z4中的至少一者為式(Z-1)所表示之基團，
Figure 109142390-A0305-02-0192-3
 式(Z-1)中，Q1表示碳數1~30的有機基，A1表示包含包含乙烯性不飽和鍵之基團之基團，n1表示1以上的整數，*表示與其他結構的鍵結部位。 The curable resin composition as claimed in claim 1, wherein Z2 in formula (3-2) is a group represented by formula (Z-1), and at least one of Z3 and Z4 in formula (3-3) is a group represented by formula (Z-1),
Figure 109142390-A0305-02-0192-3
 In formula (Z-1), Q1 represents an organic group having 1 to 30 carbon atoms, A1 represents a group containing an ethylenically unsaturated bond, n1 represents an integer greater than 1, and * represents a bonding site with other structures. 如請求項2所述之硬化性樹脂組成物，其中式(Z-1)中的Q1為選自包括式(A2-1)~式(A2-5)所表示之結構之群組中的至少一種結構，
Figure 109142390-A0305-02-0193-4
 式(A2-1)~(A2-5)中，RA211~RA214、RA221~RA224、RA231~RA238、RA241~RA248及RA251~RA258分別獨立地表示氫原子、烷基、環狀烷基、烷氧基、羥基、氰基、鹵化烷基或鹵素原子，LA231及LA241分別獨立地表示單鍵、羰基、磺醯基、2價飽和烴基、2價不飽和烴基、雜原子、雜環基或鹵化伸烷基，RA211~RA214中的至少一個、RA221~RA224中的至少一個、RA231~RA238中的至少一個、RA241~RA248中的至少一個及RA251~RA258中的至少一個可以為與上述式(Z-1)中的A1的鍵結部位，*分別獨立地表示與其他結構的鍵結部位。 The hardening resin composition as described in claim 2, wherein Q1 in formula (Z-1) is at least one structure selected from the group consisting of structures represented by formulas (A2-1) to (A2-5),
Figure 109142390-A0305-02-0193-4
 In formulas (A2-1) to (A2-5), R A211 to R A214 , R A221 to R A224 , R A231 to R A238 , R A241 to R A248 , and R A251 to R A258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group, or a halogen atom; L A231 and L A241 each independently represent a single bond, a carbonyl group, a sulfonyl group, a divalent saturated alkyl group, a divalent unsaturated alkyl group, a heteroatom, a heterocyclic group, or a halogenated alkylene group; at least one of R A211 to R A214 , at least one of R A221 to R A224 , at least one of R A231 to R A238 , R At least one of A241 to R A248 and at least one of R A251 to R A258 can be a bonding site with A1 in the above formula (Z-1), and * independently represents a bonding site with other structures. 一種硬化性樹脂組成物，其係包括包含下述式(1-1)所表示之重複單元且包含選自包括下述式(2-1)所表示之重複單元、下述式(2-2)所表示之重複單元、下述式(2-3)所表示之重複單元及下述式(2-4)所表示之重複單元之群組中的至少一種重複單元之樹脂及溶劑；前述樹脂係包含選自包括下述式(3-1)所表示之重複單元、下述式(3 -2)所表示之重複單元、下述式(3-3)所表示之重複單元及下述式(3-4)所表示之重複單元之群組中的至少一種重複單元，作為包含式(1-1)所表示之重複單元之重複單元，包含式(5-1)所表示之重複單元，
Figure 109142390-A0305-02-0194-5
 式(1-1)中，Y1表示烴基，Ar1表示可以具有縮合環結構之芳香族烴基，Y2表示單鍵或烴基；式(2-1)中，X1表示4價連接基，A1及A2分別獨立地表示氧原子或-NRN-，R1及R2分別獨立地表示1價有機基，RN表示氫原子或烴基；式(2-2)中，X2表示4價連接基；式(2-3)中，X3表示3價連接基；式(2-4)中，X4表示3價連接基，A4表示氧原子或-NRN-，R4表示1 價有機基，RN表示氫原子或烴基；
Figure 109142390-A0305-02-0195-6
 式(3-1)中，X5表示4價連接基，R3及R4分別獨立地表示1價有機基，Z1表示2價連接基，R3、R4及Z1中的至少一個包含包含乙烯性不飽和鍵之基團；式(3-2)中，X6表示4價連接基，Z2表示具有包含乙烯性不飽和鍵之基團之2價連接基；式(3-3)中，X7及X8分別獨立地表示3價連接基，Z3及Z4分別獨立地表示2價連接基，Z3及Z4中的至少一者表示具有包含乙烯性不飽和鍵之基團之2價連接基；式(3-4)中，X7及X8分別獨立地表示3價連接基，Z3及Z4分別獨立 地表示2價連接基，R5及R6分別獨立地表示1價有機基，Z3及Z4中的至少一者表示具有包含乙烯性不飽和鍵之基團之2價連接基，R5、R6、Z3及Z4中的至少一個包含包含乙烯性不飽和鍵之基團；
Figure 109142390-A0305-02-0196-7
 式(5-1)中，L51為式(L-1)所表示之結構，L52表示2價有機基；
Figure 109142390-A0305-02-0196-8
 式(L-1)中，Y1表示烴基，Ar1表示可以具有縮合環結構之芳香族烴基，Y2表示單鍵或烴基，*表示與其他結構的鍵結部位。 A curable resin composition comprises a resin including a repeating unit represented by the following formula (1-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (2-1), a repeating unit represented by the following formula (2-2), a repeating unit represented by the following formula (2-3), and a repeating unit represented by the following formula (2-4), and a solvent; the resin comprising at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), a repeating unit represented by the following formula (3-3), and a repeating unit represented by the following formula (3-4), as a repeating unit including the repeating unit represented by the following formula (1-1), and comprising a repeating unit represented by the following formula (5-1),
Figure 109142390-A0305-02-0194-5
 In formula (1-1), Y1 represents a alkyl group, Ar1 represents an aromatic alkyl group which may have a condensed ring structure, and Y2 represents a single bond or a alkyl group; in formula (2-1), X1 represents a 4-valent linking group, A1 and A2 each independently represent an oxygen atom or -NR N -, R1 and R2 each independently represent a monovalent organic group, and RN represents a hydrogen atom or a alkyl group; in formula (2-2), X2 represents a 4-valent linking group; in formula (2-3), X3 represents a trivalent linking group; in formula (2-4), X4 represents a trivalent linking group, A4 represents an oxygen atom or -NR N -, R4 represents a monovalent organic group, and RN represents a hydrogen atom or a alkyl group;
Figure 109142390-A0305-02-0195-6
 In formula (3-1), X5 represents a 4-valent linking group, R3 and R4 each independently represent a univalent organic group, Z1 represents a divalent linking group, and at least one of R3 , R4 and Z1 contains a group containing an ethylenically unsaturated bond; in formula (3-2), X6 represents a 4-valent linking group, and Z2 represents a divalent linking group having a group containing an ethylenically unsaturated bond; in formula (3-3), X7 and X8 each independently represent a trivalent linking group, Z3 and Z4 each independently represent a divalent linking group, and at least one of Z3 and Z4 represents a divalent linking group having a group containing an ethylenically unsaturated bond; in formula (3-4), X7 and X8 each independently represent a trivalent linking group, and Z3 and Z4 each independently represent a divalent linking group. R 5 and R 6 each independently represent a divalent linking group, R 5 and R 6 each independently represent a monovalent organic group, at least one of Z 3 and Z 4 represents a divalent linking group having a group containing an ethylenically unsaturated bond, and at least one of R 5 , R 6 , Z 3 and Z 4 contains a group containing an ethylenically unsaturated bond;
Figure 109142390-A0305-02-0196-7
 In formula (5-1), L 51 is the structure represented by formula (L-1), and L 52 represents a divalent organic group;
Figure 109142390-A0305-02-0196-8
 In formula (L-1), Y1 represents a alkyl group, Ar1 represents an aromatic alkyl group which may have a condensed ring structure, Y2 represents a single bond or a alkyl group, and * represents a bonding site with other structures. 如請求項4所述之硬化性樹脂組成物，其中式(3-1)中的Z1為式(Z-1)所表示之基團，式(3-2)中的Z2為式(Z-1)所表示之基團，式(3-3)中的Z3及Z4中的至少一者為式(Z-1)所表示之基團，式(3-4)中的Z3及Z4中的至少一者為式(Z-1)所表示之基團，
Figure 109142390-A0305-02-0196-9
 式(Z-1)中，Q1表示碳數1~30的有機基，A1表示包含包含乙烯性不飽和鍵之基團之基團，n1表示1以上的整數，*表示與其他結構的鍵結部位。 The curable resin composition as described in claim 4, wherein Z1 in formula (3-1) is a group represented by formula (Z-1), Z2 in formula (3-2) is a group represented by formula (Z-1), at least one of Z3 and Z4 in formula (3-3) is a group represented by formula (Z-1), and at least one of Z3 and Z4 in formula (3-4) is a group represented by formula (Z-1),
Figure 109142390-A0305-02-0196-9
 In formula (Z-1), Q1 represents an organic group having 1 to 30 carbon atoms, A1 represents a group containing an ethylenically unsaturated bond, n1 represents an integer greater than 1, and * represents a bonding site with other structures. 如請求項5所述之硬化性樹脂組成物，其中 式(Z-1)中的Q1為選自包括式(A2-1)~式(A2-5)所表示之結構之群組中的至少一種結構，
Figure 109142390-A0305-02-0197-10
 式(A2-1)~(A2-5)中，RA211~RA214、RA221~RA224、RA231~RA238、RA241~RA248及RA251~RA258分別獨立地表示氫原子、烷基、環狀烷基、烷氧基、羥基、氰基、鹵化烷基或鹵素原子，LA231及LA241分別獨立地表示單鍵、羰基、磺醯基、2價飽和烴基、2價不飽和烴基、雜原子、雜環基或鹵化伸烷基，RA211~RA214中的至少一個、RA221~RA224中的至少一個、RA231~RA238中的至少一個、RA241~RA248中的至少一個及RA251~RA258中的至少一個可以為與上述式(Z-1)中的A1的鍵結部位，*分別獨立地表示與其他結構的鍵結部位。 The hardening resin composition as described in claim 5, wherein Q1 in formula (Z-1) is at least one structure selected from the group consisting of structures represented by formulas (A2-1) to (A2-5),
Figure 109142390-A0305-02-0197-10
 In formulas (A2-1) to (A2-5), R A211 to R A214 , R A221 to R A224 , R A231 to R A238 , R A241 to R A248 , and R A251 to R A258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group, or a halogen atom; L A231 and L A241 each independently represent a single bond, a carbonyl group, a sulfonyl group, a divalent saturated alkyl group, a divalent unsaturated alkyl group, a heteroatom, a heterocyclic group, or a halogenated alkylene group; at least one of R A211 to R A214 , at least one of R A221 to R A224 , at least one of R A231 to R A238 , R At least one of A241 to R A248 and at least one of R A251 to R A258 can be a bonding site with A1 in the above formula (Z-1), and * independently represents a bonding site with other structures. 如請求項1至請求項6之任一項所述之硬化性樹脂組成物，其中前述式(1-1)所表示之重複單元的含量相對於樹脂的總質量為0.1質 量%~60質量%。 A curable resin composition as described in any one of claim 1 to claim 6, wherein the content of the repeating unit represented by the aforementioned formula (1-1) is 0.1% by mass to 60% by mass relative to the total mass of the resin. 如請求項1至請求項6之任一項所述之硬化性樹脂組成物，其係包含聚合性化合物。 The hardening resin composition as described in any one of claim 1 to claim 6 comprises a polymerizable compound. 如請求項1至請求項6之任一項所述之硬化性樹脂組成物，其係用於形成再配線層用層間絕緣膜。 The curable resin composition as described in any one of claim 1 to claim 6 is used to form an interlayer insulating film for a redistribution layer. 一種硬化膜，其係將請求項1至請求項6之任一項所述之硬化性樹脂組成物硬化而成。 A cured film, which is formed by curing the curable resin composition described in any one of claim 1 to claim 6. 一種積層體，其係具有兩層以上的請求項10所述之硬化膜，並且在任意前述硬化膜彼此之間具有金屬層。 A laminate having two or more layers of the hardened film described in claim 10, and having a metal layer between any of the aforementioned hardened films. 一種硬化膜的製造方法，其係包括將請求項1至請求項6之任一項所述之硬化性樹脂組成物適用於基板上以形成膜之膜形成步驟。 A method for manufacturing a cured film, comprising a film forming step of applying the curable resin composition described in any one of claim 1 to claim 6 to a substrate to form a film. 如請求項12所述之硬化膜的製造方法，其係包括在50~450℃下對前述膜進行加熱之步驟。 The method for manufacturing a hardened film as described in claim 12 includes the step of heating the aforementioned film at 50-450°C. 一種半導體器件，其係具有請求項10所述之硬化膜或請求項11所述之積層體。 A semiconductor device having the hardened film described in claim 10 or the laminated body described in claim 11. 一種樹脂，其係包含下述式(1-1)所表示之重複單元且包含選自包括下述式(3-2)所表示之重複單元及下述式(3-3)所表示之重複單元之群組中的至少一種重複單元；
Figure 109142390-A0305-02-0199-11
 式(1-1)中，Y1表示2價連接基，Ar1表示可以具有縮合環結構之芳香族烴基，Y2表示單鍵或2價連接基；式(3-2)中，X6表示4價基團，Z2表示具有包含乙烯性不飽和鍵之基團之2價連接基；式(3-3)中，X7及X8分別獨立地表示3價連接基，Z3及Z4分別獨立地表示2價連接基，Z3及Z4中的至少一者表示具有包含乙烯性不飽和鍵之基團之2價連接基。 A resin comprising a repeating unit represented by the following formula (1-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-2) and a repeating unit represented by the following formula (3-3);
Figure 109142390-A0305-02-0199-11
 In formula (1-1), Y1 represents a divalent linking group, Ar1 represents an aromatic hydrocarbon group which may have a condensed ring structure, and Y2 represents a single bond or a divalent linking group; in formula (3-2), X6 represents a tetravalent group, and Z2 represents a divalent linking group having a group containing an ethylenic unsaturated bond; in formula (3-3), X7 and X8 each independently represent a trivalent linking group, Z3 and Z4 each independently represent a divalent linking group, and at least one of Z3 and Z4 represents a divalent linking group having a group containing an ethylenic unsaturated bond. 如請求項15所述之樹脂，其中式(3-2)中的Z2為式(Z-1)所表示之基團，式(3-3)中的Z3及Z4中的至少一者為式(Z-1)所表示之基團，
Figure 109142390-A0305-02-0199-12
 式(Z-1)中，Q1表示碳數1~30的有機基，A1表示包含包含乙烯性不飽和鍵之基團之基團，n1表示1以上的整數，*表示與其他結構的鍵結部 位。 The resin as described in claim 15, wherein Z2 in formula (3-2) is a group represented by formula (Z-1), and at least one of Z3 and Z4 in formula (3-3) is a group represented by formula (Z-1),
Figure 109142390-A0305-02-0199-12
 In formula (Z-1), Q1 represents an organic group having 1 to 30 carbon atoms, A1 represents a group containing an ethylenically unsaturated bond, n1 represents an integer greater than 1, and * represents a bonding site with other structures. 如請求項16所述之樹脂，其中式(Z-1)中的Q1為選自包括式(A2-1)~式(A2-5)所表示之結構之群組中的至少一種結構，
Figure 109142390-A0305-02-0200-13
 式(A2-1)~(A2-5)中，RA211~RA214、RA221~RA224、RA231~RA238、RA241~RA248及RA251~RA258分別獨立地表示氫原子、烷基、環狀烷基、烷氧基、羥基、氰基、鹵化烷基或鹵素原子，LA231及LA241分別獨立地表示單鍵、羰基、磺醯基、2價飽和烴基、2價不飽和烴基、雜原子、雜環基或鹵化伸烷基，RA211~RA214中的至少一個、RA221~RA224中的至少一個、RA231~RA238中的至少一個、RA241~RA248中的至少一個及RA251~RA258中的至少一個可以為與上述式(Z-1)中的A1的鍵結部位，*分別獨立地表示與其他結構的鍵結部位。 The resin as claimed in claim 16, wherein Q1 in formula (Z-1) is at least one structure selected from the group consisting of structures represented by formulas (A2-1) to (A2-5),
Figure 109142390-A0305-02-0200-13
 In formulas (A2-1) to (A2-5), R A211 to R A214 , R A221 to R A224 , R A231 to R A238 , R A241 to R A248 , and R A251 to R A258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group, or a halogen atom; L A231 and L A241 each independently represent a single bond, a carbonyl group, a sulfonyl group, a divalent saturated alkyl group, a divalent unsaturated alkyl group, a heteroatom, a heterocyclic group, or a halogenated alkylene group; at least one of R A211 to R A214 , at least one of R A221 to R A224 , at least one of R A231 to R A238 , R At least one of A241 to R A248 and at least one of R A251 to R A258 can be a bonding site with A1 in the above formula (Z-1), and * independently represents a bonding site with other structures. 一種樹脂，其係包含下述式(1-1)所表示之重複單元且包 含選自包括下述式(3-1)所表示之重複單元、下述式(3-2)所表示之重複單元、下述式(3-3)所表示之重複單元及下述式(3-4)所表示之重複單元之群組中的至少一種重複單元，作為包含式(1-1)所表示之重複單元之重複單元，包含式(5-1)所表示之重複單元，
Figure 109142390-A0305-02-0201-14
 式(1-1)中，Y1表示烴基，Ar1表示可以具有縮合環結構之芳香族烴基，Y2表示單鍵或烴基； 式(3-1)中，X5表示4價連接基，R3及R4分別獨立地表示1價有機基，Z1表示2價連接基，R3、R4及Z1中的至少一個包含包含乙烯性不飽和鍵之基團；式(3-2)中，X6表示4價基團，Z2表示具有包含乙烯性不飽和鍵之基團之2價連接基；式(3-3)中，X7及X8分別獨立地表示3價連接基，Z3及Z4分別獨立地表示2價連接基，Z3及Z4中的至少一者表示具有包含乙烯性不飽和鍵之基團之2價連接基；式(3-4)中，X7及X8分別獨立地表示3價連接基，Z3及Z4分別獨立地表示2價連接基，R5及R6分別獨立地表示1價有機基，Z3及Z4中的至少一者表示具有包含乙烯性不飽和鍵之基團之2價連接基，R5、R6、Z3及Z4中的至少一個包含包含乙烯性不飽和鍵之基團；
Figure 109142390-A0305-02-0202-15
 式(5-1)中，L51為式(L-1)所表示之結構，L52表示2價有機基；
Figure 109142390-A0305-02-0202-16
 式(L-1)中，Y1表示烴基，Ar1表示可以具有縮合環結構之芳香族烴基，Y2表示單鍵或烴基，*表示與其他結構的鍵結部位。 A resin comprising a repeating unit represented by the following formula (1-1) and at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), a repeating unit represented by the following formula (3-3) and a repeating unit represented by the following formula (3-4), as a repeating unit including the repeating unit represented by the following formula (1-1), comprising a repeating unit represented by the following formula (5-1),
Figure 109142390-A0305-02-0201-14
 In formula (1-1), Y1 represents an alkyl group, Ar1 represents an aromatic alkyl group which may have a condensed ring structure, and Y2 represents a single bond or an alkyl group; In formula (3-1), X5 represents a 4-valent linking group, R3 and R4 each independently represent a 1-valent organic group, Z1 represents a 2-valent linking group, and at least one of R3 , R4 and Z1 contains a group containing an ethylenic unsaturated bond; In formula (3-2), X6 represents a 4-valent group, and Z2 represents a 2-valent linking group having a group containing an ethylenic unsaturated bond; In formula (3-3), X7 and X8 each independently represent a 3-valent linking group, Z3 and Z4 each independently represent a 2-valent linking group, and Z3 and Z4 each independently represent a 3-valent linking group. At least one of X7 and X8 represents a divalent connecting group having a group containing an ethylenic unsaturated bond; in formula (3-4), X7 and X8 each independently represent a trivalent connecting group, Z3 and Z4 each independently represent a divalent connecting group, R5 and R6 each independently represent a monovalent organic group, at least one of Z3 and Z4 represents a divalent connecting group having a group containing an ethylenic unsaturated bond, and at least one of R5 , R6 , Z3 and Z4 contains a group containing an ethylenic unsaturated bond;
Figure 109142390-A0305-02-0202-15
 In formula (5-1), L 51 is the structure represented by formula (L-1), and L 52 represents a divalent organic group;
Figure 109142390-A0305-02-0202-16
 In formula (L-1), Y1 represents a alkyl group, Ar1 represents an aromatic alkyl group which may have a condensed ring structure, Y2 represents a single bond or a alkyl group, and * represents a bonding site with other structures. 如請求項18所述之樹脂，其中 式(3-1)中的Z1為式(Z-1)所表示之基團，式(3-2)中的Z2為式(Z-1)所表示之基團，式(3-3)中的Z3及Z4中的至少一者為式(Z-1)所表示之基團，式(3-4)中的Z3及Z4中的至少一者為式(Z-1)所表示之基團，
Figure 109142390-A0305-02-0203-17
 式(Z-1)中，Q1表示碳數1~30的有機基，A1表示包含包含乙烯性不飽和鍵之基團之基團，n1表示1以上的整數，*表示與其他結構的鍵結部位。 The resin as described in claim 18, wherein Z1 in formula (3-1) is a group represented by formula (Z-1), Z2 in formula (3-2) is a group represented by formula (Z-1), at least one of Z3 and Z4 in formula (3-3) is a group represented by formula (Z-1), and at least one of Z3 and Z4 in formula (3-4) is a group represented by formula (Z-1),
Figure 109142390-A0305-02-0203-17
 In formula (Z-1), Q1 represents an organic group having 1 to 30 carbon atoms, A1 represents a group containing an ethylenically unsaturated bond, n1 represents an integer greater than 1, and * represents a bonding site with other structures. 如請求項19所述之樹脂，其中式(Z-1)中的Q1為選自包括式(A2-1)~式(A2-5)所表示之結構之群組中的至少一種結構，
Figure 109142390-A0305-02-0203-18
 式(A2-1)~(A2-5)中，RA211~RA214、RA221~RA224、RA231~RA238、RA241~RA248及RA251~RA258分別獨立地表示氫原子、烷基、環狀烷基、烷氧基、 羥基、氰基、鹵化烷基或鹵素原子，LA231及LA241分別獨立地表示單鍵、羰基、磺醯基、2價飽和烴基、2價不飽和烴基、雜原子、雜環基或鹵化伸烷基，RA211~RA214中的至少一個、RA221~RA224中的至少一個、RA231~RA238中的至少一個、RA241~RA248中的至少一個及RA251~RA258中的至少一個可以為與上述式(Z-1)中的A1的鍵結部位，*分別獨立地表示與其他結構的鍵結部位。The resin as claimed in claim 19, wherein Q1 in formula (Z-1) is at least one structure selected from the group consisting of structures represented by formulas (A2-1) to (A2-5),
Figure 109142390-A0305-02-0203-18
 In formulas (A2-1) to (A2-5), R A211 to R A214 , R A221 to R A224 , R A231 to R A238 , R A241 to R A248 , and R A251 to R A258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group, or a halogen atom; L A231 and L A241 each independently represent a single bond, a carbonyl group, a sulfonyl group, a divalent saturated alkyl group, a divalent unsaturated alkyl group, a heteroatom, a heterocyclic group, or a halogenated alkylene group; at least one of R A211 to R A214 , at least one of R A221 to R A224 , at least one of R A231 to R A238 , R At least one of A241 to R A248 and at least one of R A251 to R A258 can be a bonding site with A1 in the above formula (Z-1), and * independently represents a bonding site with other structures.
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