TWI802640B - Photosensitive resin composition, resin, cured film, laminate, method for producing cured film, semiconductor element - Google Patents

Photosensitive resin composition, resin, cured film, laminate, method for producing cured film, semiconductor element Download PDF

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TWI802640B
TWI802640B TW108102651A TW108102651A TWI802640B TW I802640 B TWI802640 B TW I802640B TW 108102651 A TW108102651 A TW 108102651A TW 108102651 A TW108102651 A TW 108102651A TW I802640 B TWI802640 B TW I802640B
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group
formula
resin composition
photosensitive resin
organic group
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TW108102651A
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TW201934614A (en
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川端健志
吉田健太
岩井悠
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日商富士軟片股份有限公司
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    • 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
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • C08G73/22—Polybenzoxazoles
    • 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
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • 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
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Abstract

一種感光性樹脂組成物、樹脂、硬化膜、積層體、硬化膜之製造方法及半導體元件，該感光性樹脂組成物包含選自聚醯亞胺前驅物及聚苯并㗁唑前驅物之聚合物前驅物及光活性化合物，聚合物前驅物具有包括在由來自於四羧酸、四羧酸衍生物、二羧酸及二羧酸衍生物的至少一種之構成單元以及來自於二胺的至少一種之構成單元構成之聚合物前驅物的側鏈經由連接基鍵結之磺酸基以及與聚合物前驅物的末端鍵結之磺酸基之群組中的至少一種。A photosensitive resin composition, a resin, a cured film, a laminate, a method for producing a cured film, and a semiconductor element, the photosensitive resin composition comprising a polymer selected from polyimide precursors and polybenzoxazole precursors Precursor and photoactive compound, the polymer precursor has at least one structural unit derived from tetracarboxylic acid, tetracarboxylic acid derivative, dicarboxylic acid and dicarboxylic acid derivative and at least one from diamine At least one of the group consisting of a sulfonic acid group bonded to the side chain of the polymer precursor constituted by a linker and a sulfonic acid group bonded to a terminal of the polymer precursor.

Description

感光性樹脂組成物、樹脂、硬化膜、積層體、硬化膜之製造方法、半導體元件Photosensitive resin composition, resin, cured film, laminate, method for producing cured film, semiconductor element

本發明係關於一種感光性樹脂組成物、樹脂、硬化膜、積層體、硬化膜之製造方法、半導體元件。The present invention relates to a photosensitive resin composition, a resin, a cured film, a laminate, a method for producing a cured film, and a semiconductor element.

由於使聚醯亞胺前驅物、聚苯并㗁唑前驅物等環化而硬化之聚醯亞胺樹脂、聚苯并㗁唑樹脂的耐熱性或絕緣性等優異，可適用於各種用途（例如參閱非專利文獻1、2）。其用途並無特別限定，但是在構裝用半導體元件的領域中，可舉出利用於絕緣膜及其保護膜或密封材的材料。又，亦可用作柔性基板的基底薄膜或覆蓋層等。 通常上述聚醯亞胺樹脂及聚苯并㗁唑樹脂相對於溶劑的溶解性降低。因此，可舉出通常使用以環化反應前的聚合物前驅物（聚醯亞胺前驅物或聚苯并㗁唑前驅物）的狀態溶解於溶劑中並塗佈於基板等來適用之方法之一例。之後，進行加熱而使聚合物前驅物環化，能夠形成硬化之樹脂層（硬化膜）。Polyimide resins and polybenzoxazole resins cured by cyclization of polyimide precursors and polybenzoxazole precursors are excellent in heat resistance and insulation, and can be used in various applications (such as Refer to non-patent literature 1, 2). The use thereof is not particularly limited, but in the field of semiconductor elements for packaging, materials used for insulating films, protective films thereof, or sealing materials can be mentioned. Moreover, it can also be used as a base film, a cover layer, etc. of a flexible board|substrate. Generally, the above-mentioned polyimide resin and polybenzoxazole resin have low solubility in solvents. Therefore, it is possible to use a method in which a polymer precursor (polyimide precursor or polybenzoxazole precursor) before the cyclization reaction is generally dissolved in a solvent and applied to a substrate or the like. an example. After that, heating is performed to cyclize the polymer precursor to form a cured resin layer (cured film).

關於如上述的聚合物前驅物，例如記載於專利文獻1中。專利文獻1中，揭示有利用鹵化劑將二羧酸或二羧酸衍生物進行鹵化之後與二胺進行反應時調整鹵化劑、反應系統中所含有之水及原料的量。藉此，能夠加快聚合物前驅物的環化速度。同一文獻中，還揭示有在聚合物前驅物附加特定的酸基。 [先前技術文獻] [專利文獻]The above-mentioned polymer precursor is described in Patent Document 1, for example. Patent Document 1 discloses adjusting the amounts of the halogenating agent, water contained in the reaction system, and raw materials when reacting with diamine after halogenating dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent. Thereby, the cyclization speed of the polymer precursor can be accelerated. The same document also discloses that a specific acid group is added to a polymer precursor. [Prior Art Literature] [Patent Document]

[專利文獻1]國際公開WO2017/104672號小冊子 [非專利文獻][Patent Document 1] International Publication No. WO2017/104672 Pamphlet [Non-patent literature]

[非專利文獻1]Science & technology Co.,Ltd.“聚醯亞胺的高機能化及應用技術”2008年4月 [非專利文獻2]柿本雅明/監修、CMC Technical Library“聚醯亞胺材料的基礎及開發”2011年11月發行[Non-Patent Document 1] Science & technology Co., Ltd. "Higher Functionalization and Application Technology of Polyimide" April 2008 [Non-Patent Document 2] Masaki Kakimoto/Supervisor, CMC Technical Library "Basics and Development of Polyimide Materials", November 2011 issue

聚合物前驅物能夠如上述那樣藉由環化來使其硬化，但是由於其特性，保存時繼續環化而有時缺乏樹脂的穩定性。 因此，本發明的目的在於提供一種保存穩定性優異之感光性樹脂組成物、樹脂、硬化膜、積層體、硬化膜之製造方法及半導體元件。The polymer precursor can be hardened by cyclization as described above, but due to its characteristics, the cyclization continues during storage and the stability of the resin may be lacking. Therefore, an object of the present invention is to provide a photosensitive resin composition, a resin, a cured film, a laminate, a method for producing a cured film, and a semiconductor element excellent in storage stability.

基於上述課題，本發明人進行了深入研究之結果，發現藉由對構成感光性樹脂組成物之聚合物前驅物以特定的形態導入磺酸基，可解決上述課題。具體而言，藉由下述機構＜1＞，較佳為藉由＜2＞～＜18＞解決了上述課題。Based on the above-mentioned problems, the present inventors conducted intensive studies and found that the above-mentioned problems can be solved by introducing sulfonic acid groups in a specific form into the polymer precursor constituting the photosensitive resin composition. Specifically, the above-mentioned problems are solved by the following means <1>, preferably <2> to <18>.

＜1＞一種感光性樹脂組成物，其包含選自聚醯亞胺前驅物及聚苯并㗁唑前驅物之聚合物前驅物及光活性化合物，其中，上述聚合物前驅物具有包括在由來自於四羧酸、四羧酸衍生物、二羧酸及二羧酸衍生物的至少一種之構成單元以及來自於二胺的至少一種之構成單元構成之上述聚合物前驅物的側鏈經由連接基鍵結之磺酸基以及與上述聚合物前驅物的末端鍵結之磺酸基之群組中的至少一種。 ＜2＞如＜1＞所述之感光性樹脂組成物，其中 上述聚合物前驅物包含由下述式（1）表示之構成單元或由式（2）表示之構成單元， [化學式1]

Figure 02_image001
式（1）中，A1 及A2 分別獨立地表示氧原子或NH，R111 表示2價的有機基，R115 表示4價的有機基，R113 及R114 分別獨立地表示氫原子或1價的有機基， [化學式2]
Figure 02_image003
式（2）中，R121 表示2價的有機基，R122 表示4價的有機基，R123 及R124 分別獨立地表示氫原子或1價的有機基。 ＜3＞如＜2＞所述之感光性樹脂組成物，其中 上述聚合物前驅物包含由式（1）表示之構成單元。 ＜4＞如＜1＞～＜3＞中任一項所述之感光性樹脂組成物，其中 上述聚合物前驅物具有由式（1-1）、式（1-2）、式（1-3）、式（2-1）、式（2-2）及式（2-3）中的任一個所表示之部位， [化學式3]
Figure 02_image005
式中，A1 及A2 分別獨立地表示氧原子或NH，R111 表示2價的有機基，R115 表示4價的有機基，R113 及R114 分別獨立地表示氫原子或1價的有機基，X1 、X2 及X3 分別獨立地表示連接基，*表示與聚醯亞胺前驅物的主鏈的鍵結位置，ns表示1～4的整數， [化學式4]
Figure 02_image007
式中，R121 表示2價的有機基，R122 表示4價的有機基，R123 及R124 分別獨立地表示氫原子或1價的有機基，X4 、X5 及X6 分別獨立地表示連接基，*表示與聚苯并㗁唑前驅物的主鏈的鍵結位置，ns表示1～4的整數。 ＜5＞如＜1＞～＜4＞中任一項所述之感光性樹脂組成物，其中 上述聚合物前驅物中所含有之磺酸基的合計數係總構成單元的合計數的0.05%以上且15.0%以下。 ＜6＞如＜1＞～＜5＞中任一項所述之感光性樹脂組成物，其還包含自由基聚合性化合物。 ＜7＞如＜1＞～＜6＞中任一項所述之感光性樹脂組成物，其還包含硬化促進劑。 ＜8＞如＜1＞～＜7＞中任一項所述之感光性樹脂組成物，其中 上述光活性化合物包含光自由基聚合起始劑。 ＜9＞如＜1＞～＜8＞中任一項所述之感光性樹脂組成物，其用於顯影。 ＜10＞如＜1＞～＜9＞中任一項所述之感光性樹脂組成物，其用於使用包含有機溶劑之顯影液進行顯影之用途。 ＜11＞如＜1＞～＜10＞中任一項所述之感光性樹脂組成物，其用於再配線層用層間絕緣膜的形成。 ＜12＞一種樹脂，其包括選自聚醯亞胺前驅物及聚苯并㗁唑前驅物之聚合物前驅物之樹脂，其中 上述聚合物前驅物具有由式（1-1）、式（1-2）、式（1-3）、式（2-1）式（2-2）或式（2-3）中的任一個所表示之部位， [化學式5]
Figure 02_image009
式中，A1 及A2 分別獨立地表示氧原子或NH，R111 表示2價的有機基，R115 表示4價的有機基，R113 及R114 分別獨立地表示氫原子或1價的有機基，X1 、X2 及X3 分別獨立地表示連接基，*表示與聚醯亞胺前驅物的主鏈的鍵結位置，ns表示1～4的整數， [化學式6]
Figure 02_image011
式中，R121 表示2價的有機基，R122 表示4價的有機基，R123 及R124 分別獨立地表示氫原子或1價的有機基，X4 、X5 及X6 分別獨立地表示連接基，*表示與聚苯并㗁唑前驅物的主鏈的鍵結位置，ns表示1～4的整數。 ＜13＞一種硬化膜，其將＜1＞～＜11＞中任一項所述之感光性樹脂組成物進行硬化而成。 ＜14＞一種積層體，其具有2層以上的＜13＞所述之硬化膜。 ＜15＞如＜14＞所述之積層體，其中 在上述硬化膜之間具有金屬層。 ＜16＞一種硬化膜的製造方法，其包括使用＜1＞～＜11＞中任一項所述之感光性樹脂組成物之步驟。 ＜17＞如＜16＞所述之硬化膜之製造方法，其具有： 將上述感光性樹脂組成物適用於基板而成為層狀之感光性樹脂組成物層形成步驟； 對上述感光性樹脂組成物層進行曝光之曝光步驟；及 對經上述曝光之感光性樹脂組成物層進行顯影處理之顯影處理步驟。 ＜18＞一種半導體元件，其具有＜13＞所述之硬化膜或＜14＞或者＜15＞所述之積層體。 [發明效果]<1> A photosensitive resin composition comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor and a photoactive compound, wherein the above polymer precursor has The side chain of the above-mentioned polymer precursor composed of at least one structural unit of tetracarboxylic acid, tetracarboxylic acid derivative, dicarboxylic acid and dicarboxylic acid derivative, and at least one structural unit derived from diamine via a linking group At least one of the group of bonded sulfonic acid groups and the group of bonded sulfonic acid groups to the terminal of the polymer precursor. <2> The photosensitive resin composition as described in <1>, wherein the polymer precursor contains a structural unit represented by the following formula (1) or a structural unit represented by the formula (2), [Chemical formula 1]
Figure 02_image001
In formula (1), A 1 and A 2 independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 independently represent a hydrogen atom or Monovalent organic group, [chemical formula 2]
Figure 02_image003
In formula (2), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. <3> The photosensitive resin composition according to <2>, wherein the polymer precursor contains a structural unit represented by formula (1). <4> The photosensitive resin composition according to any one of <1> to <3>, wherein the above-mentioned polymer precursor has the formula (1-1), formula (1-2), formula (1- 3), the site represented by any one of formula (2-1), formula (2-2) and formula (2-3), [chemical formula 3]
Figure 02_image005
In the formula, A 1 and A 2 independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 independently represent a hydrogen atom or a monovalent An organic group, X 1 , X 2 and X 3 independently represent a linking group, * represents the bonding position with the main chain of the polyimide precursor, ns represents an integer of 1 to 4, [chemical formula 4]
Figure 02_image007
In the formula, R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group, X 4 , X 5 and X 6 independently represents a linking group, * represents the bonding position with the main chain of the polybenzoxazole precursor, and ns represents an integer of 1-4. <5> The photosensitive resin composition according to any one of <1> to <4>, wherein the total number of sulfonic acid groups contained in the polymer precursor is 0.05% of the total number of the total structural units Above and below 15.0%. <6> The photosensitive resin composition according to any one of <1> to <5>, further containing a radical polymerizable compound. <7> The photosensitive resin composition as described in any one of <1>-<6> which further contains a hardening accelerator. <8> The photosensitive resin composition according to any one of <1> to <7>, wherein the photoactive compound contains a photoradical polymerization initiator. <9> The photosensitive resin composition according to any one of <1> to <8>, which is used for image development. <10> The photosensitive resin composition according to any one of <1> to <9>, which is used for image development using a developer containing an organic solvent. <11> The photosensitive resin composition as described in any one of <1>-<10> used for formation of the interlayer insulating film for rewiring layers. <12> A resin comprising a resin selected from the polymer precursors of polyimide precursors and polybenzoxazole precursors, wherein the above polymer precursors have formula (1-1), formula (1 -2), formula (1-3), formula (2-1), formula (2-2) or the site represented by any one of formula (2-3), [chemical formula 5]
Figure 02_image009
In the formula, A 1 and A 2 independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 independently represent a hydrogen atom or a monovalent An organic group, X 1 , X 2 and X 3 independently represent a linking group, * represents the bonding position with the main chain of the polyimide precursor, ns represents an integer of 1 to 4, [Chemical Formula 6]
Figure 02_image011
In the formula, R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group, X 4 , X 5 and X 6 independently represents a linking group, * represents the bonding position with the main chain of the polybenzoxazole precursor, and ns represents an integer of 1-4. <13> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <11>. <14> A laminate having two or more layers of the cured film described in <13>. <15> The laminate according to <14>, which has a metal layer between the cured films. <16> A method for producing a cured film including the step of using the photosensitive resin composition according to any one of <1> to <11>. <17> The method for producing a cured film according to <16>, comprising: a step of forming a layered photosensitive resin composition layer by applying the photosensitive resin composition to a substrate; an exposure step of exposing the exposed photosensitive resin composition layer; and a development treatment step of performing a development treatment on the exposed photosensitive resin composition layer. <18> A semiconductor element comprising the cured film described in <13> or the laminate described in <14> or <15>. [Invention effect]

藉由本發明，能夠提供一種保存穩定性優異之感光性樹脂組成物以及樹脂、硬化膜、積層體、硬化膜之製造方法及半導體元件。另外，藉由本發明，能夠提供新型樹脂來實現材料的豊富化。According to the present invention, a photosensitive resin composition excellent in storage stability, a resin, a cured film, a laminate, a method for producing a cured film, and a semiconductor element can be provided. In addition, according to the present invention, it is possible to provide a new type of resin to realize enrichment of materials.

本說明書中，“～”是指將記載於其前後之數值作為下限值及上限值而包含之範圍的定義而使用。 本發明中的結構要件的說明有時基於本發明的代表性實施形態而進行，但本發明並不限定於該等實施形態。 關於本說明書中的基團（原子團）的標記，未記述經取代及未經取代之標記係同時包含不具有取代基者和具有取代基者。例如，“烷基”不僅包含不具有取代基之烷基（未經取代的烷基），還包含具有取代基之烷基（取代烷基）。 本說明書中“曝光”只要無特別限定，除了利用光的曝光以外，利用電子束、離子束等粒子束之描繪亦包含於曝光中。又，作為使用於曝光之光，通常可舉出以水銀燈的明線光譜、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。 本說明書中，“（甲基）丙烯酸酯”表示“丙烯酸酯”及“甲基丙烯酸酯”這兩者或其中任一個，“（甲基）丙烯酸”表示“丙烯酸”及“甲基丙烯酸”這兩者或其中任一個，“（甲基）丙烯醯基”表示“丙烯醯基”及“甲基丙烯醯基”這兩者或其中任一個。 本說明書中，“步驟”這一術語，不僅是獨立的步驟，而且即使於無法與其他步驟明確區分之情況下，若可實現對該步驟所期待之作用，則亦包含於本術語中。 本說明書中，固體成分係相對於組成物的總質量中除了溶劑以外的成分的質量百分率。又，只要沒有特別記載，則固體成分濃度是指25℃下的濃度。 本說明書中，只要沒有特別記載，則重量平均分子量（Mw）及數平均分子量（Mn）基於凝膠滲透層析法（GPC測量），並作為苯乙烯換算值而定義。本說明書中，重量平均分子量（Mw）及數平均分子量（Mn）例如能夠利用HLC-8220（TOSOH CORPORATION製），並作為管柱而使用保護管柱HZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000及TSKgel Super HZ2000（TOSOH CORPORATION製）而求出。只要沒有特別記載，則將洗提液設為利用THF（四氫呋喃）測量者。又，只要沒有特別記載，則將檢測設為使用UV線（紫外線）的波長254nm檢測器者。In this specification, "-" is used for the definition of the range which uses the numerical value described before and after it as a lower limit and an upper limit. The description of the constituent elements in the present invention may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments. Regarding the notation of a group (atomic group) in this specification, the notation of substitution and non-substitution includes both those without a substituent and those with a substituent. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Unless otherwise specified, "exposure" in this specification includes not only exposure by light but also drawing by particle beams such as electron beams and ion beams. In addition, as the light used for exposure, there are usually actinic rays or radiation such as bright line spectrum of a mercury lamp, excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid". Both or any of them, "(meth)acryl" means both or either of "acryl" and "methacryl". In this specification, the term "step" is not only an independent step, but also includes in this term as long as the expected action of the step can be achieved even when it cannot be clearly distinguished from other steps. In the present specification, the solid content refers to the mass percentage of components other than the solvent relative to the total mass of the composition. In addition, unless otherwise specified, the solid content concentration refers to the concentration at 25°C. In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as styrene-equivalent values based on gel permeation chromatography (GPC measurement). In this specification, weight average molecular weight (Mw) and number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) were used to obtain them. Unless otherwise specified, the eluent was measured with THF (tetrahydrofuran). In addition, unless otherwise specified, detection was performed using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays).

本發明的感光性樹脂組成物（以下，有時簡稱為“本發明的組成物”或“本發明的樹脂組成物”）的特徵為，其包含選自聚醯亞胺前驅物及聚苯并㗁唑前驅物之聚合物前驅物及光活性化合物，聚合物前驅物具有包括在由來自於四羧酸、四羧酸衍生物、二羧酸及二羧酸衍生物的至少一種之構成單元以及來自於二胺的至少一種之構成單元構成之聚合物前驅物的側鏈（主鏈結構的側鏈）經由連接基鍵結之磺酸基以及與聚合物前驅物的末端（主鏈結構的末端）鍵結之磺酸基之群組中的至少一種。以下，以構成本組成物的較佳的實施形態之成分組成為中心，對本發明進行詳細說明。The photosensitive resin composition of the present invention (hereinafter, sometimes simply referred to as "the composition of the present invention" or "the resin composition of the present invention") is characterized in that it contains polyimide precursors and polybenzoic acid A polymer precursor and a photoactive compound of a azole precursor, the polymer precursor has at least one structural unit from tetracarboxylic acid, tetracarboxylic acid derivative, dicarboxylic acid and dicarboxylic acid derivative and The side chain (the side chain of the main chain structure) of the polymer precursor composed of at least one structural unit derived from diamine, the sulfonic acid group bonded via the linker and the terminal of the polymer precursor (the end of the main chain structure) ) at least one of the group of bonded sulfonic acid groups. Hereinafter, the present invention will be described in detail centering on the component composition constituting a preferred embodiment of the present composition.

＜聚合物前驅物＞ 本發明的感光性樹脂組成物包含選自聚醯亞胺前驅物及聚苯并㗁唑前驅物中之聚合物前驅物。作為聚合物前驅物，由來自於四羧酸、四羧酸衍生物、二羧酸及二羧酸衍生物的至少一種之構成單元以及來自於二胺的至少一種之構成單元構成。其中，由來自於四羧酸等之構成單元及來自於二胺之構成單元構成係指該等構成單元佔聚合物前驅物的構成單元的大多數，聚合物前驅物的總構成單元均不必由該等構成單元構成。例如，只要總構成單元的70莫耳%以上、進一步為80莫耳%以上、尤其為90莫耳%以上為上述構成單元，則滿足上述要件。 作為來自於四羧酸、四羧酸衍生物之結構，可舉出包括後述之式（1）的R115 及相鄰之4個羰基之結構，作為來自於二羧酸、二羧酸衍生物之構成單元，可舉出包括後述之式（2）的R121 及相鄰之2個羰基之構成單元。作為二胺的結構，可舉出包括後述之式（1）的R111 及相鄰之2個NH之構成單元及包括後述之式（2）的R122 及相鄰之2個NH基之構成單元。亦即，本發明的感光性樹脂組成物中，一實施形態中，向上述R115 、R122 、R111 、R121 的至少一部分經由連接基導入磺酸基為較佳。作為此時的連接基，可舉出後述之式（Ls）的*1 -Li-Lt-*2 的例。其中，*1 係主鏈結構側，*2 係磺酸基側。在聚合物前驅物之中，聚醯亞胺前驅物為較佳。<Polymer Precursor> The photosensitive resin composition of the present invention contains a polymer precursor selected from polyimide precursors and polybenzoxazole precursors. The polymer precursor is composed of a structural unit derived from at least one of tetracarboxylic acid, tetracarboxylic acid derivative, dicarboxylic acid, and dicarboxylic acid derivative, and at least one structural unit derived from diamine. Among them, the composition of structural units derived from tetracarboxylic acid and the like and structural units derived from diamine means that these structural units account for the majority of the structural units of the polymer precursor, and the total structural units of the polymer precursor do not have to be composed of These constituent units constitute. For example, the above-mentioned requirements are met if 70 mol% or more of the total structural units, further 80 mol% or more, especially 90 mol% or more are the above-mentioned structural units. As the structure derived from tetracarboxylic acid and tetracarboxylic acid derivatives, the structure including R 115 and adjacent four carbonyl groups in the formula (1) described later can be mentioned, and the structure derived from dicarboxylic acid and dicarboxylic acid derivatives can be mentioned. The structural unit includes a structural unit including R 121 and two adjacent carbonyl groups in the formula (2) described later. Examples of the structure of the diamine include a constitutional unit including R 111 of the formula (1) described below and two adjacent NH groups, and a structure including R 122 of the formula (2) described below and two adjacent NH groups. unit. That is, in one embodiment of the photosensitive resin composition of the present invention, it is preferable to introduce a sulfonic acid group into at least a part of the above-mentioned R 115 , R 122 , R 111 , and R 121 via a linking group. Examples of the linking group in this case include * 1 -Li-Lt-* 2 in the formula (Ls) described later. Among them, * 1 is the side of the main chain structure, and * 2 is the side of the sulfonic acid group. Among the polymer precursors, polyimide precursors are preferred.

本發明中，上述聚合物前驅物在其末端及側鏈的至少任一處以特定的形態具有磺酸基。其中，磺酸基係（i）在聚合物前驅物的側鏈經由連接基鍵結之磺酸基或者（ii）在與聚合物前驅物的末端鍵結之磺酸基。如上所述規定推測為具有以下的技術性意義。亦即，關於（i）磺酸基在側鏈經由連接基鍵結之方面，與未經由連接基而導入有磺酸基者進行比較，能夠期待磺酸基的運動性良好且相對於保存穩定性之效果較大之類的作用。關於（ii）與聚合物前驅物的末端鍵結之磺酸基，同樣地能夠期待磺酸基的運動性良好且相對於保存穩定性之效果較大之類的作用。另外，本發明中“磺酸基”係狹隘的磺酸基、亦即在碳骨架上鍵結有-SO3 H基之結構，與胺基磺酸結構或磺酸單酯結構不同。樹脂具有作為強酸基的磺酸基，藉此能夠期待發揮作為高酸基的作用。另外，上述聚合物前驅物中，可以有除了碳骨架以外鍵結之-SO3 H基，但是沒有除了與碳骨架以外鍵結之-SO3 H基為較佳。 另外，以下有時將滿足上述條件之部位稱為“包含磺酸基之部位”。In the present invention, the above-mentioned polymer precursor has a sulfonic acid group in a specific form in at least any one of its terminal and side chain. Wherein, the sulfonic acid group is (i) a sulfonic acid group bonded to a side chain of the polymer precursor via a linker or (ii) a sulfonic acid group bonded to a terminal of the polymer precursor. The above-mentioned regulations presumably have the following technical meanings. That is, regarding (i) the sulfonic acid group is bonded to the side chain via a linking group, compared with a sulfonic acid group introduced without a linking group, it can be expected that the sulfonic acid group has good mobility and is relatively stable in storage. The effect of sex is greater and the like. With respect to (ii) the sulfonic acid group bonded to the terminal of the polymer precursor, similar effects such as good mobility of the sulfonic acid group and a large effect on storage stability can be expected. In addition, the "sulfonic acid group" in the present invention refers to a narrow sulfonic acid group, that is, a structure in which a -SO 3 H group is bonded to a carbon skeleton, and is different from an sulfamic acid structure or a sulfonic acid monoester structure. Since the resin has a sulfonic acid group as a strong acid group, it can be expected to function as a high acid group. In addition, in the above-mentioned polymer precursor, there may be -SO 3 H groups bonded to other than the carbon skeleton, but it is preferable to have no -SO 3 H groups bonded to other than the carbon skeleton. In addition, a site satisfying the above conditions may be referred to as "a site containing a sulfonic acid group" hereinafter.

作為包含上述磺酸基之部位的較佳的實施形態可舉出下述式（Ls）的結構。 *1 -Li-Lt-（SO3 H）ns 式（Ls） *1 係成為主鏈之結構（例如芳香環）側的鍵結位置。Li及Lt分別獨立地為連接基或單鍵，至少一個係連接基。另外，在成為主鏈之結構與式（Ls）的部位之間亦可以存在對詳細內容進行後述之連接基L且連接基Lh，但是不存在為較佳。式（Ls）可以與1個構成單元的側鏈和/或1個末端僅鍵結1個，亦可以鍵結2個以上。鍵結2個以上之情況下，各個式（Ls）可以相同，亦可以不同。本發明中，式（Ls）與1個構成單元的側鏈和/或1個末端僅鍵結1個為較佳。 尤其，式（Ls）與側鏈鍵結之情況下，式（Ls）與來自於四羧酸、四羧酸衍生物、二羧酸、二羧酸衍生物的至少一種之構成單元鍵結為較佳。 作為主鏈的一例，可舉出後述之式（1）中的-C（=O）-R115 -C（=O）-NH-R111 -NH-或後述之式（2）中的-NH-R122 -NH-C（=O）-R121 -C（=O）-。更具體而言，可例示式（Ls）與R115 、R111 、R122 、R121 的任一個鍵結之態樣。 Li係雜原子或具有雜原子之連接基，具有雜原子之連接基為較佳。作為具有雜原子之連接基，例如可舉出醯胺基（CONH）、酯基（COO）、脲基（NHCONH）、胺基甲酸酯基（NHCOO）、醯亞胺基（CONHCO）等。該等氫原子可以經取代基（例如後述之取代基T）取代，但是未經取代為較佳。另外，Li不會因連接基的標記的順序而被限定，例如相對於特定的連接方向，CONH可以為NHCO，COO可以為OCO，NHCOO可以為OCONH。 作為Lt，可舉出由碳原子及氫原子構成之連接基。Lt較佳為對詳細內容進行後述之連接基L中由碳原子及氫原子構成之連接基。Lt係碳數1～22者為較佳，1～18者為更佳，1～10者為進一步較佳。另外，Lt係烴基為較佳，伸烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、伸烯基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、伸芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、芳基伸烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳）為更佳，伸芳基為進一步較佳。 連接基Lt還可以存在具有雜原子之連接基Lh，亦可以不存在具有雜原子之連接基Lh。又，連接基Lt不妨礙在發揮本發明的效果之範圍具有羥基、羧酸、胺基、鹵素原子等取代基。Lh的詳細內容進行後述。 ns係1～4的整數，1或2為較佳，1為更佳。 式（Ls）的式量係14～300為較佳，50～200為更佳。The structure of the following formula (Ls) is mentioned as a preferable embodiment of the site|part containing the said sulfonic acid group. * 1 -Li-Lt-(SO 3 H) ns formula (Ls) * 1 is the bonding position on the side of the structure (such as aromatic ring) that becomes the main chain. Li and Lt are each independently a linking group or a single bond, and at least one of them is a linking group. In addition, linking group L and linking group Lh, which will be described in detail later, may exist between the structure serving as the main chain and the site of formula (Ls), but it is preferable not to exist. In the formula (Ls), only one side chain and/or one terminal of one constituent unit may be bonded, or two or more may be bonded. In the case of two or more bonds, each formula (Ls) may be the same or different. In the present invention, it is preferable that only one side chain and/or one terminal of one structural unit is bonded to the formula (Ls). In particular, when the formula (Ls) is bonded to the side chain, the formula (Ls) is bonded to at least one structural unit derived from tetracarboxylic acid, tetracarboxylic acid derivative, dicarboxylic acid, and dicarboxylic acid derivative as better. As an example of the main chain, -C(=O)-R 115 -C(=O)-NH-R 111 -NH- in formula (1) described later or - in formula (2) described later can be mentioned. NH-R 122 -NH-C(=O)-R 121 -C(=O)-. More specifically, an aspect in which formula (Ls) is bonded to any one of R 115 , R 111 , R 122 , and R 121 can be exemplified. Li-based heteroatoms or linking groups with heteroatoms, preferably linking groups with heteroatoms. As a linking group which has a heteroatom, an amido group (CONH), an ester group (COO), a urea group (NHCONH), a urethane group (NHCOO), an amido group (CONHCO), etc. are mentioned, for example. These hydrogen atoms may be substituted by substituents (such as the substituent T described later), but are preferably unsubstituted. In addition, Li is not limited by the labeling order of the linker. For example, with respect to a specific connection direction, CONH can be NHCO, COO can be OCO, and NHCOO can be OCONH. Examples of Lt include linking groups composed of carbon atoms and hydrogen atoms. Lt is preferably a linking group composed of carbon atoms and hydrogen atoms among the linking group L described later in detail. The carbon number of the Lt series is preferably 1-22, more preferably 1-18, and still more preferably 1-10. In addition, Lt-based hydrocarbon groups are preferred, alkylene groups (preferably having 1 to 12 carbons, more preferably 1 to 6, further preferably 1 to 3), alkenylenes (preferably having 2 to 12 carbons), , 2-6 is more preferred, 2-3 is further preferred), arylalkylene (6-22 carbons is preferred, 6-18 is more preferred, 6-10 is further preferred), arylalkylene (C7-23 is preferable, 7-19 is more preferable, and 7-11 is still more preferable), and an aryl extended group is still more preferable. In the linker Lt, there may be a linker Lh having a heteroatom, or there may be no linker Lh having a heteroatom. In addition, the linking group Lt does not prevent having a substituent such as a hydroxyl group, a carboxylic acid, an amino group, or a halogen atom within the range in which the effects of the present invention are exerted. Details of Lh will be described later. ns is an integer of 1 to 4, preferably 1 or 2, and more preferably 1. The formula weight of the formula (Ls) is preferably 14-300, more preferably 50-200.

＜＜聚醯亞胺前驅物＞＞ 作為聚醯亞胺前驅物，包含由下述式（1）表示之構成單元為較佳。 [化學式7]

Figure 02_image013
A1 及A2 分別獨立地表示氧原子或NH，R111 表示2價的有機基，R115 表示4價的有機基，R113 及R114 分別獨立地表示氫原子或1價的有機基。<<Polyimide Precursor>> It is preferable that the polyimide precursor contains a structural unit represented by the following formula (1). [chemical formula 7]
Figure 02_image013
A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.

A1 及A2 分別獨立地為氧原子或NH，氧原子為較佳。 R111 表示2價的有機基。作為2價的有機基，可例示直鏈或支鏈的脂肪族基、環狀的脂肪族基及芳香族基、雜芳香族基或包括該等組合之基團，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的芳香族基或包括該等組合之基團為較佳，碳數6～20的芳香族基為更佳。A 1 and A 2 are each independently an oxygen atom or NH, preferably an oxygen atom. R 111 represents a divalent organic group. Examples of divalent organic groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups including combinations thereof. A chain aliphatic group, a branched aliphatic group with 3 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons or a group including a combination thereof is Preferably, an aromatic group having 6 to 20 carbon atoms is more preferred.

＜＜＜R111 ＞＞＞ R111 由二胺衍生為較佳。作為在聚醯亞胺前驅物的製造中所使用之二胺，可舉出直鏈或支鏈脂肪族、環狀脂肪族或芳香族二胺等。二胺可以僅使用一種，亦可以使用2種以上。 具體而言，二胺包含碳數2～20的直鏈脂肪族基、碳數3～20的支鏈或環狀脂肪族基、碳數6～20的芳香族基或由該等組合結構之基團為較佳，包含碳數6～20的芳香族基之二胺為更佳。作為芳香族基的例，可舉出下述芳香族基。<<<R 111 >>> R 111 is preferably derived from diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Diamine may use only 1 type, and may use 2 or more types. Specifically, the diamine contains a straight-chain aliphatic group with 2 to 20 carbons, a branched or cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or a combination of these A group is preferred, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferred. Examples of the aromatic group include the following aromatic groups.

[化學式8]

Figure 02_image015
[chemical formula 8]
Figure 02_image015

式中，A為單鍵或選自可以被氟原子取代之碳數1～10的脂肪族羥基、-O-、-C（=O）-、-S-、-S（=O）2 -、-NHCO-以及選自該等組合中之基團為較佳，單鍵或選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-C（=O）-、-S-、-SO2 -中之基團為更佳，選自包括-CH2 -、-O-、-S-、-SO2 -、-C（CF3 ）2-及-C（CH3 ）2 -之群組中之2價基團為進一步較佳。In the formula, A is a single bond or selected from aliphatic hydroxyl groups with 1 to 10 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -S(=O) 2 - , -NHCO- and groups selected from these combinations are preferred, single bonds or selected from alkylene groups with 1 to 3 carbons that may be substituted by fluorine atoms, -O-, -C(=O)- , -S-, -SO 2 - are more preferred, selected from the group including -CH 2 -, -O-, -S-, -SO 2 -, -C(CF 3 ) 2- and -C( The divalent group in the group of CH 3 ) 2 - is further preferred.

作為二胺，具體而言可舉出選自1,2-二胺基乙烷、1,2-二胺基丙烷、1,3-二胺基丙烷、1,4-二胺基丁烷及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’-二甲基環己基甲烷及異佛爾酮二胺；間苯二胺及對苯二胺、二胺基甲苯、4,4’-二胺基聯苯及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’-二胺基二苯基甲烷及3,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基碸及3,3-二胺基二苯基碸、4,4’-二胺基二苯硫醚及3,3’-二胺基二苯硫醚、4,4’-二胺基二苯甲酮及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、3,3’-二甲氧基-4,4’-二胺基聯苯、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、2,4-二胺基枯烯及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、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、二胺基苯甲酸的酯、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。Specific examples of diamines include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminocyclohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclopentane Cyclohexane or 1,4-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'-dimethyl Cyclohexylmethane and isophorone diamine; m-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4 ,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4 ,4'-diaminodiphenylsulfide and 3,3-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 4,4'-diaminobenzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2' -Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 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)pyridine, bis(4-amino-3-hydroxyphenyl)pyridine, 4,4'-diamino-terphenyl, 4,4'-bis(4- Aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, bis[4-( 2-aminophenoxy)phenyl]pyridine, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-bis Methyl-4,4'-diaminodiphenylphenyl, 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'-di Aminodiphenylmethane, 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) terpene, 4,4'-dimethyl-3,3'-diaminodiphenylene, 3,3',5 ,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2-(3',5'-diaminobenzoyloxy)ethyl methacrylate, 2,4-diamino Aminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-Trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminoferene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, 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)tetrafluoroheptane, 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-trifluoromethyl phenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylbenzene oxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylphenoxide, 4,4'-bis(3-amino-5-trifluoromethyl phenylphenoxy)diphenylphenoxide, 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', At least one diamine selected from 6,6'-hexafluorobenzidine and 4,4'-diaminoquaterphenyl.

又，以下所示之二胺（DA-1）～（DA-18）亦為較佳。Moreover, diamine (DA-1)-(DA-18) shown below is also preferable.

[化學式9]

Figure 02_image017
[chemical formula 9]
Figure 02_image017

[化學式10]

Figure 02_image019
[chemical formula 10]
Figure 02_image019

又，作為較佳的例，亦可舉出於主鏈具有至少2個以上的伸烷基二醇單元之二胺。較佳為於一分子中組合包含2個以上的乙二醇鏈、丙二醇鏈中的任一個或兩者之二胺，更佳為不包含芳香環之二胺。作為具體例，可舉出JEFFAMINE（註冊商標）KH-511、JEFFAMINE（註冊商標）ED-600、JEFFAMINE（註冊商標）ED-900、JEFFAMINE（註冊商標）ED-2003、JEFFAMINE（註冊商標）EDR-148、JEFFAMINE（註冊商標）EDR-176、D-200、D-400、D-2000、D-4000（以上為產品名，HUNTSMAN公司製）、1-（2-（2-（2-胺基丙氧基）乙氧基）丙氧基）丙烷-2-胺、1-（1-（1-（2-胺基丙氧基）丙烷-2-基）氧基）丙烷-2-胺等，但並不限定於該等。 以下示出JEFFAMINE（註冊商標）KH-511、JEFFAMINE（註冊商標）ED-600、JEFFAMINE（註冊商標）ED-900、JEFFAMINE（註冊商標）ED-2003、JEFFAMINE（註冊商標）EDR-148、JEFFAMINE（註冊商標）EDR-176的結構。Moreover, the diamine which has at least 2 or more alkylene glycol units in a main chain can also be mentioned as a preferable example. It is preferable to combine diamine containing any one or both of two or more ethylene glycol chains and propylene glycol chains in one molecule, and it is more preferable to use a diamine not containing an aromatic ring. Specific examples include JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR- 148. JEFFAMINE (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (the above are product names, manufactured by HUNTSMAN), 1-(2-(2-(2-amino Propoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propane-2-amine, etc. , but not limited to such. JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( registered trademark) structure of EDR-176.

[化學式11]

Figure 02_image021
[chemical formula 11]
Figure 02_image021

上述中，x、y、z為平均值。In the above, x, y, and z are average values.

從所得到之硬化膜的柔軟性的觀點考慮，R111 由-Ar0 -L0 -Ar0 -表示為較佳。其中，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 表示單鍵、可以經氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-S（=O）2 -、-NHCO-以及選自該等組合之基團。較佳的範圍的定義與上述A相同。From the viewpoint of the flexibility of the obtained cured film, R 111 is preferably represented by -Ar 0 -L 0 -Ar 0 -. Among them, Ar 0 are each independently an aromatic hydrocarbon group (preferably having 6-22 carbon atoms, more preferably having 6-18 carbon atoms, and particularly preferably having 6-10 carbon atoms), and preferably a phenylene group. L 0 represents a single bond, an aliphatic hydrocarbon group with 1 to 10 carbons that may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) 2 -, -NHCO- and groups selected from such combinations. The definition of the preferable range is the same as that of A above.

從i射線透射率的觀點考慮，R111 係由下述式（51）或式（61）表示之2價的有機基為較佳。尤其，從i射線透射率、易獲得的觀點考慮，由式（61）表示之2價的有機基為更佳。 [化學式12]

Figure 02_image023
R50 ～R57 分別獨立地為氫原子、氟原子或1價的有機基，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。 當R50 ～R57 為1價的有機基時，可舉出碳數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。 [化學式13]
Figure 02_image025
R58 及R59 分別獨立地為氟原子、氟甲基、二氟甲基或三氟甲基。 作為賦予式（51）或（61）的結構之二胺化合物，可舉出二甲基-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。可以使用該等中的一種，亦可以組合使用2種以上。From the viewpoint of i-ray transmittance, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, a divalent organic group represented by formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. [chemical formula 12]
Figure 02_image023
R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, methyl, fluoromethyl, difluoromethyl or trifluoromethyl . When R 50 to R 57 are monovalent organic groups, examples include unsubstituted alkyl groups with 1 to 10 carbons (preferably 1 to 6 carbons), unsubstituted alkyl groups with 1 to 10 carbons (preferably carbon 1 to 6) fluorinated alkyl groups, etc. [chemical formula 13]
Figure 02_image025
R 58 and R 59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group. Examples of the diamine compound giving the structure of formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4, 4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

＜＜＜R115 ＞＞＞ 式（1）中的R115 表示4價的有機基。作為4價的有機基，包含芳香環之基團為較佳，由下述式（5）或式（6）表示之基團為更佳。 [化學式14]

Figure 02_image027
R112 的定義與A相同，較佳的範圍亦相同。<<<R 115 >>> R 115 in the formula (1) represents a tetravalent organic group. As the tetravalent organic group, a group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. [chemical formula 14]
Figure 02_image027
The definition of R112 is the same as that of A, and the preferred range is also the same.

關於由式（1）中的R115 表示之4價的有機基，具體而言，可舉出從四羧酸二酐去除酸二酐基之後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2種以上。四羧酸二酐係由下述式（7）表示之化合物為較佳。 [化學式15]

Figure 02_image029
R115 表示4價的有機基。R115 的定義與式（1）的R115 相同。As for the tetravalent organic group represented by R 115 in the formula (1), specifically, a tetracarboxylic acid residue remaining after removing an acid dianhydride group from a tetracarboxylic dianhydride, etc. are mentioned. Tetracarboxylic dianhydride may use only 1 type, and may use 2 or more types. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7). [chemical formula 15]
Figure 02_image029
R 115 represents a tetravalent organic group. The definition of R 115 is the same as that of R 115 in the formula (1).

作為四羧酸二酐的具體例，可例示選自均苯四甲酸、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的碳數1～6的烷基衍生物和碳數1～6的烷氧基衍生物中之至少一種。Specific examples of tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3 ',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethylbenzene Ketone 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'-oxodiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 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-naphthalene tetracarboxylic 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 -Phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1, At least one of 2,3,4-benzenetetracarboxylic dianhydride and these alkyl derivatives having 1 to 6 carbons and alkoxy derivatives having 1 to 6 carbons.

又，作為較佳例還可舉出下述中所示出之四羧酸二酐（DAA-1）～（DAA-5）。 [化學式16]

Figure 02_image031
Moreover, tetracarboxylic dianhydride (DAA-1) - (DAA-5) shown below can also be mentioned as a preferable example. [chemical formula 16]
Figure 02_image031

＜＜＜R113 及R114 ＞＞＞ 式（1）中的R113 及R114 分別獨立地表示氫原子或1價的有機基。R113 及R114 的至少一個包含自由基聚合性基為較佳，兩者包含自由基聚合性基為更佳。作為自由基聚合性基，為藉由自由基的作用，能夠進行交聯反應之基團，且作為較佳的例子，可舉出具有乙烯性不飽和鍵之基團。 作為具有乙烯性不飽和鍵之基團，可舉出乙烯基、烯丙基、（甲基）丙烯醯基、由下述式（III）表示之基團等。<<< R 113 and R 114 >>> R 113 and R 114 in the formula (1) each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R 113 and R 114 contains a radical polymerizable group, and it is more preferable that both contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a group having an ethylenically unsaturated bond is mentioned as a preferable example. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth)acryl group, a group represented by the following formula (III), and the like.

[化學式17]

Figure 02_image033
[chemical formula 17]
Figure 02_image033

R200 表示氫原子或甲基，甲基為更佳。 R201 表示碳數2～12的伸烷基、-CH2 CH（OH）CH2 -或碳數4～30的（聚）氧伸烷基（作為伸烷基，碳數1～12為較佳，1～6為更佳，1～3為特佳；重複數係1～12為較佳，1～6為更佳，1～3為特佳）。另外，（聚）氧伸烷基係指氧伸烷基或聚氧伸烷基。 較佳的R201 的例中，可舉出伸乙基、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 係甲基，R201 係伸乙基。R 200 represents a hydrogen atom or a methyl group, more preferably a methyl group. R 201 represents an alkylene group with 2 to 12 carbons, -CH 2 CH(OH)CH 2 - or a (poly)oxyalkylene group with 4 to 30 carbons (as an alkylene group, a relatively high carbon number of 1 to 12 Excellent, 1-6 is more preferred, 1-3 is particularly preferred; repetition number is 1-12 is preferred, 1-6 is more preferred, 1-3 is especially preferred). In addition, the (poly)oxyalkylene group refers to an oxyalkylene group or a polyoxyalkylene group. Among preferred R201 examples, ethylidene, propylidene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, Hexamethylene, octamethylene, dodecamethylene, -CH 2 CH(OH)CH 2 -, ethylidene, propylidene, trimethylene, -CH 2 CH(OH)CH 2 - are better. Especially preferably, R 200 is a methyl group, and R 201 is an ethylenyl group.

作為聚醯亞胺前驅物的較佳的實施形態，可舉出作為R113 或R114 的1價的有機基除了後述之磺酸基以外具有1、2或3個、較佳為1個酸基之脂肪族基、芳香族基及芳基烷基等。具體而言，可舉出具有酸基之碳數6～20的芳香族基、具有酸基之碳數7～25的芳基烷基。更具體而言，可舉出具有酸基之苯基及具有酸基之苄基。酸基係羥基為較佳。亦即，R113 或R114 係具有羥基之基團為較佳。 作為由R113 或R114 表示之1價的有機基，可較佳地使用提高顯影液的溶解度之取代基。 從對水性顯影液的溶解性的觀點考慮，R113 或R114 係氫原子、2-羥基苄基、3-羥基苄基及4-羥基苄基為更佳。As a preferred embodiment of the polyimide precursor, it can be mentioned that the monovalent organic group as R 113 or R 114 has 1, 2 or 3, preferably 1 acid in addition to the sulfonic acid group described later. Aliphatic groups, aromatic groups, arylalkyl groups, etc. Specifically, an aromatic group having 6 to 20 carbon atoms having an acid group, and an arylalkyl group having 7 to 25 carbon atoms having an acid group are mentioned. More specifically, there may be mentioned a phenyl group having an acidic group and a benzyl group having an acidic group. Acid-based hydroxyl groups are preferred. That is, R 113 or R 114 is preferably a group having a hydroxyl group. As the monovalent organic group represented by R 113 or R 114 , a substituent that increases the solubility of the developer can be preferably used. From the viewpoint of solubility in an aqueous developer, R 113 or R 114 is more preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, and 4-hydroxybenzyl.

從對有機溶劑的溶解度的觀點考慮，R113 或R114 係1價的有機基為較佳。作為1價的有機基，包含直鏈或支鏈烷基、環狀烷基、芳香族基為較佳，被芳香族基取代之烷基為更佳。 烷基的碳數係1～30為較佳（當為環狀時為3以上）。烷基可以係直鏈、支鏈、環狀中的任一個。作為直鏈或支鏈烷基，例如，可舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十二烷基、十四烷基，十八烷基、異丙基、異丁基、第二丁基、第三丁基、1-乙基戊基及2-乙基己基。環狀烷基可以係單環環狀烷基，亦可以係多環環狀烷基。作為單環環狀的烷基，例如，可舉出環丙基、環丁基、環戊基、環己基、環庚基及環辛基。作為多環環狀的烷基，例如，可舉出金剛烷基、降莰基、莰基、莰烯基（camphenyl）、十氫萘基、三環癸烷基、四環癸烷基、莰二醯基、二環己基及蒎烯基（pinenyl）。其中，從兼顧與高靈敏度化的觀點考慮，環己基為最佳。又，作為被芳香族基取代之烷基，被後述之芳香族基取代之直鏈烷基為較佳。 作為芳香族基，可舉出經取代或未經取代之苯環、萘環、戊搭烯環、茚環、薁環、庚搭烯環、茚烯環、苝環、稠五苯環、苊烯環、菲環、蒽環、稠四苯環、䓛環、三伸苯環、茀環、聯苯環、吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡啶環、吡𠯤環、嘧啶環、噠𠯤環、吲哚𠯤環、吲哚環、苯并呋喃環、苯并噻吩環、異苯并呋喃環、喹𠯤環、喹啉環、酞𠯤環、萘啶環、喹㗁啉環、喹唑啉環、異喹啉環、咔唑環、啡啶環、吖啶環、啡啉環、噻蒽環、色烯環、口山口星環、啡㗁噻環、啡噻𠯤環或啡𠯤環。苯環為最佳。From the viewpoint of solubility in organic solvents, R 113 or R 114 is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, and an aromatic group, and an alkyl group substituted with an aromatic group is more preferable. The carbon number of the alkyl group is preferably 1 to 30 (3 or more when cyclic). The alkyl group may be any of linear, branched and cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, Alkyl, octadecyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, camphenyl, camphenyl (camphenyl), decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, camphenyl Diacyl, dicyclohexyl and pinenyl. Among them, cyclohexyl group is most preferable from the viewpoint of balance and high sensitivity. Also, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable. Examples of the aromatic group include substituted or unsubstituted benzene rings, naphthalene rings, pentadene rings, indene rings, azulene rings, heptadene rings, indenene rings, perylene rings, condensed pentaphenyl rings, acenaphthene rings, etc. Alkene ring, phenanthrene ring, anthracene ring, condensed tetraphenyl ring, fenene ring, three phenylene ring, oxene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring , Pyridine ring, pyrimidine ring, dat ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinol ring, quinoline ring, phthalein ring, naphthalene ring Pyridine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthracene ring, thianthrene ring, chromene ring, mouth mountain mouth star ring, phenanthrene ring ring, brown thiol 𠯤 ring or brown 𠯤 ring. The benzene ring is the best.

又，聚醯亞胺前驅物中，於構成單元中具有氟原子亦為較佳。聚醯亞胺前驅物中的氟原子含量為10質量%以上為較佳，20質量%以下為較佳。上限並無特別限制，實際上為50質量%以下。Moreover, in a polyimide precursor, it is also preferable to have a fluorine atom in a structural unit. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less. The upper limit is not particularly limited, but is actually 50% by mass or less.

又，以提高與基板的密接性為目的，可以使具有矽氧烷結構之脂肪族基與由式（1）表示之單元共聚合。具體而言，作為二胺成分，可舉出雙（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。Moreover, for the purpose of improving the adhesiveness with a board|substrate, you may copolymerize the aliphatic group which has a siloxane structure, and the unit represented by formula (1). Specifically, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are mentioned as a diamine component.

由式（1）表示之構成單元係由式（1-A）表示之構成單元為較佳。 [化學式18]

Figure 02_image035
A11 及A12 表示氧原子或NH，R111 及R112 分別獨立地表示2價的有機基，R113 及R114 分別獨立地表示氫原子或1價的有機基，R113 及R114 中的至少一個為包含自由基聚合性基之基團，自由基聚合性基為較佳。The structural unit represented by formula (1) is preferably a structural unit represented by formula (1-A). [chemical formula 18]
Figure 02_image035
A 11 and A 12 represent an oxygen atom or NH, R 111 and R 112 each independently represent a divalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, among R 113 and R 114 At least one of them is a group containing a radical polymerizable group, preferably a radical polymerizable group.

A11 、A12 、R111 、R113 及R114 的定義分別獨立地與式（1）中的A1 、A2 、R111 、R113 及R114 相同，較佳範圍亦相同。 R112 的定義與式（5）中的R112 相同，較佳範圍亦相同。The definitions of A 11 , A 12 , R 111 , R 113 and R 114 are independently the same as those of A 1 , A 2 , R 111 , R 113 and R 114 in formula (1), and the preferred ranges are also the same. The definition of R 112 is the same as that of R 112 in formula (5), and the preferred range is also the same.

聚醯亞胺前驅物中，由式（1）表示之構成單元可以為1種，但是亦可以為2種以上。又，亦可以包含由式（1）表示之構成單元的結構異構物。又，聚醯亞胺前驅物除了上述式（1）的構成單元以外，還可以包含其他種類的構成單元。In the polyimide precursor, the structural unit represented by the formula (1) may be one type, or two or more types. Moreover, the structural isomer of the structural unit represented by formula (1) may be included. In addition, the polyimide precursor may contain other types of structural units in addition to the structural units of the above-mentioned formula (1).

聚醯亞胺前驅物具有由式（1-1a）、式（1-2a）、式（1-3a）中的任一個所表示之部位（構成單元或末端結構）為較佳。 [化學式19]

Figure 02_image037
式中，A1 、A2 、R111 、R113 、R114 、R115 的定義與式（1）中的定義相同，較佳者亦相同。*表示與聚醯亞胺前驅物的主鏈的鍵結位置。Ls係上述式（Ls）。此時，式（Ls）的Li在式（1-1a）中係*1 -NHCO為較佳。在式（1-2a）、式（1-3a）中係*1 -COO或*1 -CONH為較佳。The polyimide precursor preferably has a site (constituent unit or terminal structure) represented by any one of formula (1-1a), formula (1-2a), and formula (1-3a). [chemical formula 19]
Figure 02_image037
In the formula, the definitions of A 1 , A 2 , R 111 , R 113 , R 114 , and R 115 are the same as those in formula (1), and the preferred ones are also the same. * indicates the bonding position with the main chain of the polyimide precursor. Ls is the above formula (Ls). In this case, Li in the formula (Ls) is preferably * 1 -NHCO in the formula (1-1a). In formula (1-2a) and formula (1-3a), * 1 -COO or * 1 -CONH is preferable.

聚醯亞胺前驅物具有由式（1-1）、式（1-2）、式（1-3）中的任一個所表示之部位為更佳。 [化學式20]

Figure 02_image039
式中，A1 、A2 、R111 、R113 、R114 、R115 的定義與式（1）中的定義相同，較佳的範圍亦相同。X1 、X2 及X3 分別獨立地表示連接基，*表示與聚醯亞胺前驅物的主鏈的鍵結位置，ns的定義與式Ls相同。 X1 、X2 及X3 分別獨立地表示具有碳原子之連接基，X1 、X2 及X3 經碳原子與磺酸基鍵結為較佳。 X1 、X2 及X3 係具有上述連接基Lt之基團為較佳或將氧原子、羰基及-NRN -中的至少一個與連接基Lt組合之基團為較佳。此時，在連接基Lt側鍵結有磺酸基。RN 的詳細內容進行後述，但是其中，RN 係氫原子為較佳。 式（1-3）中的X3 係連接基Lt為較佳。另一方面，式（1-1）中的X1 除了連接基Lt以外具有與主鏈的NH連接之羰基為較佳。式（1-2）中的X2 亦相同且除了連接基Lt以外具有與主鏈的羰基連接之氧原子或-NRN -為較佳。 作為本發明的一實施形態，可例示鍵結有式（1-1）、式（1-2）、式（1-3）之主鏈的構成單元的A1 、A2 、R111 、R113 、R114 、R115 與式（1-1）、式（1-2）、式（1-3）中的A1 、A2 、R111 、R113 、R114 、R115 相同的基團或相同的原子之形態。It is more preferable that the polyimide precursor has a site represented by any one of formula (1-1), formula (1-2), and formula (1-3). [chemical formula 20]
Figure 02_image039
In the formula, the definitions of A 1 , A 2 , R 111 , R 113 , R 114 , and R 115 are the same as those in formula (1), and the preferred ranges are also the same. X 1 , X 2 and X 3 each independently represent a linking group, * represents a bonding position with the main chain of the polyimide precursor, and the definition of ns is the same as that of formula Ls. X 1 , X 2 and X 3 each independently represent a linking group having a carbon atom, and X 1 , X 2 and X 3 are preferably bonded to a sulfonic acid group via a carbon atom. X 1 , X 2 and X 3 are preferably groups having the above-mentioned linking group Lt or combinations of at least one of an oxygen atom, a carbonyl group and -NR N - with the linking group Lt. At this time, a sulfonic acid group is bonded to the side of the linker Lt. Details of RN will be described later, but among them, RN is preferably a hydrogen atom. The X 3 linker Lt in the formula (1-3) is preferred. On the other hand, X 1 in the formula (1-1) preferably has a carbonyl group linked to NH of the main chain in addition to the linker Lt. X 2 in the formula (1-2) is also the same and preferably has an oxygen atom connected to the carbonyl group of the main chain or -NR N - in addition to the linker Lt. As an embodiment of the present invention, A 1 , A 2 , R 111 , R 113 , R 114 , R 115 are the same groups as A 1 , A 2 , R 111 , R 113 , R 114 , and R 115 in formula (1-1), formula (1-2), and formula (1-3). Groups or identical atomic forms.

X1 、X2 、X3 、Lt在發揮本發明的效果之範圍內亦可以具有取代基T。取代基T為複數個時亦可以彼此鍵結或者經由連接基L或不經由連接基L與式中的環鍵結而形成環。但是，不具有取代基為較佳。X 1 , X 2 , X 3 , and Lt may have a substituent T within the range in which the effect of the present invention is exhibited. When there are plural substituents T, they may be bonded to each other or bonded to the ring in the formula via a linker L or not via a linker L to form a ring. However, it is preferable not to have a substituent.

作為在構成聚醯亞胺前驅物的主鏈之芳香環（R115 、R111 的較佳的結構）導入包含磺酸基之部位之試劑，使用具有*1 -Lt-（SO3 H）ns 的結構之化合物為較佳。若例示導入試劑，可舉出磺基苯甲酸、胺基苯磺酸、胺基乙烷磺酸、羥基乙烷磺酸、羥基丙烷磺酸、丙烷磺內酯、丁烷磺內酯。導入包含磺酸基之部位之方法並無特別限定，但是能夠依據需要使上述試劑與觸媒一同與聚醯亞胺前驅物進行反應或在其合成過程中進行反應來得到。其在後記聚苯并㗁唑前驅物亦相同。As a reagent for introducing a site containing a sulfonic acid group into the aromatic ring (preferable structure of R 115 and R 111 ) constituting the main chain of the polyimide precursor, use * 1 -Lt-(SO 3 H) ns Compounds with the structure of are preferred. Examples of introducing reagents include sulfobenzoic acid, aminobenzenesulfonic acid, aminoethanesulfonic acid, hydroxyethanesulfonic acid, hydroxypropanesulfonic acid, propane sultone, and butane sultone. The method of introducing a site containing a sulfonic acid group is not particularly limited, but it can be obtained by reacting the above-mentioned reagent with a catalyst together with a polyimide precursor or during its synthesis, as required. The same applies to the polybenzoxazole precursor described later.

本發明中，聚醯亞胺前驅物的構成單元中，亦可以包含直接在主鏈的芳香環導入有磺酸基者，亦可以不包含直接在主鏈的芳香環導入有磺酸基者。在發揮本發明的效果之範圍內，可以為該種直接連接之磺酸基，可以理解為例如即使成為10%以下、進一步為1%以下的構成單元中具有該種直接連接之磺酸基之聚醯亞胺前驅物，藉由條件或應用亦可充分發揮本發明的效果。In the present invention, the constituent units of the polyimide precursor may include those in which sulfonic acid groups are directly introduced into the aromatic rings of the main chain, or may not include those in which sulfonic acid groups are directly introduced into the aromatic rings in the main chain. Within the scope of exerting the effects of the present invention, such directly-connected sulfonic acid groups may be used. For example, even if 10% or less, and further 1% or less of constituent units have such directly-connected sulfonic acid groups The polyimide precursor can also fully exert the effects of the present invention depending on the conditions or applications.

作為取代基T，可舉出環狀或直鏈或者支鏈的烷基（碳數1～24為較佳，1～12為更佳，1～6為特佳）、環狀或直鏈或者支鏈的烯基（碳數2～24為較佳，2～12為更佳，2～6為特佳）、烷氧基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、芳基烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳）、羥基、胺基（碳數0～24為較佳，0～12為更佳，0～6為特佳）、硫醇基、羧基、醯基（碳數2～12為較佳，2～6為更佳，2～3為特佳）、醯氧基（碳數2～12為較佳，2～6為更佳，2～3為特佳）、芳醯基（碳數7～23為較佳，7～19為更佳，7～11為特佳）、芳基烷基（碳數7～23為較佳，7～19為更佳，7～11為特佳）、（甲基）丙烯醯基、（甲基）丙烯醯氧基、鹵素原子（例如、氟原子、氯原子、溴原子、碘原子）、氧代基（=O）、亞胺基（=NRN ）、亞烷基（=C（RN ）2 ）等。在取代基T的伸烷基鏈亦可以存在雜原子。在取代基T的烷基、烯基、芳基、芳基烷基還可以取代其他取代基。 RN 係氫原子或有機基，作為有機基，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）、芳基烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳）為較佳。該有機基還可以具有取代基T。As the substituent T, cyclic or straight-chain or branched-chain alkyl groups (preferably 1-24 carbons, more preferably 1-12, particularly preferably 1-6), cyclic or straight-chain or Branched chain alkenyl (preferably 2-24 carbons, more preferably 2-12, particularly preferably 2-6), alkoxy (preferably 1-12 carbons, more preferably 1-6, 1 to 3 is more preferred), arylalkyl (7 to 23 carbons is preferred, 7 to 19 is more preferred, 7 to 11 is further preferred), hydroxyl, amino group (0 to 24 carbons is Preferably, 0-12 is more preferred, 0-6 is particularly preferred), thiol group, carboxyl group, acyl group (2-12 carbon number is preferred, 2-6 is more preferred, 2-3 is especially preferred) , acyloxy (preferably 2-12 carbons, more preferably 2-6, particularly preferably 2-3), aryl (preferably 7-23 carbons, more preferably 7-19, 7 ～11 is particularly preferred), arylalkyl (7-23 carbons is preferred, 7-19 is more preferred, 7-11 is particularly preferred), (meth)acryl, (meth)acryl Oxygen group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), oxo group (=O), imino group (=NR N ), alkylene group (=C(R N ) 2 ) wait. Heteroatoms may also be present in the alkylene chain of the substituent T. Alkyl, alkenyl, aryl, arylalkyl in the substituent T can also substitute other substituents. R N is a hydrogen atom or an organic group. As an organic group, an alkyl group (preferably 1 to 12 carbons, more preferably 1 to 6, more preferably 1 to 3), alkenyl (2 to 12 carbons is Preferably, 2-6 is more preferred, 2-3 is further preferred), aryl (6-22 carbons is preferred, 6-18 is more preferred, 6-10 is further preferred), aryl alkane A group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 11 carbon atoms) is more preferred. This organic group may also have a substituent T.

連接基L係環狀或直鏈或者支鏈的伸烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、環狀或直鏈或者支鏈的伸烯基（碳數2～12為較佳，2～6為更佳）、伸芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、芳基伸烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳）、雜伸芳基（碳數1～12為較佳，1～6為更佳，1～4為進一步較佳；作為雜原子，例如可舉出氮原子、氧原子、硫原子）、氧原子、硫原子、羰基、-NRN -或其組合之基團。構成連接基L之原子的數除了氫原子以外，1～24為較佳，1～12為更佳，1～6為特佳。連接基的連接原子數係10以下為較佳，8以下為更佳。作為下限係1以上。上述連接原子數係指位於連接規定的結構部之間且與連接有關之最少的原子數。例如，-CH2 -C（=O）-O-的情況下，構成連接基之原子的數不包括氫原子為4，但是連接原子數係3。The linker L is a cyclic or straight chain or branched chain alkylene group (preferably 1 to 12 carbons, more preferably 1 to 6, and further preferably 1 to 3), cyclic or straight chain or branched Alkenylene (preferably 2-12 carbons, more preferably 2-6), arylylene (preferably 6-22 carbons, more preferably 6-18, further preferably 6-10) , arylalkylene (preferably 7-23 carbons, more preferably 7-19, further preferably 7-11), heteroarylalkylene (preferably 1-12 carbons, more preferably 1-6 Preferably, 1 to 4 are more preferred; Examples of heteroatoms include nitrogen atom, oxygen atom, sulfur atom), oxygen atom, sulfur atom, carbonyl group, -NR N - or a combination thereof. The number of atoms constituting the linking group L is preferably 1-24, more preferably 1-12, and particularly preferably 1-6, except hydrogen atoms. The number of linking atoms in the linking group is preferably 10 or less, more preferably 8 or less. The lower limit is 1 or more. The above-mentioned number of linking atoms refers to the minimum number of atoms located between structural parts specified for linking and related to linking. For example, in the case of -CH 2 -C(=O)-O-, the number of atoms constituting the linking group is 4 excluding hydrogen atoms, but the number of linking atoms is 3.

作為包含雜原子之連接基Lh，可舉出氧原子、硫原子、羰基、硫羰基、磺醯基、-NRN -或包括該等組合之連接基。構成包含雜原子之連接基Lh之原子的數係1～12為較佳，1～6為更佳，1～3為特佳。包含雜原子之連接基Lh的存在於特定的基團中之原子的數係1～12為較佳，1～6為更佳，1～3為特佳。RN 的定義與上述相同。Examples of the linking group Lh containing a heteroatom include an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group, a sulfonyl group, -NR N- , or a linking group including a combination thereof. The number of atoms constituting the heteroatom-containing linking group Lh is preferably 1-12, more preferably 1-6, and particularly preferably 1-3. The number of atoms present in the specific group of the linking group Lh including a heteroatom is preferably 1-12, more preferably 1-6, and particularly preferably 1-3. The definition of RN is the same as above.

聚醯亞胺前驅物中所含有之磺酸基的合計數係總構成單元的合計數的0.05%以上為較佳，0.1%以上為更佳，0.2%以上為進一步較佳，0.3%以上為更進一步較佳，0.35%以上為更進一步較佳，0.4%以上為尤其進一步較佳，亦可以為50莫耳%以上、70莫耳%以上、90莫耳%以上。上限可以為100%以下，但是20.0%以下為較佳，15.0%以下為更佳，10.0%以下為進一步較佳，8.0%以下為更進一步較佳，6.0%以下為更進一步較佳，5.0%以下為尤其進一步較佳。藉由將該磺酸基的比例設為上述範圍，更有效地發揮保存穩定性與銅腐蝕性的兩個方面。The total number of sulfonic acid groups contained in the polyimide precursor is preferably 0.05% or more, more preferably 0.1% or more, more preferably 0.2% or more, and 0.3% or more of the total number of total structural units. More preferably, 0.35% or more is more preferably, 0.4% or more is especially more preferably, and may be 50 mol% or more, 70 mol% or more, or 90 mol% or more. The upper limit may be 100% or less, but 20.0% or less is more preferred, 15.0% or less is more preferred, 10.0% or less is still more preferred, 8.0% or less is still more preferred, 6.0% or less is still more preferred, 5.0% The following are especially more preferable. By making the ratio of this sulfonic acid group into the said range, both aspects of storage stability and copper corrosion property can be exhibited more effectively.

聚醯亞胺前驅物中，具有上述磺酸基（較佳為式（Ls）的基團）之構成單元可以佔構成聚醯亞胺前驅物之構成單元中的全部，但是亦可以具有局部不同之構成單元。具有包含上述磺酸基之部位（較佳為式（Ls）的基團）之構成單元係總構成單元的0.05%以上為較佳，0.1%以上為更佳，0.2%以上為進一步較佳，0.3%以上為更進一步較佳，0.35%以上為更進一步較佳，0.4%以上為尤其進一步較佳，亦可以為50莫耳%以上、70莫耳%以上、90莫耳%以上。上限可以為100%以下，但是20.0%以下為較佳，15.0%以下為更佳，10.0%以下為進一步較佳，8.0%以下為更進一步較佳，6.0%以下為更進一步較佳，5.0%以下為尤其進一步較佳。In the polyimide precursor, the constituent units having the above-mentioned sulfonic acid group (preferably a group of formula (Ls)) may account for all of the constituent units constituting the polyimide precursor, but may also have partial differences the constituent unit. The structural unit having a site (preferably a group of formula (Ls)) containing the above-mentioned sulfonic acid group is preferably 0.05% or more of the total structural units, more preferably 0.1% or more, and still more preferably 0.2% or more, More preferably 0.3% or more, more preferably 0.35% or more, even more preferably 0.4% or more, and may be 50 mol% or more, 70 mol% or more, or 90 mol% or more. The upper limit may be 100% or less, but 20.0% or less is more preferred, 15.0% or less is more preferred, 10.0% or less is still more preferred, 8.0% or less is still more preferred, 6.0% or less is still more preferred, 5.0% The following are especially more preferable.

以下示出聚醯亞胺前驅物中的具有磺酸基之結構的例。本發明並不限定於該等是不言而喻的。 ＜＜＜在聚醯亞胺前驅物的末端（主鏈末端）鍵結有磺酸基之態樣＞＞＞ [化學式21]

Figure 02_image041
[化學式22]
Figure 02_image043
Examples of structures having sulfonic acid groups in polyimide precursors are shown below. It goes without saying that the present invention is not limited to these. ＜<<The aspect in which a sulfonic acid group is bonded to the end (main chain end) of the polyimide precursor >>> [Chemical formula 21]
Figure 02_image041
[chemical formula 22]
Figure 02_image043

＜＜＜在聚醯亞胺前驅物的側鏈（主鏈結構的側鏈）鍵結有磺酸基之態樣＞＞＞ [化學式23]

Figure 02_image045
＜<<The aspect in which a sulfonic acid group is bonded to the side chain of the polyimide precursor (the side chain of the main chain structure)>>> [Chemical formula 23]
Figure 02_image045

作為本發明中的聚醯亞胺前驅物的一實施形態，可例示總構成單元的50莫耳%以上、進一步為70莫耳%以上、尤其為90莫耳%以上係由式（1）表示之構成單元或在側鏈具有磺酸基之構成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 in the present invention, 50 mol% or more of the total structural units, further 70 mol% or more, especially 90 mol% or more are represented by formula (1) The polyimide precursor of the structural unit or the structural unit having a sulfonic acid group in the side chain. The upper limit is actually 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。 聚醯亞胺前驅物的分子量的分散度（Mw/Mn）係1.5～3.5為較佳，2～3為更佳。The weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, even more preferably from 10,000 to 50,000. Also, the number average molecular weight (Mn) is preferably from 800 to 250,000, more preferably from 2,000 to 50,000, still more preferably from 4,000 to 25,000. The molecular weight dispersion (Mw/Mn) of the polyimide precursor is preferably 1.5-3.5, more preferably 2-3.

聚醯亞胺前驅物能夠藉由使二羧酸或二羧酸衍生物與二胺反應而得到。較佳為使用鹵化劑對二羧酸或二羧酸衍生物進行鹵化之後，能夠使其與二胺反應而得到。 聚醯亞胺前驅物的製造方法中，進行反應時，使用有機溶劑為較佳。有機溶劑可以係一種，亦可以係2種以上。 作為有機溶劑，能夠依原料適當設定，可例示吡啶、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 polyimide precursor can be obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine. Preferably, dicarboxylic acid or a dicarboxylic acid derivative can be reacted with a diamine after halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent. In the method for producing a polyimide precursor, it is preferable to use an organic solvent for the reaction. The organic solvent may be one type, or two or more types. As an organic solvent, it can be set suitably according to a raw material, Pyridine, diglyme (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone can be illustrated.

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，使四氫呋喃等聚醯亞胺前驅物溶解於可溶性溶劑，藉此能夠進行固體析出。When producing the polyimide precursor, it is preferable to include the step of precipitating solid. Specifically, the polyimide precursor in the reaction liquid is precipitated in water, and the polyimide precursor such as tetrahydrofuran is dissolved in a soluble solvent, whereby solid precipitation can be performed.

＜＜聚苯并㗁唑前驅物＞＞ 聚苯并㗁唑前驅物包含由下述式（2）表示之構成單元為較佳。 [化學式24]

Figure 02_image047
R121 表示2價的有機基，R122 表示4價的有機基，R123 及R124 分別獨立地表示氫原子或1價的有機基。<<Polybenzoxazole precursor>> It is preferable that the polybenzoxazole precursor contains a structural unit represented by the following formula (2). [chemical formula 24]
Figure 02_image047
R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.

R121 表示2價的有機基。作為2價的有機基，包含脂肪族基（碳數1～24為較佳，1～12為更佳，1～6為特佳）及芳香族基（碳數6～22為較佳，6～14為更佳，6～12為特佳）中的至少一種之基團為較佳。作為構成R121 之芳香族基，可舉出上述式（1）的R111 的例。作為上述脂肪族基，直鏈脂肪族基為較佳。R121 源自4,4’-氧代二苯甲醯氯為較佳。 R122 表示4價的有機基。作為4價的有機基，其定義與上述式（1）中的R115 相同，較佳的範圍亦相同。R122 源自2,2’-雙（3-胺基-4-羥基苯基）六氟丙烷為較佳。 R123 及R124 分別獨立地表示氫原子或1價的有機基，其定義與上述式（1）中的R113 及R114 相同，較佳的範圍亦相同。R 121 represents a divalent organic group. The divalent organic groups include aliphatic groups (preferably 1-24 carbons, more preferably 1-12, particularly preferably 1-6) and aromatic groups (preferably 6-22 carbons, 6 -14 is more preferred, 6-12 is particularly preferred) at least one group is preferred. Examples of the aromatic group constituting R 121 include R 111 in the above formula (1). As the aforementioned aliphatic group, a straight-chain aliphatic group is preferred. R 121 is preferably derived from 4,4'-oxodibenzoyl chloride. R 122 represents a tetravalent organic group. As a tetravalent organic group, its definition is the same as that of R 115 in the above formula (1), and the preferable range is also the same. R 122 is preferably derived from 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group, and their definitions are the same as those of R 113 and R 114 in the above formula (1), and their preferred ranges are also the same.

聚苯并㗁唑前驅物具有由下述式（2-1a）、（2-2a）、（2-3a）表示之部位為較佳。 [化學式25]

Figure 02_image049
式中，R121 、R122 、R123 、R124 的定義與式（2）中的定義相同，較佳者亦相同。*表示與聚苯并㗁唑前驅物的主鏈的鍵結位置。Ls係上述式（Ls）的基團。其中，式（2-1a）的情況下，式（Ls）的Li係*1―NHCO為較佳。式（2-2a）的情況下，係*1―COO或CONH為較佳。式（2-3a）的情況下，Li係*1―OCO為較佳。式（Ls）中，與其他Lt或ns有關之規定的定義與式（1）的情況相同。另外，在此*1係R121 或R122 側的鍵結位置。The polybenzoxazole precursor preferably has a site represented by the following formulas (2-1a), (2-2a), and (2-3a). [chemical formula 25]
Figure 02_image049
In the formula, the definitions of R 121 , R 122 , R 123 , and R 124 are the same as those in formula (2), and the preferred ones are also the same. * indicates the bonding position with the main chain of the polybenzoxazole precursor. Ls is a group of the above formula (Ls). Among them, in the case of the formula (2-1a), the Li-based *1-NHCO of the formula (Ls) is preferable. In the case of formula (2-2a), the system *1-COO or CONH is preferable. In the case of formula (2-3a), Li-based *1-OCO is preferable. In the formula (Ls), the definition of the provisions related to other Lt or ns is the same as that of the formula (1). In addition, *1 here refers to the bonding position on the R121 or R122 side.

聚苯并㗁唑前驅物具有由下述式（2-1）、（2-2）、（2-3）表示之部位為進一步較佳。 [化學式26]

Figure 02_image051
式中，R121 、R122 、R123 及R124 的定義與式（2）相同。X4 、X5 及X6 分別獨立地表示連接基，*表示與聚苯并㗁唑前驅物的主鏈的鍵結位置，ns表示1～4的整數。 X4 、X5 及X6 分別獨立地表示具有碳原子之連接基，X4 、X5 及X6 經碳原子與磺酸基鍵結為較佳。 X4 、X5 及X6 係與連接基Lt或它們組合氧原子、羰基及-NRN -中的至少一個之基團為較佳。ns係1或2為較佳，1為更佳。 X4 、X5 、X6 、Lt在發揮本發明的效果之範圍內亦可以具有取代基T。It is still more preferable that the polybenzoxazole precursor has a site represented by the following formulas (2-1), (2-2), and (2-3). [chemical formula 26]
Figure 02_image051
In the formula, the definitions of R 121 , R 122 , R 123 and R 124 are the same as those in formula (2). X 4 , X 5 , and X 6 each independently represent a linking group, * represents a bonding position with the main chain of the polybenzoxazole precursor, and ns represents an integer of 1-4. X 4 , X 5 and X 6 independently represent a linking group having a carbon atom, and X 4 , X 5 and X 6 are preferably bonded to a sulfonic acid group through a carbon atom. It is preferable that X 4 , X 5 and X 6 are at least one of the linking group Lt or their combination of oxygen atom, carbonyl group and -NR N -. ns is preferably 1 or 2, and 1 is more preferred. X 4 , X 5 , X 6 , and Lt may have a substituent T within the range in which the effects of the present invention are exerted.

聚苯并㗁唑前驅物中的包含磺酸基之部位的數的比例與在上述聚醯亞胺前驅物中規定者相同。將包含磺酸基之部位導入聚苯并㗁唑前驅物之試劑或其導入方法亦與在上述聚醯亞胺前驅物中敘述者相同。The ratio of the number of sites containing sulfonic acid groups in the polybenzoxazole precursor is the same as that specified in the above-mentioned polyimide precursor. The reagent or method for introducing a site containing a sulfonic acid group into the polybenzoxazole precursor is also the same as that described in the above-mentioned polyimide precursor.

以下示出聚苯并㗁唑前驅物中的具有磺酸基之結構的例。本發明並不限定於該等是不言而喻的。 ＜＜＜在聚苯并㗁唑前驅物的末端鍵結有磺酸基之態樣＞＞＞ [化學式27]

Figure 02_image053
＜＜＜在聚苯并㗁唑前驅物的側鏈鍵結有磺酸基之態樣＞＞＞ [化學式28]
Figure 02_image055
Examples of structures having sulfonic acid groups in polybenzoxazole precursors are shown below. It goes without saying that the present invention is not limited to these. ＜＜＜The aspect in which a sulfonic acid group is bonded to the end of the polybenzoxazole precursor＞＞＞ [Chemical formula 27]
Figure 02_image053
＜＜＜The aspect in which a sulfonic acid group is bonded to the side chain of the polybenzoxazole precursor＞＞＞ [Chemical formula 28]
Figure 02_image055

聚苯并㗁唑前驅物除了上述式（2）的構成單元以外還可以包含其他種類的構成單元。 從能夠抑制伴隨閉環之硬化膜的翹曲的產生之觀點考慮，前驅物包含由下述式（SL）表示之二胺殘基來作為其他種類的構成單元為較佳。The polybenzoxazole precursor may contain other types of structural units in addition to the structural units of the above formula (2). It is preferable that the precursor contains a diamine residue represented by the following formula (SL) as another type of structural unit from the viewpoint of being able to suppress the occurrence of warpage of the cured film accompanying ring closure.

[化學式29]

Figure 02_image057
Z具有a結構和b結構，R1s 為氫原子或碳數1～10的烴基（較佳為碳數1～6，更佳為碳數1～3），R2s 為碳數1～10的烴基（較佳為碳數1～6，更佳為碳數1～3），R3s 、R4s 、R5s 、R6s 中的至少一個為芳香族基（較佳為碳數6～22，更佳為碳數6～18，特佳為碳數6～10），剩餘部分為氫原子或碳數1～30（較佳為碳數1～18，更佳為碳數1～12，特佳為碳數1～6）的有機基，且可以分別相同亦可以不同。a結構及b結構的聚合可以係嵌段聚合或隨機聚合。Z部分中，較佳為a結構為5～95莫耳%，b結構為95～5莫耳%，a+b為100莫耳%。[chemical formula 29]
Figure 02_image057
Z has a structure and b structure, R 1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbons (preferably 1 to 6 carbons, more preferably 1 to 3 carbons), R 2s is a hydrocarbon group with 1 to 10 carbons Hydrocarbyl (preferably 1-6 carbons, more preferably 1-3 carbons), at least one of R 3s , R 4s , R 5s , R 6s is an aromatic group (preferably 6-22 carbons, More preferably 6-18 carbons, especially preferably 6-10 carbons), the remainder is hydrogen atoms or 1-30 carbons (preferably 1-18 carbons, more preferably 1-12 carbons, especially Preferably, they are organic groups having 1 to 6 carbon atoms, and may be the same or different. The polymerization of structure a and structure b can be block polymerization or random polymerization. In the Z fraction, preferably, the a structure is 5-95 mol%, the b structure is 95-5 mol%, and a+b is 100 mol%.

式（SL）中，作為較佳的Z，可舉出b結構中的R5s 及R6s 為苯基者。又，由式（SL）表示之結構的分子量係400～4,000為較佳，500～3,000為更佳。分子量能夠藉由通常所使用之凝膠滲透層析法求出。藉由將上述分子量設為上述範圍，能夠兼備降低聚苯并㗁唑前驅物的脫水閉環後的彈性模數，且抑制翹曲之效果和提高溶解性之效果。In the formula (SL), preferred Z includes those in which R 5s and R 6s in the structure b are phenyl groups. Moreover, the molecular weight of the structure represented by formula (SL) is preferably 400-4,000, more preferably 500-3,000. The molecular weight can be determined by the commonly used gel permeation chromatography. By setting the molecular weight to the above-mentioned range, it is possible to reduce the elastic modulus after dehydration and ring-closure of the polybenzoxazole precursor, suppress warpage, and improve solubility.

作為其他種類的構成單元包含由式（SL）表示之二胺殘基之情況下，從提高鹼可溶性之觀點考慮，前驅物還包含從四羧酸二酐去除酸二酐基之後殘存之四羧酸殘基來作為構成單元為較佳。作為該等四羧酸殘基的例，可舉出式（1）中的R115 的例。When the diamine residue represented by the formula (SL) is included as another type of structural unit, the precursor also includes tetracarboxylic acid dianhydride remaining after removing the acid dianhydride group from the viewpoint of improving alkali solubility. An acid residue is preferably used as a constituent unit. Examples of such tetracarboxylic acid residues include the example of R 115 in formula (1).

聚苯并㗁唑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。 聚苯并㗁唑前驅物的分子量的分散度（Mw/Mn）係1.5～3.5為較佳，2～3為更佳。The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, further preferably from 10,000 to 50,000. Moreover, the number average molecular weight (Mn) becomes like this. Preferably it is 800-250,000, More preferably, it is 2,000-50,000, More preferably, it is 4,000-25,000. The molecular weight dispersion (Mw/Mn) of the polybenzoxazole precursor is preferably 1.5-3.5, more preferably 2-3.

感光性樹脂組成物中的聚合物前驅物的含量相對於組成物的總固體成分係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，50質量%以上為更進一步較佳，60質量%以上為更進一步較佳，70質量%以上為進一步更較佳。上限中，感光性樹脂組成物中的聚合物前驅物的含量相對於組成物的總固體成分係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%以下為更進一步較佳。 感光性樹脂組成物可以僅包含1種聚合物前驅物，亦可以包含2種以上。當含有2種以上時，總量成為上述範圍為較佳。The content of the polymer precursor in the photosensitive resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and 50% by mass relative to the total solid content of the composition. The above is more preferable, 60 mass % or more is still more preferable, and 70 mass % or more is still more preferable. In the upper limit, the content of the polymer precursor in the photosensitive resin composition is preferably 99.5% by mass or less, more preferably 99% by mass or less, and still more preferably 98% by mass or less, relative to the total solid content of the composition. It is still more preferable that it is 97 mass % or less, and it is still more preferable that it is 95 mass % or less. The photosensitive resin composition may contain only one type of polymer precursor, or may contain two or more types. When containing 2 or more types, it is preferable that the total amount becomes the said range.

＜溶劑＞ 本發明的感光性樹脂組成物含有溶劑為較佳。溶劑能夠任意使用公知者。溶劑較佳為有機溶劑。作為有機溶劑，可舉出酯類、醚類、酮類、芳香族烴類、亞碸類、醯胺類等化合物。 作為酯類，例如作為較佳者，可舉出乙酸乙酯、乙酸正丁酯、乙酸異丁酯、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-氧代丁酸乙酯等。 作為醚類，例如作為較佳者，可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。 作為酮類，例如作為較佳者，可舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮等。 作為芳香族烴類，例如作為較佳者，可舉出甲苯、二甲苯、苯甲醚、檸檬烯等。 作為亞碸類，例如作為較佳者，可舉出二甲基亞碸。 作為醯胺類，作為較佳者，可舉出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-二甲基甲醯胺等。<Solvent> It is preferable that the photosensitive resin composition of this invention contains a solvent. As a solvent, a known one can be used arbitrarily. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, phenylenes, and amides. As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, etc. Esters, 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 (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate , ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionates (for example, 2- 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 2- Ethyl alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate Esters, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve. 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 monopropylene ether acetate etc. As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. are mentioned as preferable ones. Examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like as preferred ones. As the thionines, for example, dimethyl thionine is preferable. As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylformamide, etc.

關於溶劑，從塗佈面狀的改良等的觀點考慮，混合2種以上之形態亦為較佳。 本發明中，由選自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2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。Regarding the solvent, it is also preferable to mix two or more types from the viewpoint of the improvement of the coating surface shape and the like. In the present invention, by being selected from 3-ethoxy methyl propionate, 3-ethoxy ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Esters, Methyl 3-Methoxypropionate, 2-Heptanone, Cyclohexanone, Cyclopentanone, γ-Butyrolactone, Dimethylsulfene, Ethyl Carbitol Acetate, Butyl Carbitol One solvent among alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or a mixed solvent composed of two or more of them is preferred. It is particularly preferable to use dimethylsulfoxide and γ-butyrolactone at the same time.

關於溶劑的含量，從塗佈性的觀點考慮，設為本發明的感光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，成為5～75質量%之量為更佳，成為10～70質量%之量為進一步較佳，成為40～70質量%為更進一步較佳。溶劑含量依據塗膜的所期望的厚度及塗佈方法來進行調節即可。 溶劑可以僅含有一種，亦可以含有2種以上。當含有2種以上溶劑時，其總計為上述範圍為較佳。Regarding the content of the solvent, from the viewpoint of coatability, the total solid content concentration of the photosensitive resin composition of the present invention is preferably 5 to 80% by mass, more preferably 5 to 75% by mass. Preferably, it is more preferably 10 to 70% by mass, and still more preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method. A solvent may contain only 1 type, and may contain 2 or more types. When two or more solvents are contained, it is preferable that the total is within the above-mentioned range.

＜光活性化合物＞ 本發明中，感光性樹脂組成物包含光活性化合物。作為光活性化合物的例，可舉出光聚合起始劑、光酸產生劑及光硬化促進劑。＜Photoactive compounds＞ In the present invention, the photosensitive resin composition contains a photoactive compound. As an example of a photoactive compound, a photoinitiator, a photoacid generator, and a photohardening accelerator are mentioned.

＜＜光聚合起始劑＞＞ 本發明的感光性樹脂組成物中可以含有光聚合起始劑。光聚合起始劑係光自由基聚合起始劑為較佳。 作為能夠使用於本發明中的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，對從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，可以係與光激發之增感劑產生一些作用，並產生活性自由基之活性劑。 光自由基聚合起始劑至少含有一種於約300～800nm（較佳為330～500nm）的範圍內至少具有約50莫耳吸光係數之化合物為較佳。化合物的莫耳吸光係數能夠利用公知的方法來進行測量。例如，藉由紫外可見分光光度計（Varian公司製Cary-5 spectrophotometer），並使用乙酸乙酯溶劑而於0.01g/L的濃度下進行測量為較佳。＜＜Photopolymerization Initiator＞＞ The photosensitive resin composition of this invention may contain a photoinitiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. The radical photopolymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to rays from an ultraviolet region to a visible region is preferable. In addition, it can be an active agent that interacts with a photoexcited sensitizer to generate active free radicals. It is preferable that the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 in the range of about 300-800 nm (preferably 330-500 nm). The molar absorptivity of a compound can be measured by a known method. For example, it is preferable to perform measurement at a concentration of 0.01 g/L with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., Ltd.) using ethyl acetate solvent.

藉由本發明的感光性樹脂組成物包含光自由基聚合起始劑，將本發明的感光性樹脂組成物適用於半導體晶圓等基板而形成感光性樹脂組成物層之後，照射光，藉此發生因所產生之自由基引起之硬化，並能夠降低光照射部中的溶解性。因此，例如具有如下優點，亦即經由具有僅遮蔽電極部之圖案之光遮罩對感光性樹脂組成物層進行曝光，藉此依電極的圖案能夠簡單地製作溶解性不同之區域。Since the photosensitive resin composition of the present invention contains a photoradical polymerization initiator, the photosensitive resin composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then irradiated with light to generate Hardening due to the generated free radicals can reduce the solubility in the light-irradiated part. Therefore, for example, there is an advantage that, by exposing the photosensitive resin composition layer through a photomask having a pattern that shields only the electrode portion, regions having different solubility can be easily produced depending on the electrode pattern.

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、硬化合物、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。關於該等的詳細內容，能夠參閱日本特開2016-027357號公報的0165～0182段的記載，並將該內容編入本說明書中。As the photoradical polymerization initiator, known compounds can be used arbitrarily, for example, halogenated hydrocarbon derivatives (such as compounds having a triazole skeleton, compounds having a oxadiazole skeleton, compounds having a trihalomethyl group, etc. ), acyl phosphine compounds such as acyl phosphine oxide, hexaarylbiimidazole, oxime derivatives and other oxime compounds, organic peroxides, hard compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone Compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. For such details, the description in paragraphs 0165 to 0182 of JP-A-2016-027357 can be referred to, and the content is incorporated into this specification.

作為酮化合物，例如，可例示日本特開2015-087611號公報的0087段中所記載之化合物，並將該內容編入本說明書中。市售品中，還可較佳地使用KAYACURE DETX（Nippon Kayaku Co.,Ltd.製）。As the ketone compound, for example, compounds described in paragraph 0087 of JP-A-2015-087611 can be exemplified, and the content thereof is incorporated in the present specification. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

作為光自由基聚合起始劑，還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，還能夠使用日本特開平10-291969號公報中所記載之胺基苯乙酮系起始劑、日本專利第4225898號中所記載之醯基氧化膦系起始劑。 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（產品名：均為BASF公司製）。 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：均為BASF公司製）。 作為胺基苯乙酮系起始劑，還能夠使用極大吸收波長與365nm或405nm等波長光源匹配之日本特開2009-191179號公報中所記載之化合物。 作為醯基膦系起始劑，可舉出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：均為BASF公司製）。 作為茂金屬化合物，例示IRGACURE-784（BASF公司製）等。As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in JP-A-4225898 can also be used. As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCURE 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all are manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, commercially available IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all are manufactured by BASF Corporation) can be used. As the aminoacetophenone-based initiator, compounds described in Japanese Patent Application Laid-Open No. 2009-191179 whose maximum absorption wavelength matches a light source with a wavelength of 365 nm or 405 nm can also be used. Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. Moreover, commercially available IRGACURE-819 or IRGACURE-TPO (product name: both are manufactured by BASF Corporation) can be used. As a metallocene compound, IRGACURE-784 (manufactured by BASF Corporation) etc. are illustrated.

作為光自由基聚合起始劑，更佳為舉出肟化合物。藉由使用肟化合物，能夠進一步有效地提高曝光寬容度。肟化合物中，曝光寬容度（曝光餘裕度）較廣，且還作為光硬化促進劑而發揮功能，因此為特佳。 作為肟化合物的具體例，能夠使用日本特開2001-233842號公報中所記載之化合物、日本特開2000-080068號公報中所記載之化合物、日本特開2006-342166號公報中所記載之化合物。 作為較佳的肟化合物，例如可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-酮以及2-乙氧基羰氧基亞胺基-1-苯基丙烷-1-酮等。本發明的感光性樹脂組成物中，尤其將肟化合物（肟系的光聚合起始劑）用作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。 [化學式30]

Figure 02_image059
市售品中，還能夠較佳地使用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號公報中所記載之光自由基聚合起始劑2）。又，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）。 進而，還能夠使用具有氟原子之肟化合物。作為該等肟化合物的具體例，可舉出日本特開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段所記載之化合物（C-3）等。 作為最佳之肟化合物，可舉出日本特開2007-269779號公報中所示出之具有既定取代基之肟化合物、日本特開2009-191061號公報中所示出之具有硫芳基之肟化合物等。More preferably, an oxime compound is mentioned as a photoradical polymerization initiator. By using an oxime compound, exposure latitude can be improved more effectively. Among the oxime compounds, since the exposure latitude (exposure margin) is wide and also functions as a photocuring accelerator, it is especially preferable. As specific examples of oxime compounds, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, and compounds described in JP-A-2006-342166 can be used. . As preferred oxime compounds, for example, compounds of the following structures, 3-benzoyloxyiminobutan-2-one, 3-acetyloxyiminobutan-2-one, 3-Propionyloxyiminobutan-2-one, 2-Acetyloxyiminopentan-3-one, 2-Acetyloxyimino-1-phenylpropane-1- Ketones, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-tosyloxy)iminobutan-2-one, and 2-ethoxycarbonyl Oxyimino-1-phenylpropan-1-one, etc. In the photosensitive resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photoradical polymerization initiator. The oxime-based photopolymerization initiator has a >C=NOC(=O)- linking group in the molecule. [chemical formula 30]
Figure 02_image059
Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are made by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, JP 2012-014052 Photoradical polymerization initiator 2) described in the No. 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 be used. Moreover, DFI-091 (made by DAITO CHEMIX Co., Ltd.) can be used. Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, JP-A-2014-500852, Compound (C-3) described in Paragraph 0101 of Publication No. 2013-164471, etc. Preferred oxime compounds include oxime compounds having predetermined substituents shown in JP-A-2007-269779 and oximes having a thioaryl group shown in JP-A-2009-191061 compound etc.

從曝光靈敏度的觀點考慮，光自由基聚合起始劑係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之化合物。 更佳的光自由基聚合起始劑係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之至少一種化合物為進一步較佳，使用茂金屬化合物或肟化合物為更進一步較佳，肟化合物為更進一步較佳。 又，光自由基聚合起始劑還能夠使用二苯甲酮、N,N’-四甲基-4,4’-二胺基二苯甲酮（米蚩酮（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-口末啉基苯基）-丁酮-1,2-甲基-1-[4-（甲硫基）苯基]-2-口末啉基-丙酮-1等芳香族酮、烷基蒽醌等與芳香環進行縮環而成的醌類、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，還能夠使用由下述式（I）表示之化合物。 [化學式31]

Figure 02_image061
式（I）中，RI00 係由碳數1～20的烷基、藉由1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、由碳數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、藉由1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 係由式（II）表示之基團，或者係與RI00 相同的基團，RI02 ～RI04 各自獨立地為碳數1～12的烷基、碳數1～12的烷氧基或鹵素。 [化學式32]
Figure 02_image063
式中，RI05 ～RI07 與上述式（I）的RI02 ～RI04 相同。From the viewpoint of exposure sensitivity, photoradical polymerization initiators are selected from the group consisting of trihalomethyl tristannium 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 their derivatives, cyclopentadienyl - Compounds in the group of benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds. More preferable photoradical polymerization initiators are trihalomethyl trisalpine 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 selected from the group consisting of trihalomethyl tristannium compounds, α-aminoketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds It is further preferred to use at least one compound among them, it is further preferred to use a metallocene compound or an oxime compound, and it is further preferred to use an oxime compound. In addition, as the photoradical polymerization initiator, N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-perolylphenyl)-butanone-1 ,2-methyl-1-[4-(methylthio)phenyl]-2-pornolinyl-acetone-1 and other aromatic ketones, alkylanthraquinones and other quinones formed by condensation with aromatic rings Benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. Moreover, the compound represented by following formula (I) can also be used. [chemical formula 31]
Figure 02_image061
In formula (I), R I00 is an alkyl group with 1 to 20 carbons, an alkyl group with 2 to 20 carbons interrupted by one or more oxygen atoms, an alkoxy group with 1 to 12 carbons, benzene A group consisting of an alkyl group with 1 to 20 carbons, an alkoxy group with 1 to 12 carbons, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group with 2 to 12 carbons, and a group formed by one or more oxygen atoms Interrupted phenyl or biphenyl group substituted by at least one of the alkyl group with 2 to 18 carbons and the alkyl group with 1 to 4 carbons, R I01 is a group represented by formula (II), or it is the same as R I00 In the same group, R I02 to R I04 are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or a halogen. [chemical formula 32]
Figure 02_image063
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還能夠使用國際公開WO2015/125469號的0048～0055段中所記載之化合物。In addition, as the photoradical polymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication WO2015/125469 can also be used.

包含光聚合起始劑之情況下，其含量相對於本發明的感光性樹脂組成物的總固體成分係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包含1種，亦可以包含2種以上。含有2種以上的光聚合起始劑之情況下，其總計係上述範圍為較佳。When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5% to the total solid content of the photosensitive resin composition of the present invention. -15 mass %, More preferably, it is 1.0-10 mass %. A photoinitiator may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of photoinitiators, it is preferable that the sum total is the said range.

＜＜光酸產生劑＞＞ 本發明中，作為光活性化合物，能夠使用光酸產生劑。作為具體例，能夠適當選擇藉由光陽離子聚合的光起始劑、光自由基聚合的起始劑、色素類光消色劑、光變色劑或者微光抗蝕劑等中所使用之光化射線或放射線的照射產生酸之公知的化合物及該等混合物而使用。例如能夠舉出重氮鹽、鏻鹽、鋶鹽、錪鹽、醯亞胺磺酸鹽、肟磺酸鹽、重氮二碸、二碸、鄰硝基苄基磺酸鹽。包含光酸產生劑之情況下，其含量相對於本發明的感光性樹脂組成物的總固體成分係0.1～30質量%為較佳，更佳為0.5～15質量%，進一步較佳為0.5～10質量%，更進一步較佳為0.5～5質量%。光酸產生劑可以僅包含1種，亦可以包含2種以上。含有2種以上的光酸產生劑之情況下，其總計係上述範圍為較佳。＜＜Photoacid generator＞＞ In the present invention, a photoacid generator can be used as the photoactive compound. As a specific example, it is possible to appropriately select the photochemical agent used in a photoinitiator for cationic polymerization, an initiator for photoradical polymerization, a pigment-based photodecolorizer, a photochromic agent, or a shimmering resist. Known compounds and mixtures thereof that generate acids by radiation or radiation are used. Examples include diazonium salts, phosphonium salts, percite salts, iodonium salts, imide sulfonates, oxime sulfonates, diazonium disulfides, disulfides, and o-nitrobenzyl sulfonates. When a photoacid generator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, and still more preferably 0.5 to 30% by mass relative to the total solid content of the photosensitive resin composition of the present invention. 10% by mass, more preferably 0.5 to 5% by mass. A photoacid generator may contain only 1 type, and may contain 2 or more types. When containing 2 or more types of photo-acid generators, it is preferable that the sum total is the said range.

＜＜光硬化促進劑＞＞ 本發明中所使用之感光性樹脂組成物亦可以包含光硬化促進劑。本發明中的光硬化促進劑係藉由曝光產生鹼者，在常溫常壓的通常的條件下不顯示活性，但是作為外部刺激而進行電磁波的照射和加熱，則只要是產生鹼（鹼性物質）者就無特別限定。藉由曝光而產生之鹼作為藉由對聚合物前驅物進行加熱而硬化時的觸媒而發揮作用，因此能夠較佳地使用。 本發明中，作為光硬化促進劑能夠使用公知者。例如能夠舉出非離子性的化合物，其為如過渡金屬化合物錯合物或具有銨鹽等的結構者或藉由脒部分與羧酸形成鹽而被潛在化者那樣，藉由鹼成分形成鹽而中和之離子性的化合物或藉由胺基甲酸酯衍生物、肟酯衍生物、醯化合物等胺基甲酸酯鍵結或肟鍵結等而鹼成分被潛在化者。＜＜Photohardening Accelerator＞＞ The photosensitive resin composition used in the present invention may also contain a photohardening accelerator. The photohardening accelerator in the present invention is one that generates a base by exposure, and does not show activity under normal conditions of normal temperature and pressure, but as long as it generates a base (alkaline substance) when it is irradiated with electromagnetic waves and heated as an external stimulus ) are not particularly limited. The base generated by exposure functions as a catalyst when the polymer precursor is cured by heating, so it can be preferably used. In this invention, a well-known thing can be used as a photocuring accelerator. For example, nonionic compounds can be mentioned, which are transition metal compound complexes, those having a structure such as ammonium salt, or those that are latent by forming a salt with an amidine moiety and a carboxylic acid, and form a salt with an alkali component. The neutralized ionic compound has a latent base component through a carbamate bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound, or an oxime bond.

作為本發明之光硬化促進劑，例如可舉出如日本特開2009-080452號公報及國際公開第2009/123122號小冊子中揭示那樣具有桂皮酸醯胺結構之光硬化促進劑、如日本特開2006-189591號公報及日本特開2008-247747號公報中揭示那樣具有胺基甲酸酯結構之光硬化促進劑、如日本特開2007-249013號公報及日本特開2008-003581號公報中揭示那樣具有肟結構、胺甲醯基肟結構之光硬化促進劑等，但是並不限定於該等，除此以外亦能夠使用公知的光硬化促進劑的結構。As the photohardening accelerator of the present invention, for example, a photohardening accelerator having a cinnamic acid amide structure as disclosed in JP-A-2009-080452 and International Publication No. 2009/123122 pamphlet, such as JP-A 2006-189591 A and JP 2008-247747 A photohardening accelerator having a urethane structure, as disclosed in JP 2007-249013 A and JP 2008-003581 A Such photocuring accelerators having an oxime structure and a carbamoyl oxime structure, etc., are not limited thereto, and other structures of known photocuring accelerators can also be used.

此外，作為光硬化促進劑，可舉出日本特開2012-093746號公報的0185～0188、0199～0200及0202段中所記載之化合物、日本特開2013-194205號公報的0022～0069段中所記載之化合物、日本特開2013-204019號公報的0026～0074段中所記載之化合物、以及國際公開WO2010/064631號公報的0052段中所記載之化合物作為例子。In addition, examples of photohardening accelerators include compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of JP-A-2012-093746, and compounds described in paragraphs 0022-0069 of JP-A-2013-194205. The compounds described, the compounds described in paragraphs 0026 to 0074 of JP 2013-204019 A, and the compounds described in paragraph 0052 of International Publication WO2010/064631 A are exemplified.

作為光硬化促進劑的市售品，還能夠使用WPBG-266、WPBG-300、WPGB-345、WPGB-140、WPBG-165、WPBG-027、PBG-018、WPGB-015、WPBG-041、WPGB-172、WPGB-174、WPBG-166、WPGB-158、WPGB-025、WPGB-168、WPGB-167及WPBG-082（Wako Pure Chemical Industries，Ltd.製）。Commercially available photocuring accelerators include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB -172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167 and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.).

使用光硬化促進劑之情況下，組成物中的光硬化促進劑的含量相對於組成物的總固體成分係0.1～50質量%為較佳。下限係0.5質量%以上為更佳，1質量%以上為進一步較佳。上限係30質量%以下為更佳，20質量%以下為進一步較佳。 光硬化促進劑能夠使用1種或2種以上。當使用2種以上時，總量係上述範圍為較佳。When using a photocuring accelerator, it is preferable that content of the photocuring accelerator in a composition is 0.1-50 mass % with respect to the total solid content of a composition. 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 photohardening accelerator can use 1 type or 2 or more types. When using 2 or more types, it is preferable that the total amount is in the said range.

＜熱自由基聚合起始劑＞ 本發明的感光性樹脂組成物於不脫離本發明的宗旨之範圍內可以含有熱自由基聚合起始劑。 熱自由基聚合起始劑係藉由熱的能量而產生自由基，並開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，能夠進行聚合物前驅物的環化，並且進行聚合物前驅物的聚合反應，因此能夠實現更高度的耐熱化。 作為熱自由基聚合起始劑，具體而言，可舉出日本特開2008-063554號公報的0074～0118段中所記載之化合物。＜Thermal radical polymerization initiator＞ The photosensitive resin composition of this invention may contain a thermal radical polymerization initiator in the range which does not deviate from the summary of this invention. Thermal free radical polymerization initiators are compounds that generate free radicals by thermal energy and initiate or accelerate the polymerization reaction of polymerizable compounds. By adding a thermal radical polymerization initiator, the cyclization of the polymer precursor can proceed, and the polymerization reaction of the polymer precursor can proceed, so higher heat resistance can be achieved. Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

當含有熱自由基聚合起始劑時，其含量相對於本發明的感光性樹脂組成物的總固體成分係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%。熱自由基聚合起始劑可以僅含有1種，亦可以含有2種以上。當含有2種以上的熱自由基聚合起始劑時，其總計係上述範圍為較佳。When a thermal radical polymerization initiator is contained, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.1 to 20% by mass relative to the total solid content of the photosensitive resin composition of the present invention. 5 to 15% by mass. The thermal radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more thermal radical polymerization initiators are contained, it is preferable that the total is within the above-mentioned range.

＜聚合性化合物＞ ＜＜自由基聚合性化合物＞＞ 本發明的感光性樹脂組成物包含自由基聚合性化合物為較佳。 自由基聚合性化合物能夠使用具有自由基聚合性基之化合物。作為自由基聚合性基，可舉出乙烯基苯基、乙烯基、（甲基）丙烯醯基及烯丙基等具有乙烯性不飽和鍵之基團。自由基聚合性基係（甲基）丙烯醯基為較佳。＜Polymerizable compound＞ ＜＜Radical polymerizable compound＞＞ It is preferable that the photosensitive resin composition of this invention contains a radically polymerizable compound. As the radical polymerizable compound, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as vinylphenyl, vinyl, (meth)acryl, and allyl. The radical polymerizable group is preferably a (meth)acryl group.

自由基聚合性化合物所具有之自由基聚合性基的數可以為1個，亦可以為2個以上，但是自由基聚合性化合物具有2個以上的自由基聚合性基為較佳，具有3個以上為更佳。上限係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 that the radical polymerizable compound has may be 1, or may be 2 or more, but the radical polymerizable compound has 2 or more radical polymerizable groups, preferably 3 or more radical polymerizable groups. The above is better. The upper limit is preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less.

自由基聚合性化合物的分子量係2000以下為較佳，1500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係100以上為較佳。The molecular weight of the radically polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.

從顯影性的觀點考慮，本發明的感光性樹脂組成物包含至少一種具有2個以上的聚合性基之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官能的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。另外，自由基聚合性化合物的官能基數係指一分子中的自由基聚合性基的數。From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one kind of radically polymerizable compound having two or more polymerizable groups, and contains at least one kind of radically polymerizable compound having three or more functions. Sexual compounds are more preferred. Moreover, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or more radical polymerizable compound. In addition, the number of functional groups in a radical polymerizable compound means the number of radical polymerizable groups in one molecule.

作為自由基聚合性化合物的具體例，可舉出不飽和羧酸（例如，丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、異巴豆酸、馬來酸等）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，還可較佳地使用具有羥基或胺基、巰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、與單官能或多官能的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者醯胺類與單官能或多官能的醇類、胺類、硫醇類的加成反應物、還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者醯胺類與單官能或多官能的醇類、胺類、硫醇類的取代反應物亦為較佳。又，作為另一例，替代上述不飽和羧酸，能夠使用被不飽和膦酸、苯乙烯等乙烯基苯衍生物、乙烯醚、烯丙醚等取代之化合物組。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，並將該等內容編入本說明書中。Specific examples of radically polymerizable compounds include unsaturated carboxylic acids (for example, 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 polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyamine compounds. Also, it is also preferable to use unsaturated carboxylic acid esters or amides having affinity substituents such as hydroxyl groups, amine groups, and mercapto groups. Addition reactants of monofunctional or polyfunctional isocyanates or epoxy groups, and monofunctional Dehydration condensation reaction products of functional or polyfunctional carboxylic acids, etc. Also, addition reactants of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and halogens Also preferred are unsaturated carboxylate esters of detachable substituents such as toluenesulfonyloxy groups or substitution reactants of amides with monofunctional or polyfunctional alcohols, amines, and thiols. Also, as another example, instead of the above-mentioned unsaturated carboxylic acid, a compound group substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, and the like can be used. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and these contents are incorporated into this specification.

又，自由基聚合性化合物在常壓下具有100℃以上的沸點之化合物亦為較佳。作為其例，能夠舉出聚乙二醇二（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後進行（甲基）丙烯酸酯化之化合物、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）丙烯酸胺基甲酸酯類、日本特開昭48-064183號公報、日本特公昭49-043191號公報、日本特公昭52-030490號公報中所記載之聚酯丙烯酸酯類，作為環氧樹脂與（甲基）丙烯酸的反應產物的環氧丙烯酸酯類等多官能的丙烯酸酯或甲基丙烯酸酯、以及該等的混合物。此外，日本特開2008-292970號公報的0254～0257段中所記載之化合物亦為較佳。又，還能夠舉出使多官能羧酸與（甲基）丙烯酸縮水甘油酯等具有環狀醚基及乙烯性不飽和鍵之化合物進行反應而獲得的多官能（甲基）丙烯酸酯等。 又，作為除了上述以外的較佳的自由基聚合性化合物，還能夠使用日本特開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2個以上的含有乙烯性不飽和鍵之基團之化合物或卡多樹脂。 進而，作為其他例，還能夠舉出日本特公昭46-043946號公報、日本特公平1-040337號公報、日本特公平1-040336號公報中所記載之既定的不飽和化合物、日本特開平2-025493號公報中所記載之乙烯基膦酸系化合物等。又，還能夠使用日本特開昭61-022048號公報中所記載之包含全氟烷基的化合物。進而，還能夠使用“Journal of the Adhesion Society of Japan”vol.20、No.7、300頁～308頁（1984年）中作為光聚合性單體及寡聚物所介紹者。Moreover, the compound which has a boiling point of 100 degreeC or more under normal pressure is also preferable as a radical polymerizable compound. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol tri (Meth)acrylate, Neopentylthritol tetra(meth)acrylate, Dineopentylthritol penta(meth)acrylate, Dineopentylthritol hexa(meth)acrylate, Hexylene glycol (meth)acrylate base) acrylate, trimethylolpropane tris(acryloxypropyl) ether, tris(acryloxyethyl) isocyanurate, glycerin or trimethylolethane, etc. in polyfunctional alcohols Compounds that undergo (meth)acrylation after adding ethylene oxide or propylene oxide, Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Patent Application Publication No. 51-037193 (Meth)acrylic urethanes described in the gazette, Japanese Patent Application Publication No. 48-064183, Japanese Patent Publication No. 49-043191, polyester acrylic acid described in Japanese Patent Publication No. 52-030490 Esters, polyfunctional acrylates or methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferable. Moreover, the polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid and the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, etc. are mentioned. In addition, as preferable radical polymerizable compounds other than the above-mentioned ones, there can also be used those with fenugreek described in JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. A compound or cardo resin having a ring and having two or more ethylenically unsaturated bond-containing groups. Furthermore, as other examples, predetermined unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 1-040337, Japanese Patent Publication No. 1-040336, Japanese Patent Laid-Open No. 2 -Vinylphosphonic acid-based compounds described in Publication No. 025493, etc. Also, compounds containing a perfluoroalkyl group described in JP-A-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, pages 300 to 308 (1984) can also be used.

除了上述以外，還能夠較佳地使用日本特開2015-034964號公報的0048～0051段中所記載之化合物，並將該等內容編入本說明書中。In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 can also be preferably used, and these contents are incorporated in this specification.

又，日本特開平10-062986號公報中作為式（1）及式（2）且與其具體例一同記載之在多官能醇加成環氧乙烷或環氧丙烷之後進行（甲基）丙烯酸酯化之化合物亦能夠用作自由基聚合性化合物。Also, in Japanese Patent Application Laid-Open No. 10-062986, it is described as formula (1) and formula (2) together with specific examples thereof, after adding ethylene oxide or propylene oxide to polyfunctional alcohol, performing (meth)acrylate Chemicalized compounds can also be used as radically polymerizable compounds.

另外，日本特開2015-187211號公報的0104～0131段中所記載之化合物亦能夠用作其他自由基聚合性化合物，該等內容編入本說明書中。In addition, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as other radically polymerizable compounds, and these contents are incorporated in 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）及該等的（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。亦能夠使用該等的寡聚物類型。As a radically polymerizable compound, diperythritol triacrylate (a commercial item is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), diperythritol tetraacrylate (a commercial item is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), diperythritol penta(meth)acrylate (the commercially available product is KAYARAD D -310; manufactured by Nippon Kayaku Co., Ltd.), diperythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical Co., Ltd.) and the structure in which (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferable. These oligomer types can also be used.

作為自由基聚合性化合物的市售品，例如可舉出Sartomer Company,Inc製的作為具有4個伸乙氧基鏈之4官能丙烯酸酯之SR-494、作為具有4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6個伸戊氧基鏈之6官能丙烯酸酯之DPCA-60、作為具有3個異伸丁氧基鏈之3官能丙烯酸酯之TPA-330、胺基甲酸酯寡聚物UAS-10、胺基甲酸酯寡聚物UAB-140（NIPPON PAPER INDUSTRIES CO.,LTD.製）、NK ESTER M-40G、NK ESTER 4G、NK ESTER M-9300、NK ESTER 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。Commercially available radically polymerizable compounds include, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethoxylate chains, and SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains. Sartomer Company, Inc. SR-209, 231, 239 of functional methyl acrylate, Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having 6 TPA-330, urethane oligomer UAS-10, urethane oligomer 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.), 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2-032293號公報、日本特公平2-016765號公報中所記載之那樣的胺基甲酸酯丙烯酸酯類、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號公報中所記載之具有環氧乙烷系骨架之胺基甲酸酯化合物類亦為較佳。另外，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1-105238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 the radical polymerizable compound, as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 2-032293, and Japanese Patent Publication No. 2-016765 Urethane acrylates, 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. Oxyethane-based urethane compounds are also preferred. In addition, as the radically polymerizable compound, compounds having an amino group in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-1-105238 can also be used. Compounds with structure or sulfide structure.

自由基聚合性化合物可以為羧基、磷酸基等具有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中，脂肪族聚羥基化合物與不飽和羧酸的酯為較佳，使脂肪族聚羥基化合物的未反應的羥基與非芳香族羧酸酐反應而具有酸基之自由基聚合性化合物為更佳。特佳為使脂肪族多羥基化合物的未反應的羥基與非芳香族羧酸酐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係作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，可舉出M-510、M-520等。 具有酸基之自由基聚合性化合物的較佳的酸值係0.1～40mgKOH/g，特佳為5～30mgKOH/g。自由基聚合性化合物的酸值只要在上述範圍內，則製造或操作性優異，進而顯影性優異。又，聚合性亦良好。The radically polymerizable compound may be a radically polymerizable compound having an acidic group such as a carboxyl group or a phosphoric acid group. Among radically polymerizable compounds having acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, which have acid groups by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic acid anhydrides. A radically polymerizable compound is more preferable. Particularly preferred is a radically polymerizable compound having an acid group by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. compound. As a commercial item, M-510, M-520, etc. are mentioned, for example as TOAGOSEI CO., Ltd. polyacid-modified acrylic oligomer. The preferable acid value of the radically polymerizable compound which has an acid group is 0.1-40 mgKOH/g, especially preferably 5-30 mgKOH/g. If the acid value of a radically polymerizable compound exists in the said range, it will be excellent in manufacture and handleability, and also will be excellent in developability. Moreover, polymerizability is also favorable.

從抑制伴隨硬化膜的彈性模數控制之翹曲的觀點考慮，本發明的感光性樹脂組成物能夠較佳地使用單官能自由基聚合性化合物來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、苄基（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、縮水甘油基（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、烯丙基縮水甘油醚、鄰苯二甲酸二烯丙酯、偏苯三酸三烯丙酯等烯丙基化合物類等。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為較佳。In the photosensitive resin composition of the present invention, it is preferable to use a monofunctional radical polymerizable compound as the radical polymerizable compound from the viewpoint of suppressing warpage accompanying elastic modulus control of the cured film. As the monofunctional radically polymerizable compound, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, (Meth)acrylic acid such as N-methylol(meth)acrylamide, glycidyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate Derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate Allyl compounds such as esters, etc. As the monofunctional radical polymerizable compound, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferable.

＜＜除了上述之自由基聚合性化合物以外的聚合性化合物＞＞ 本發明的感光性樹脂組成物還能夠含有上述之自由基聚合性化合物以外的聚合性化合物。作為除了上述之自由基聚合性化合物以外的聚合性化合物，可舉出具有羥甲基、烷氧甲基或醯氧甲基之化合物；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 radically polymerizable compounds mentioned above>> The photosensitive resin composition of the present invention may contain polymerizable compounds other than the above-mentioned radically polymerizable compounds. Examples of polymerizable compounds other than the radically polymerizable compounds described above include compounds having a methylol, alkoxymethyl, or acyloxymethyl group; epoxy compounds; oxetane compounds; compound.

（具有羥甲基、烷氧甲基或醯氧甲基之化合物） 作為具有羥甲基、烷氧甲基或醯氧甲基之化合物，由下述式（AM1）、（AM4）或（AM5）表示之化合物為較佳。(compounds with hydroxymethyl, alkoxymethyl or acyloxymethyl) As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferable.

[化學式33]

Figure 02_image065
（式中，t表示1～20的整數，R104 表示碳數1～200的t價的有機基，R105 表示由-OR106 或-OCO-R107 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。）[chemical formula 33]
Figure 02_image065
(In the formula, t represents an integer of 1 to 20, R 104 represents a t-valent organic group with a carbon number of 1 to 200, R 105 represents a group represented by -OR 106 or -OCO-R 107 , R 106 represents a hydrogen atom Or an organic group with 1 to 10 carbons, R 107 represents an organic group with 1 to 10 carbons.)

[化學式34]

Figure 02_image067
（式中，R404 表示碳數1～200的2價的有機基，R405 表示由-OR406 或-OCO-R407 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。）[chemical formula 34]
Figure 02_image067
(In the formula, R 404 represents a divalent organic group with 1 to 200 carbons, R 405 represents a group represented by -OR 406 or -OCO-R 407 , R 406 represents a hydrogen atom or an organic group with 1 to 10 carbons group, R 407 represents an organic group with 1 to 10 carbons.)

[化學式35]

Figure 02_image069
（式中，u表示3～8的整數，R504 表示碳數1～200的u價的有機基，R505 表示由-OR506 或、-OCO-R507 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 35]
Figure 02_image069
(In the formula, u represents an integer of 3 to 8, R 504 represents a u-valent organic group with a carbon number of 1 to 200, R 505 represents a group represented by -OR 506 or -OCO-R 507 , R 506 represents hydrogen atom or an organic group with 1 to 10 carbons, R 507 represents an organic group with 1 to 10 carbons.)

作為由式（AM4）表示之化合物的具體例，可舉出46DMOC、46DMOEP（以上為產品名，ASAHI ORGANIC CHEMICALS INDUSTRY CO.,LTD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，Honshu Chemical Industry Co.,Ltd.製）、NIKALAC MX-290（以上為產品名，Sanwa Chemical Co.,Ltd.製）、2,6-dimethoxymethyl-4-t-butylphenol（2,6-二甲氧基甲基-4-第三丁基苯酚）、2,6-dimetoxymethyl-p-cresol（2,6-二甲氧基甲基-對甲酚）、2,6-diacethoxymethyl-p-cresol（2,6-二乙醯氧基甲基-對甲酚）等。Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above are product names, manufactured by ASAHI ORGANIC CHEMICALS INDUSTRY CO., LTD), 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 (the above are product names, Honshu Chemical Industry Co.,Ltd .), NIKALAC MX-290 (the above is the product name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol (2,6-dimethoxymethyl-4-th Tributylphenol), 2,6-dimetoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacethoxymethyl-p-cresol (2,6-diacetyloxy methyl-p-cresol), etc.

又，作為由式（AM5）表示之化合物的具體例，可舉出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，Honshu Chemical Industry Co.,Ltd.製）、TM-BIP-A（產品名，ASAHI ORGANIC CHEMICALS INDUSTRY CO.,LTD製）、NIKALAC MX-280、NIKALAC MX-270、NIKALAC MW-100LM（以上為產品名，Sanwa Chemical Co.,Ltd.製）。In addition, specific examples of the compound represented by the 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 (the above are product names, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (product name, manufactured by ASAHI ORGANIC CHEMICALS INDUSTRY CO., LTD.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (the above 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，係於一分子中具有2個以上的環氧基之化合物為較佳。環氧基於200℃以下進行交聯反應，並且由於不會引起源自交聯之脫水反應而難以引起膜收縮。因此，藉由含有環氧化合物，可有效地抑制組成物的低溫硬化及翹曲。(epoxy compounds (compounds with epoxy groups)) As an epoxy compound, it is preferable that it is a compound which has 2 or more epoxy groups in one molecule. Epoxy undergoes a crosslinking reaction at a temperature below 200°C, and since it does not cause a dehydration reaction resulting from crosslinking, it is difficult to cause film shrinkage. Therefore, low-temperature hardening and warpage of the composition can be effectively suppressed by containing the epoxy compound.

環氧化合物含有聚環氧乙烷基為較佳。藉此，彈性模數進一步降低，並且能夠抑制翹曲。聚環氧乙烷基係指環氧乙烷的構成單元數係2以上者，構成單元數係2～15為較佳。The epoxy compound preferably contains a polyethylene oxide group. Thereby, the modulus of elasticity is further reduced, and warpage can be suppressed. The polyethylene oxide group refers to those whose constituent units of ethylene oxide are 2 or more, preferably 2 to 15 constituent units.

作為環氧化合物的例，能夠舉出雙酚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基型環氧樹脂；聚丙二醇二環氧丙基醚等聚伸烷基二醇基型環氧樹脂；聚甲基（縮水甘油基丙基）矽氧烷等含環氧基的聚矽氧等，但是並不限定於該等。具體而言，可舉出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（以上為產品名，DIC Corporation製）、RIKARESIN（註冊商標）BEO-60E（產品名，New Japan Chemical Co.,Ltd.製）、EP-4003S、EP-4000S（以上為產品名，ADEKA CORPORATION製）等。該等中，從抑制翹曲及耐熱性優異之方面考慮，含有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含有聚環氧乙烷基，因此為較佳。Examples of epoxy compounds include bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol based epoxy resins such as propylene glycol diglycidyl ether; polypropylene glycol diepoxy resins; Polyalkylene glycol-based epoxy resins such as propyl ether; epoxy group-containing polysiloxanes such as polymethyl(glycidylpropyl)siloxane, etc., but are not limited to these. Specifically, 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) Trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (the above are product names, manufactured by DIC Corporation), RIKARESIN (registered Trademark) BEO-60E (product name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (the above are product names, manufactured by ADEKA CORPORATION), etc. Among these, the epoxy resin containing a polyethylene oxide group is preferable from the point which suppresses warpage and is excellent in heat resistance. For example, since EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain polyethylene oxide groups, they are preferable.

（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，能夠舉出於一分子中具有2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，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，或者可以混合2種以上。(Oxetane compounds (compounds having an oxetanyl group)) Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethoxetane, 1,4-bis{ [(3-Ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4- Benzene dicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc. 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 may be used alone or in combination. more than one species.

（苯并㗁𠯤化合物（具有聚苯并㗁唑基之化合物）） 苯并㗁𠯤化合物因源自開環加成反應之交聯反應而於硬化時不產生脫氣，進而減少熱收縮而抑制產生翹曲，因此為較佳。(Benzozoline compounds (compounds having a polybenzoxazolyl group)) The benzo 㗁 𠯤 compound is preferable because the cross-linking reaction derived from the ring-opening addition reaction does not generate outgassing during hardening, thereby reducing heat shrinkage and suppressing warpage.

作為苯并㗁𠯤化合物的較佳的例，可舉出B-a型苯并㗁𠯤、B-m型苯并㗁𠯤（以上為產品名，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，或者可以混合2種以上。Preferable examples of benzophenone compounds include B-a type benzophenone, B-m type benzophenone (the above are product names, manufactured by Shikoku Chemicals Corporation), polyhydroxystyrene resin benzophenone Adducts, novolak-type dihydrobenzo㗁𠯤 compounds. These can be used individually or in mixture of 2 or more types.

含有聚合性化合物之情況下，其含量相對於本發明的感光性樹脂組成物的總固體成分係大於0質量%且60質量%以下為較佳。下限係5質量%以上為更佳。上限係50質量%以下為更佳，30質量%以下為進一步較佳。 聚合性化合物可以單獨使用1種，但是亦可以混合2種以上而使用。當同時使用2種以上時，其總計量成為上述範圍為較佳。When containing a polymeric compound, it is preferable that the content is more than 0 mass % and 60 mass % or less with respect to the total solid content of the photosensitive resin composition of this invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably at most 50% by mass, and is still more preferably at most 30% by mass. Although a polymeric compound can be used individually by 1 type, it can also mix and use 2 or more types. When using 2 or more types simultaneously, it is preferable that the total amount becomes the said range.

＜遷移抑制劑＞ 本發明的感光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）的金屬離子轉移到感光性樹脂組成物層內。 作為遷移抑制劑，並無特別限制，可舉出具有雜環（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、噠𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、口末啉環、2H-吡喃環及6H-吡喃環、三𠯤環）之化合物、具有硫脲類及巰基之化合物、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、苯并三唑等三唑系化合物、1H-四唑、5-苯基四唑等四唑系化合物。＜Migration Inhibitor＞ It is preferable that the photosensitive resin composition of the present invention further includes a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress migration of metal ions originating in the metal layer (metal wiring) into the photosensitive resin composition layer. The migration inhibitor is not particularly limited, and examples include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, azole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, Azole ring, pyridine ring, pyranyl ring, pyrimidine ring, pyranyl ring, piperidine ring, piperyl ring, portoline ring, 2H-pyran ring and 6H-pyran ring, tri-alpha ring) compounds, with Thiourea and mercapto compounds, hindered phenolic compounds, salicylic acid derivatives, hydrazide derivatives. In particular, triazole-based compounds such as 1,2,4-triazole and benzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

又，亦能夠使用捕捉鹵素離子等陰離子之離子捕捉劑。In addition, an ion-trapping agent that traps anions such as halogen ions can also 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段中所記載之防鏽劑、日本特開2009-283711號公報的0073～0076段中所記載之化合物、日本特開2011-059656號公報的0052段中所記載之化合物、日本特開2012-194520號公報的0114、0116段及0118段中所記載之化合物等。As other migration inhibitors, rust inhibitors described in paragraph 0094 of JP 2013-015701 A, compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, JP 2011 - Compounds described in paragraph 0052 of Japanese Patent Application Laid-Open No. 059656, compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, and the like.

作為遷移抑制劑的具體例，能夠舉出下述化合物。 [化學式36]

Figure 02_image071
Specific examples of migration inhibitors include the following compounds. [chemical formula 36]
Figure 02_image071

當感光性樹脂組成物具有遷移抑制劑時，遷移抑制劑的含量相對於感光性樹脂組成物的總固體成分係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。 遷移抑制劑可以係僅為1種，亦可以係2種以上。當遷移抑制劑係2種以上時，其總計係上述範圍為較佳。When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and 0.1 to 1.0% relative to the total solid content of the photosensitive resin composition. Mass % is further more preferable. The migration inhibitor may be only one type, or may be two or more types. When there are two or more migration inhibitors, it is preferable that the total is within the above range.

＜聚合抑制劑＞ 本發明的感光性樹脂組成物包含聚合抑制劑為較佳。 作為聚合抑制劑，例如可較佳地使用對苯二酚、4-甲氧基苯酚、二-第三丁基-對甲酚、鄰苯三酚、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-第三丁基苯酚）、2,2’-亞甲基雙（4-甲基-6-第三丁基苯酚）、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-甲基苯酚、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）苯酚、N-亞硝基-N-（1-萘基）羥胺銨鹽、雙（4-羥基-3,5-第三丁基）苯基甲烷等。又，亦能夠使用日本特開2015-127817號公報的0060段中所記載之聚合抑制劑及國際公開WO2015/125469號的0031～0046段中所記載之化合物。 又，還能夠使用下述化合物（Me為甲基）。 [化學式37]

Figure 02_image073
當本發明的感光性樹脂組成物具有聚合抑制劑時，聚合抑制劑的含量相對於本發明的感光性樹脂組成物的總固體成分係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。 聚合抑制劑可以僅為一種，亦可以為2種以上。當聚合抑制劑為2種以上時，其總計為上述範圍為較佳。<Polymerization inhibitor> It is preferable that the photosensitive resin composition of this invention contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 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, phenanthrene, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylidene diphenylamine Amine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, ethylene glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxy Quinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N -Nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, etc. In addition, the polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication WO2015/125469 can also be used. Moreover, the following compound (Me is a methyl group) can also be used. [chemical formula 37]
Figure 02_image073
When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5 mass % relative to the total solid content of the photosensitive resin composition of the present invention, and 0.02 to 3 mass % is More preferably, 0.05 to 2.5 mass % is still more preferable. The polymerization inhibitor may be only one kind, or may be two or more kinds. When there are two or more kinds of polymerization inhibitors, the total of them is preferably within the above-mentioned range.

＜金屬接黏性改良劑＞ 本發明的感光性樹脂組成物包含用於提高與使用於電極或配線等之金屬材料的接黏性之金屬接黏性改良劑為較佳。作為金屬接黏性改良劑，可舉出矽烷偶合劑等。＜Metal Adhesion Improver＞ It is preferable that the photosensitive resin composition of the present invention contains a metal adhesion improving agent for improving the adhesion with metal materials used for electrodes, wiring, and the like. As a metal adhesion improving agent, a silane coupling agent etc. are mentioned.

作為矽烷偶合劑之例，可舉出日本特開2014-191002號公報的0062～0073段中所記載之化合物、國際公開WO2011/080992A1號的0063～0071段中所記載之化合物、日本特開2014-191252號公報的0060～0061段中所記載之化合物、日本特開2014-041264號公報的0045～0052段中所記載之化合物、國際公開WO2014/097594號的0055段中所記載之化合物。又，如日本特開2011-128358號公報的0050～0058段中所記載那樣使用不同的2種以上的矽烷偶合劑亦為較佳。又，矽烷偶合劑使用下述化合物亦為較佳。以下式中，Et表示乙基。 [化學式38]

Figure 02_image075
Examples of silane coupling agents include compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, compounds described in paragraphs 0063-0071 of International Publication WO2011/080992A1, JP-A-2014 - Compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, and compounds described in paragraph 0055 of International Publication WO2014/097594. Moreover, it is also preferable to use different 2 or more types of silane coupling agents as described in paragraph 0050-0058 of Unexamined-Japanese-Patent No. 2011-128358. Moreover, it is also preferable to use the following compounds as a silane coupling agent. In the following formulae, Et represents an ethyl group. [chemical formula 38]
Figure 02_image075

又，金屬接黏性改良劑還能夠使用日本特開2014-186186號公報的0046～0049段中所記載之化合物、日本特開2013-072935號公報的0032～0043段中所記載之硫化物系化合物。In addition, as the metal adhesion improving agent, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide-based compounds described in paragraphs 0032-0043 of JP-A-2013-072935 can also be used. compound.

金屬接黏性改良劑的含量相對於聚合物前驅物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，硬化步驟之後的硬化膜與金屬層的接黏性變良好，藉由設為上述上限值以下，硬化步驟之後的硬化膜的耐熱性、機械特性變良好。金屬接黏性改良劑可以係僅為一種，亦可以係2種以上。當使用2種以上時，其總計為上述範圍為較佳。The content of the metal adhesion modifier is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and still more preferably in the range of 0.5 to 5 parts by mass relative to 100 parts by mass of the polymer precursor. By making it more than the said lower limit, the adhesiveness of the cured film after a hardening process and a metal layer becomes favorable, and by making it below the said upper limit, the heat resistance of the cured film after a hardening process, and a mechanical characteristic become favorable. . The metal adhesion improver may be one type only, or two or more types may be used. When using 2 or more types, it is preferable that the total is the said range.

＜硬化促進劑＞ 本發明的感光性樹脂組成物亦可以包含硬化促進劑。硬化促進劑可以為熱硬化促進劑亦可以為光硬化促進劑。本發明中的硬化促進劑係藉由熱或曝光等產生鹼者（鹼產生劑）為較佳。 ＜＜熱硬化促進劑＞＞ 熱硬化促進劑係第四級銨陽離子與羧酸陰離子的鹽為較佳。該第四級銨陽離子係由下述式（Y1-1）～式（Y1-4）中的任一個所表示為較佳。 [化學式39]

Figure 02_image077
<Hardening accelerator> The photosensitive resin composition of this invention may contain a hardening accelerator. The hardening accelerator may be a thermal hardening accelerator or a photohardening accelerator. The hardening accelerator in the present invention is preferably one that generates a base by heat or exposure (base generator). <<Thermal curing accelerator>> The thermal curing accelerator is preferably a salt of quaternary ammonium cation and carboxylic acid anion. The quaternary ammonium cation is preferably represented by any one of the following formulas (Y1-1) to formula (Y1-4). [chemical formula 39]
Figure 02_image077

RY1 表示nY 價（nY 係1～12的整數）的有機基，nY 價的烴基為較佳。作為烴基，可舉出包含烷烴之nY 價的基團（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、包含烯烴之nY 價的基團（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、包含芳香族烴之nY 價的基團（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）或該等組合。RY1 係其中的芳香族烴基為較佳。在不損害本發明的效果之範圍內，RY1 可以具有前述的取代基T。 式中，RY2 ～RY5 分別獨立地表示氫原子或烴基（碳數1～36為較佳，1～24為更佳，1～12為進一步較佳）、烷基（碳數1～36為較佳，1～24為更佳，1～23為進一步較佳）、烯基（碳數2～36為較佳，2～24為更佳，2～23為進一步較佳）、炔基（碳數1～36為較佳，1～24為更佳，1～23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）為較佳。該烷基、烯基、炔基可以為環狀亦可以為鏈狀，鏈狀的情況下，可以為直鏈狀亦可以為支鏈狀。 RY6 為烷基（碳數1～36為較佳，2～24為更佳，4～18為進一步較佳）、烯基（碳數2～36為較佳，2～24為更佳，4～18為進一步較佳）、炔基（碳數2～36為較佳，2～24為更佳，4～18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）。烷基、烯基、炔基可以為環狀亦可以為鏈狀，鏈狀的情況下，可以為直鏈狀亦可以為支鏈狀。烷基、烯基、炔基、芳基中，在基團的中途或者在與母核的連接中亦可以存在包含雜原子之連接基Lh。 nY 表示1～12的整數，1～6的整數為更佳，1～3的整數為進一步較佳。 nX 表示1～12的整數，1～6的整數為較佳，1～3的整數為進一步較佳。 RY2 ～RY6 亦可以分別2個以上彼此鍵結而形成環。R Y1 represents an organic group with a valence of n Y (n Y is an integer of 1 to 12), preferably a hydrocarbon group with a valence of n Y. Examples of hydrocarbon groups include groups with n Y valences of alkanes (preferably 1 to 12 carbons, more preferably 1 to 6, and more preferably 1 to 3), and groups with n Y valences of alkenes. (2 to 12 carbons are preferred, 2 to 6 are more preferred, and 2 to 3 are further preferred), n Y valence groups containing aromatic hydrocarbons (6 to 22 carbons are preferred, 6 to 18 is more preferred, 6-10 is further preferred) or these combinations. R Y1 is preferably an aromatic hydrocarbon group. R Y1 may have the aforementioned substituent T within a range not impairing the effect of the present invention. In the formula, RY2 to RY5 independently represent a hydrogen atom or a hydrocarbon group (preferably with 1 to 36 carbons, more preferably with 1 to 24, more preferably with 1 to 12), alkyl (with 1 to 36 carbons) is preferred, 1-24 is more preferred, 1-23 is further preferred), alkenyl (2-36 carbons is preferred, 2-24 is more preferred, 2-23 is further preferred), alkynyl (preferably 1-36 carbons, more preferably 1-24, further preferably 1-23), aryl (preferably 6-22 carbons, more preferably 6-18, further preferably 6-10 better) is better. The alkyl group, alkenyl group, and alkynyl group may be cyclic or chain, and in the case of chain, may be linear or branched. R Y6 is alkyl (preferably 1-36 carbons, more preferably 2-24, further preferably 4-18), alkenyl (preferably 2-36 carbons, more preferably 2-24, 4-18 is more preferred), alkynyl (2-36 carbons is preferred, 2-24 is more preferred, 4-18 is further preferred), aryl (6-22 carbons is preferred, 6 ~18 is more preferable, and 6~10 is further preferable). An alkyl group, an alkenyl group, and an alkynyl group may be cyclic or chain, and in the case of chain, may be linear or branched. In an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, a linking group Lh containing a heteroatom may exist in the middle of the group or in the connection with the core. n Y represents the integer of 1-12, the integer of 1-6 is more preferable, and the integer of 1-3 is still more preferable. n X represents the integer of 1-12, the integer of 1-6 is preferable, and the integer of 1-3 is more preferable. Two or more of R Y2 to R Y6 may be bonded to each other to form a ring.

RY7 ～RY16 係與RN 的定義相同的基團。式（Y1-2）中，RY7 及RY8 係羧基烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳；羧基的數係1～12為較佳，1～6為更佳，1～3為進一步較佳）為較佳。RY9 係芳香族基為較佳，芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）為較佳。或者，經芳香族基取代之烷氧羰基為較佳（烷氧基係碳數1～12為較佳，1～6為更佳，1～3為進一步較佳，芳香族基係碳數6～22為較佳，6～18為更佳，6～14為進一步較佳）。式（Y1-3）中，RY11 及RY13 係氫原子為較佳。RY14 及RY15 組合2個，亦可以成為=C（NRN 2 ）2 的形的取代基（=係指藉由雙鍵與氮原子鍵結）。式（Y1-4）中，RY13 係氫原子為較佳，RY10 、RY11 、RY12 、RY16 係烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）為較佳。此時，RY11 與RY16 、RY10 與RY12 鍵結而形成環來成為雙環化合物為較佳。具體而言，可舉出二吖雙環壬烯、二吖雙環十一烯。R Y7 to R Y16 are the same groups as defined in R N . In the formula (Y1-2), R Y7 and R Y8 are carboxyalkyl groups (preferably 1-12 carbons, more preferably 1-6, more preferably 1-3; the number of carboxyl groups is 1-12 Preferably, 1 to 6 are more preferred, 1 to 3 are still more preferred) are preferred. R Y9 is preferably an aromatic group, and an aryl group (preferably 6-22 carbon atoms, more preferably 6-18 carbon atoms, and further preferably 6-10 carbon atoms). Alternatively, an alkoxycarbonyl group substituted by an aromatic group is preferred (the alkoxy group has 1 to 12 carbon atoms, 1 to 6 is more preferred, and 1 to 3 is more preferred, and the aromatic group has 6 carbon atoms. ～22 is preferable, 6～18 is more preferred, 6～14 is further preferred). In the formula (Y1-3), R Y11 and R Y13 are preferably hydrogen atoms. A combination of two RY14 and RY15 can also be a substituent in the form of =C(NR N 2 ) 2 (= refers to a nitrogen atom bonded by a double bond). In formula (Y1-4), RY13 is preferably a hydrogen atom, RY10 , RY11 , RY12 , and RY16 are alkyl groups (preferably 1-12 carbons, more preferably 1-6, 1-6 3 is further preferred) is preferred. In this case, it is preferable that RY11 and RY16 and RY10 and RY12 are bonded to form a ring to form a bicyclic compound. Specifically, diacribicyclononene and diacribicycloundecene are mentioned.

本實施形態中，與上述式（Y1-1）、式（Y1-3）及式（Y1-4）的第四級銨陽離子成對之羧酸陰離子由下述式（X1）表示為較佳。 [化學式40]

Figure 02_image079
式（X1）中，EWG表示吸電子基。In this embodiment, the carboxylate anion paired with the quaternary ammonium cation of the above formula (Y1-1), formula (Y1-3) and formula (Y1-4) is preferably represented by the following formula (X1) . [chemical formula 40]
Figure 02_image079
In formula (X1), EWG represents an electron-withdrawing group.

本實施形態中吸電子基是指，哈米特取代基常數σm表示正的值者。其中，σm於都野雄甫總說、Journal of Synthetic Organic Chemistry，Japan第23卷第8號（1965）p.631-642中進行詳細說明。此外，本實施形態中的吸電子基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，可舉出CF3 基（σm=0.43）、CF3 CO基（σm=0.63）、HC≡C基（σm=0.21）、CH2 =CH基（σm=0.06）、Ac基（σm=0.38）、MeOCO基（σm=0.37）、MeCOCH=CH基（σm=0.21）、PhCO基（σm=0.34）、H2 NCOCH2 基（σm=0.06）等。此外，Me表示甲基，Ac表示乙醯基，Ph表示苯基（以下，相同）。The electron-withdrawing group in the present embodiment refers to a Hammett's substituent constant σm showing a positive value. Among them, σm is described in detail in Mr. Tsuno Yuuo, Journal of Synthetic Organic Chemistry, Japan, Vol. 23, No. 8 (1965), p.631-642. In addition, the electron-withdrawing group in this embodiment is not limited to the substituents described in the above-mentioned documents. Examples of substituents in which σm represents a positive value include CF 3 group (σm=0.43), CF 3 CO group (σm=0.63), HC≡C group (σm=0.21), CH 2 =CH group ( σm=0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H 2 NCOCH 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係由下述式（EWG-1）～（EWG-6）表示之基團為較佳。 [化學式41]

Figure 02_image081
式（EWG-1）～（EWG-6）中，Rx1 ～Rx3 分別獨立地表示氫原子、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）、羥基或羧基。Ar表示芳香族基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）。當Rx1 ～Rx3 為烷基、烯基、芳基時，可以形成環，形成環時可以於其中途夾雜上述連接基L或具有上述雜原子之連接基Lh。該等烷基、烯基、芳基以及Ar在不損害本發明的效果之範圍內，亦可以具有取代基T。其中，Ar尤其具有羧基（較佳為1～3個）為較佳。*表示鍵結位置。 Np表示1～6的整數，1～3的整數為較佳，1或2為更佳。EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [chemical formula 41]
Figure 02_image081
In the formulas (EWG-1) to (EWG-6), R x1 to R x3 independently represent a hydrogen atom and an alkyl group (preferably 1 to 12 carbons, more preferably 1 to 6, and furthermore 1 to 3 preferably), alkenyl (preferably 2-12 carbons, more preferably 2-6, further preferably 2-3), aryl (preferably 6-22 carbons, more preferably 6-18 , 6-10 are further preferred), hydroxyl or carboxyl. Ar represents an aromatic group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 10 carbon atoms). When R x1 to R x3 are alkyl groups, alkenyl groups, or aryl groups, a ring may be formed, and the above-mentioned linking group L or the linking group Lh having the above-mentioned heteroatom may be inserted in the middle of the ring. Such an alkyl group, an alkenyl group, an aryl group, and Ar may have a substituent T within the range which does not impair the effect of this invention. Among them, Ar particularly preferably has a carboxyl group (preferably 1 to 3). * Indicates bond position. Np represents an integer of 1-6, preferably an integer of 1-3, more preferably 1 or 2.

本發明中的熱硬化促進劑的分子量較佳為100以上且小於2000，更佳為200～1000。 作為本發明中的熱硬化促進劑的具體例，除了實施例中所使用之D-1～D-3以外，還可例示WO2015/199219號公報中所記載之加熱到40℃以上時產生鹼之酸性化合物及具有pKa1係0～4的陰離子及銨陽離子之銨鹽，該等內容編入本說明書中。The molecular weight of the thermosetting accelerator in the present invention is preferably from 100 to less than 2000, more preferably from 200 to 1000. As a specific example of the thermosetting accelerator in the present invention, in addition to D-1 to D-3 used in the examples, the one described in WO2015/199219 A that generates alkali when heated to 40°C or higher can also be exemplified. Acidic compounds and ammonium salts of anions and ammonium cations having a pKa1 range of 0 to 4 are included in this specification.

使用熱硬化促進劑之情況下，組成物中的熱硬化促進劑的含量相對於組成物的總固體成分係0.01～50質量%為較佳。下限係0.05質量%以上為更佳，0.1質量%以上為進一步較佳。上限係10質量%以下為更佳，5質量%以下為進一步較佳。 熱硬化促進劑能夠使用1種或2種以上。當使用2種以上時，總量係上述範圍為較佳。又，本發明的組成物亦能夠設為實質上不包含熱硬化促進劑之結構。實質上不包含係指相對於組成物的總固體成分小於0.01質量%，小於0.005質量%為更佳。When using a thermosetting accelerator, it is preferable that content of the thermosetting accelerator in a composition is 0.01-50 mass % with respect to the total solid content of a composition. The lower limit is more preferably at least 0.05% by mass, and more preferably at least 0.1% by mass. The upper limit is more preferably at most 10% by mass, and more preferably at most 5% by mass. One type or two or more types of thermosetting accelerators can be used. When using 2 or more types, it is preferable that the total amount is in the said range. Moreover, the composition of this invention can also be set as the structure which does not contain a thermosetting accelerator substantially. Substantially not containing means less than 0.01% by mass, more preferably less than 0.005% by mass, relative to the total solid content of the composition.

＜其他添加劑＞ 本發明的感光性樹脂組成物在不損害本發明的效果之範圍內，能夠依需要對各種添加物，例如，熱酸產生劑、增感色素、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、凝聚抑制劑等進行摻合。對該等添加劑進行摻合時，將其總計摻合量設為組成物的固體成分的3質量%以下為較佳。＜Other additives＞ The photosensitive resin composition of the present invention can be used for various additives such as thermal acid generators, sensitizing pigments, chain transfer agents, surfactants, higher fatty acid derivatives, etc. , inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. are blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

＜＜熱酸產生劑＞＞ 本發明的感光性樹脂組成物可以含有熱酸產生劑。熱酸產生劑藉由加熱而產生酸，且促進聚合物前驅物的環化而進一步提高硬化膜的機械特性。關於熱酸產生劑，可舉出日本特開2013-167742號公報的0059段中所記載之化合物等。＜＜Thermal acid generator＞＞ The photosensitive resin composition of the present invention may contain a thermal acid generator. The thermal acid generator generates acid by heating, and promotes the cyclization of the polymer precursor to further improve the mechanical properties of the cured film. Examples of thermal acid generators include compounds described in paragraph 0059 of JP-A-2013-167742, and the like.

熱酸產生劑的含量相對於聚合物前驅物100質量份係0.01質量份以上為較佳，0.1質量份以上為更佳。含有0.01質量份以上的熱酸產生劑，藉此促進交聯反應及聚合物前驅物的環化，因此能夠進一步提高硬化膜的機械特性及耐化學性。又，從硬化膜的電絕緣性的觀點考慮，熱酸產生劑的含量係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。 熱酸產生劑可以僅使用一種，亦可以使用2種以上。當使用2種以上時，總量成為上述範圍為較佳。The content of the thermal acid generator is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the polymer precursor, more preferably 0.1 parts by mass or more. Containing 0.01 parts by mass or more of the thermal acid generator promotes the crosslinking reaction and the cyclization of the polymer precursor, so that the mechanical properties and chemical resistance of the cured film can be further improved. Moreover, from the viewpoint of the electrical insulation of a cured film, content of a thermal acid generator is preferably 20 parts by mass or less, More preferably, it is 15 parts by mass or less, More preferably, it is 10 parts by mass or less. A thermal acid generator may use only 1 type, and may use 2 or more types. When using 2 or more types, it is preferable that the total amount becomes the said range.

＜＜增感色素＞＞ 本發明的感光性樹脂組成物可以含有增感色素。增感色素吸收既定的活性放射線而成為電子激發狀態。成為電子激發狀態之增感色素與熱硬化促進劑、熱自由基聚合起始劑、光自由基聚合起始劑等接觸，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發生化學變化而分解，並產生自由基、酸或鹼。關於增感色素的詳細內容，能夠參閱日本特開2016-027357號公報的0161～0163段的記載，並將該內容編入本說明書中。＜＜Sensitizing pigment＞＞ The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs predetermined active radiation and becomes in an electronically excited state. The sensitizing pigment in an electronically excited state is in contact with thermal hardening accelerators, thermal radical polymerization initiators, photoradical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heat generation. Thereby, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator are chemically changed and decomposed to generate radicals, acids, or bases. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, and the content is incorporated in this specification.

當本發明的感光性樹脂組成物含有增感色素時，增感色素的含量相對於本發明的感光性樹脂組成物的總固體成分係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。增感色素可以單獨使用一種，亦可以同時使用2種以上。When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass relative to the total solid content of the photosensitive resin composition of the present invention, and 0.1 to 15% by mass is More preferably, 0.5-10 mass % is still more preferable. A sensitizing dye may be used alone or in combination of two or more.

＜＜鏈轉移劑＞＞ 本發明的感光性樹脂組成物可以含有鏈轉移劑。鏈轉移劑例如於高分子詞典第三版（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，例如使用於分子內具有SH、PH、SiH及GeH之化合物組。該等向低活性自由基供給氫而產生自由基，或者經氧化之後，藉由去質子而可產生自由基。尤其，能夠較佳地使用硫醇化合物（例如，2-巰基苯并咪唑類、2-巰基苯并噻唑類、2-巰基聚苯并㗁唑類、3-巰基三唑類、5-巰基四唑類等）。＜＜Chain transfer agent＞＞ The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in Polymer Dictionary 3rd Edition (ed. The Society of Polymer Science, Japan, 2005) pp. 683-684. As a chain transfer agent, for example, a compound group having SH, PH, SiH and GeH in the molecule is used. These donate hydrogen to low-activity free radicals to generate free radicals, or after being oxidized, free radicals can be generated by deprotonation. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptopolybenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetra azoles, etc.).

當本發明的感光性樹脂組成物含有鏈轉移劑時，鏈轉移劑的含量相對於本發明的感光性樹脂組成物的總固體成分100質量份係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。鏈轉移劑可以僅為一種，亦可以係2種以上。當鏈轉移劑為2種以上時，其總計係上述範圍為較佳。When the photosensitive 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 relative to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention, preferably 1 to 10 parts by mass. It is more preferable that it is a mass part, and it is still more preferable that it is 1-5 mass parts. 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, it is preferable that the total is within the above-mentioned range.

＜＜界面活性劑＞＞ 從進一步提高塗佈性的觀點考慮，本發明的感光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、矽酮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。 [化學式42]

Figure 02_image083
<<surfactant>> Various surfactants can be added to the photosensitive resin composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. Moreover, the following surfactants are also preferable. [chemical formula 42]
Figure 02_image083

當本發明的感光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感光性樹脂組成物的總固體成分係0.001～2.0質量%為較佳，更佳為0.005～1.0質量%。界面活性劑可以僅為一種，亦可以係2種以上。當界面活性劑為2種以上時，其總計係上述範圍為較佳。When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass relative to the total solid content of the photosensitive resin composition of the present invention. quality%. The surfactant may be only one kind, or two or more kinds. When there are two or more types of surfactants, it is preferable that the total is within the above-mentioned range.

＜＜高級脂肪酸衍生物＞＞ 為了防止因氧引起之聚合抑制，本發明的感光性樹脂組成物中可以添加如二十二酸或二十二酸醯胺那樣的高級脂肪酸衍生物而於塗佈後的乾燥過程中局部存在於組成物的表面。 當本發明的感光性樹脂組成物含有高級脂肪酸衍生物時，高級脂肪酸衍生物的含量相對於本發明的感光性樹脂組成物的總固體成分係0.1～10質量%為較佳。高級脂肪酸衍生物可以僅為一種，亦可以係2種以上。當高級脂肪酸衍生物為2種以上時，其總計係上述範圍為較佳。＜＜Higher fatty acid derivatives＞＞ In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid or behenic acid amide can be added to the photosensitive resin composition of the present invention to partially exist in the drying process after coating. the surface of the composition. When the photosensitive 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 photosensitive resin composition of the present invention. The higher fatty acid derivative may be only one kind, or may be two or more kinds. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the total is within the above-mentioned range.

＜關於其他含有物質的限制＞ 從塗佈面狀的觀點考慮，本發明的感光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。＜Restrictions on other substances contained＞ From the viewpoint of coating surface shape, the water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and still more preferably less than 0.6% by mass.

從絕緣性的觀點考慮，本發明的感光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，可舉出鈉、鉀、鎂、鈣、鐵、鉻、鎳等。當包含複數種金屬時，該等金屬的總計為上述範圍為較佳。 又，作為減少意外包含於本發明的感光性樹脂組成物之金屬雜質之方法，能夠舉出作為構成本發明的感光性樹脂組成物之原料而選擇金屬含量較少的原料，對構成本發明的感光性樹脂組成物之原料進行過濾器過濾，用聚四氟乙烯對裝置內進行內襯而在盡可能抑制了污染之條件下進行蒸餾等方法。From the viewpoint of insulation, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), more preferably less than 1 mass ppm, and less than 0.5 mass ppm. Further better. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably within the above-mentioned range. In addition, as a method for reducing the metal impurities unexpectedly contained in the photosensitive resin composition of the present invention, it is possible to select a raw material with a low metal content as a raw material constituting the photosensitive resin composition of the present invention, which is beneficial to the composition of the present invention. The raw material of the photosensitive resin composition is filtered through a filter, the interior of the device is lined with polytetrafluoroethylene, and distillation is carried out under conditions that suppress contamination as much as possible.

若考慮作為半導體材料的用途，從配線腐蝕性的觀點考慮，本發明的感光性樹脂組成物中，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係小於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總計分別為上述範圍為較佳。Considering the use as a semiconductor material, the content of halogen atoms in the photosensitive resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosion. for further improvement. Among them, those present in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions be in the above-mentioned ranges, respectively.

作為本發明的感光性樹脂組成物的收納容器能夠使用以往公知的收納容器。又，作為收納容器，以抑制雜質混入原材料或組成物中為目的，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層結構之瓶亦為較佳。作為該等容器，例如可舉出日本特開2015-123351號公報中所記載之容器。A conventionally known storage container can be used as a storage container of the photosensitive resin composition of this invention. Also, as a storage container, for the purpose of preventing impurities from mixing into raw materials or compositions, it is also preferable to use a multi-layer bottle whose inner wall is composed of 6 types of 6-layer resins, or a bottle with 6 types of resins formed into a 7-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

＜組成物的製備＞ 本發明的感光性樹脂組成物能夠藉由將上述各成分進行混合而製備。混合方法並無特別限定，能夠藉由以往公知的方法來進行。 又，以去除組成物中的垃圾或微粒等異物為目的，進行使用過濾器之過濾為較佳。過濾器孔徑係1μm以下為較佳，0.5μm以下為更佳，0.1μm以下為進一步較佳。過濾器的材質係聚四氟乙烯、聚乙烯或尼龍為較佳。過濾器可以使用用有機溶劑預先清洗者。過濾器的過濾步驟中，可以並聯或串聯連接複數種過濾器而使用。當使用複數種過濾器時，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多次。當過濾多次時，可以係循環過濾。又，可以於加壓之後進行過濾。當於加壓之後進行過濾時，進行加壓之壓力係0.05MPa以上且0.3MPa以下為較佳。 除了使用過濾器之過濾以外，還可以進行使用了吸附材料之雜質去除處理。還可以組合過濾器過濾和使用了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，可舉出矽膠、沸石等無機系吸附材料、活性碳等有機系吸附材料。 本發明的感光性樹脂組成物中，聚合物前驅物具有磺酸基，因此耐於在高溫中的保管。更適於-60℃～40℃中的保管，進一步較佳的保管溫度係-20℃～10℃。＜Preparation of composition＞ The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and it can be performed by a conventionally known method. In addition, for the purpose of removing foreign substances such as garbage and fine particles in the composition, it is preferable to perform filtration using a filter. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. Filters can be used pre-cleaned with organic solvents. In the filtration step of the filter, a plurality of types of filters can be connected in parallel or in series and used. When multiple types of filters are used, filters with different pore diameters or materials can be used in combination. Also, various materials can be filtered multiple times. When filtering multiple times, it can be circulated and filtered. In addition, filtration may be performed after pressurization. When filtering is performed after pressurization, it is preferable that the pressure for pressurization is 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine filter filtration and impurity removal treatment using an adsorbent. As the adsorbent, known adsorbents can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In the photosensitive resin composition of the present invention, since the polymer precursor has a sulfonic acid group, it is resistant to storage at high temperatures. It is more suitable for storage at -60°C to 40°C, and a further preferable storage temperature is -20°C to 10°C.

＜硬化膜、積層體、半導體元件及該等的製造方法＞ 接著，對硬化膜、積層體、半導體元件及該等的製造方法進行說明。 本發明的硬化膜藉由使本發明的感光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，且能夠設為1μm以上。又，作為上限值，能夠設為100μm以下，且還能夠設為30μm以下。<Cured films, laminates, semiconductor elements, and their manufacturing methods> Next, the cured film, laminated body, semiconductor element, and their manufacturing methods will be described. The cured film of this invention is formed by hardening the photosensitive resin composition of this invention. The film thickness of the cured film of this invention can be 0.5 micrometer or more, for example, and can be 1 micrometer or more. Moreover, as an upper limit, it can be set to 100 micrometers or less, and can also be set to 30 micrometers or less.

亦可以積層2層以上、進一步為3～7層的本發明的硬化膜而設為積層體。具有2層以上的本發明的硬化膜之積層體係於硬化膜之間具有金屬層之態樣為較佳。該等金屬層可較佳地用作再配線層等金屬配線。It is good also as a laminated body by laminating|stacking the cured film of this invention of 2 or more layers, and further 3-7 layers. It is preferable that the laminated system of the cured film of this invention which has 2 or more layers has a metal layer between cured films. These metal layers can be preferably used as metal wirings such as redistribution layers.

作為能夠適用本發明的硬化膜的領域，可舉出半導體元件的絕緣膜、再配線層用層間絕緣膜、應力緩衝膜等。此外，可舉出藉由蝕刻對密封薄膜、基板材料（柔性打印基板的基底薄膜或覆蓋層、層間絕緣膜）或者如上述的構裝用途的絕緣膜進行圖案形成等。關於該等用途，例如能夠參閱Science & technology Co.,Ltd.“聚醯亞胺的高機能化及應用技術”2008年4月、柿本雅明/監修、CMC Technical Library“聚醯亞胺材料的基礎及開發”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 基礎及應用”NTS，2010年8月等。As a field to which the cured film of this invention can be applied, the insulating film of a semiconductor element, the interlayer insulating film for rewiring layers, a stress buffer film, etc. are mentioned. In addition, patterning of sealing films, substrate materials (base films or cover layers of flexible printed circuit boards, interlayer insulating films) or insulating films for structural purposes such as those described above by etching can be mentioned. Regarding these applications, see, for example, Science & technology Co., Ltd. "Higher Functionality and Application Technology of Polyimide", April 2008, Masakimoto Kakimoto/Supervisor, CMC Technical Library "Basics of Polyimide Materials and Development" issued in November 2011, Japan Polyimide Aromatic Polymer Research Society/edited "Latest Polyimide Basics and Applications" NTS, August 2010, etc.

又，本發明中的硬化膜還能夠使用於膠印版面或網版版面等版面的製造、對成形部件的使用、電子、尤其微電子中的保護漆及介電層的製造等中。In addition, the cured film in the present invention can also be used in the production of offset printing plates, screen plates, etc., the use of molded parts, and the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

本發明的硬化膜的製造方法包括使用本發明的感光性樹脂組成物之步驟。具體而言，包括：將本發明的感光性樹脂組成物適用於基板而成為層狀之層形成步驟；及在50～500℃下對成為層狀之感光性樹脂組成物進行加熱之加熱步驟。較佳為可舉出如下硬化膜之製造方法，其還具有：上述層形成步驟之後，對上述層進行曝光之曝光步驟；及對經上述曝光之感光性樹脂組成物層（樹脂層）進行顯影處理之顯影處理步驟。該顯影之後，藉由加熱（較佳為50～500℃下進行加熱）還能夠硬化經曝光之樹脂層。另外，如上述，使用感光性樹脂組成物之情況下，藉由預先曝光來硬化組成物，之後依據需要實施所期望的加工（例如下述的積層），還能夠藉由加熱使其硬化。The manufacturing method of the cured film of this invention includes the process of using the photosensitive resin composition of this invention. Specifically, it includes: a layer forming step of applying the photosensitive resin composition of the present invention to a substrate to form a layer; and a heating step of heating the layered photosensitive resin composition at 50 to 500°C. Preferably, a method for producing a cured film may be mentioned, which further includes: an exposure step of exposing the above-mentioned layer after the above-mentioned layer forming step; and developing the photosensitive resin composition layer (resin layer) subjected to the above-mentioned exposure. The development processing step of processing. After the image development, the exposed resin layer can also be hardened by heating (preferably heating at 50 to 500° C.). Also, as described above, when using a photosensitive resin composition, the composition can be cured by exposure in advance, and then desired processing (such as lamination described below) can be performed as necessary, and can also be cured by heating.

本發明的積層體的製造方法包括本發明的硬化膜的製造方法。本發明的積層體之製造方法中，依照上述硬化膜之製造方法，在形成硬化膜之後，還再次賦予感光性樹脂組成物的層形成步驟及加熱步驟或者感光性之情況下，以上述順序進行層形成步驟、曝光步驟及顯影處理步驟（依據需要進而加熱步驟）為較佳。尤其，依次進行2～5次（亦即，總計為3～6次）的上述各步驟為較佳。藉由如此積層硬化膜，能夠設為積層體。本發明中，尤其在設置有硬化膜之部分之上或硬化膜之間或者其兩者之間設置金屬層為較佳。 以下對該等的詳細內容進行說明。The manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention. In the method for producing a laminated body of the present invention, according to the method for producing a cured film described above, after forming the cured film, the step of forming a layer of the photosensitive resin composition and the step of heating or providing photosensitivity are carried out in the above order. A layer forming step, an exposure step, and a development treatment step (if necessary, a heating step) are preferable. In particular, it is preferable to perform each of the above steps sequentially 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this way, it can be set as a laminated body. In this invention, it is preferable to provide a metal layer especially on the part provided with a cured film, between cured films, or both. The details of these will be described below.

＜＜層形成步驟＞＞ 本發明的較佳的實施形態之製造方法包括將感光性樹脂組成物適用於基板而成為層狀之層形成步驟。 基板的種類能夠依用途而適當設定，但並無特別限制，可舉出矽、氮化矽、多晶矽、氧化矽、非晶矽等半導體製作基板、石英、玻璃、光學膜、陶瓷材料、蒸鍍膜、磁性膜、反射膜、Ni、Cu、Cr、Fe等金屬基板、紙、SOG（Spin On Glass）、TFT（薄膜晶體管）陣列基板、等離子顯示面板（PDP）的電極板等。本發明中，尤其半導體製作基板為較佳，矽基板為更佳。 又，當於樹脂層的表面或金屬層的表面形成感光性樹脂組成物層時，樹脂層或金屬層成為基板。 作為將感光性樹脂組成物適用於基板之方法，塗佈為較佳。 具體而言，作為適用方法，可例示浸塗法、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。從感光性樹脂組成物層的厚度的均勻性的觀點考慮，更佳為旋轉塗佈法、狹縫塗佈法、噴塗法、噴墨法。依方法調整適當的固體成分濃度或塗佈條件，藉此能夠得到所期望的厚度的樹脂層。又，能夠依基板的形狀適當選擇塗佈方法，只要為晶圓等圓形基板，則旋塗法或噴塗法、噴墨法等為較佳，且只要為矩形基板，則狹縫塗佈法或噴塗法、噴墨法等為較佳。當為旋轉塗佈法時，例如能夠以500～2000rpm的轉速適用10秒鐘～1分鐘左右。＜＜Layer formation process＞＞ The manufacturing method of the preferable embodiment of this invention includes the layer formation process which applies a photosensitive resin composition to a board|substrate, and becomes a layer. The type of substrate can be appropriately set according to the application, but it is not particularly limited. Examples include substrates made of semiconductors such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, and vapor-deposited films. , magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, etc., paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrate, electrode plate of plasma display panel (PDP), etc. In the present invention, especially semiconductor substrates are preferred, and silicon substrates are more preferred. Moreover, when forming a photosensitive resin composition layer on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer becomes a board|substrate. Coating is preferable as a method of applying the photosensitive resin composition to a substrate. Specifically, examples of applicable methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, Slit coating method and inkjet method, etc. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting the appropriate solid content concentration or coating conditions according to the method. In addition, the coating method can be appropriately selected according to the shape of the substrate. As long as it is a circular substrate such as a wafer, the spin coating method, spray coating method, inkjet method, etc. are preferred, and as long as it is a rectangular substrate, the slit coating method is suitable. Or a spraying method, an inkjet method, etc. are preferable. In the case of a spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

＜＜乾燥步驟＞＞ 本發明之製造方法亦可以包括在形成感光性樹脂組成物層之後，亦即層形成步驟之後為了去除溶劑而進行乾燥之步驟。較佳的乾燥溫度係50～150℃，70～130℃為更佳，90～110℃為進一步較佳。作為乾燥時間，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 production method of the present invention may also include a drying step for removing the solvent after forming the photosensitive resin composition layer, that is, after the layer forming step. The preferred drying temperature is 50-150°C, more preferably 70-130°C, and more preferably 90-110°C. As drying time, 30 seconds - 20 minutes are illustrated, Preferably it is 1 minute - 10 minutes, More preferably, it is 3 minutes - 7 minutes.

＜＜曝光步驟＞＞ 本發明的製造方法可以包括對上述感光性樹脂組成物層進行曝光之曝光步驟。曝光量於能夠使感光性樹脂組成物硬化之範圍內無特別限定，例如，以波長365nm下的曝光能量換算照射100～10000mJ/cm2 為較佳，照射200～8000mJ/cm2 為更佳。 曝光波長能夠於190～1000nm的範圍內適當設定，240～550nm為較佳。 關於曝光波長，若以與光源的關係描述，則可舉出（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）電子束等。關於本發明的感光性樹脂組成物，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，能夠得到尤其高的曝光靈敏度。<<Exposure step>> The production method of the present invention may include an exposure step of exposing the above-mentioned photosensitive resin composition layer. The exposure amount is not particularly limited within the range capable of curing the photosensitive resin composition. For example, 100-10000 mJ/cm 2 is preferably irradiated in terms of exposure energy at a wavelength of 365 nm, and more preferably 200-8000 mJ/cm 2 . The exposure wavelength can be appropriately set within the range of 190 to 1000 nm, preferably 240 to 550 nm. Regarding the exposure wavelength, if described in relation to the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g Ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), broad (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm) , ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, etc. Regarding the photosensitive resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-rays is preferable. Thereby, particularly high exposure sensitivity can be obtained.

＜＜顯影處理步驟＞＞ 本發明的製造方法可以包括顯影處理步驟，對經曝光之感光性樹脂組成物層進行顯影處理。藉由進行顯影，未曝光之部分（非曝光部）被去除。關於顯影方法，只要能夠形成所期望的圖案，則無特別限定，例如，能夠採用旋覆浸沒、噴霧、浸漬、超聲波等顯影方法。 顯影使用顯影液來進行。關於顯影液，只要可去除未曝光之部分（非曝光部），則能夠使用而無特別限制。顯影液包含有機溶劑為較佳。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。ClogP值能夠通過ChemBioDraw（化學生物圖）輸入結構式而作為計算值來求出。 關於有機溶劑，作為酯類，例如可適當地舉出乙酸乙酯、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）、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，例如可適當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，例如可適當地舉出甲基乙基酮、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，例如可適當地舉出甲苯、二甲苯、大茴香醚、檸檬烯等，以及作為亞碸類，可適當地舉出二甲基亞碸。 本發明中，尤其環戊酮、γ-丁內酯為較佳，環戊酮為更佳。 顯影液的50質量%以上係有機溶劑為較佳，70質量%以上係有機溶劑為更佳，90質量%以上係有機溶劑為進一步較佳。又，顯影液的100質量%可以係有機溶劑。＜＜Development processing steps＞＞ The manufacturing method of the present invention may include a development treatment step, which is to perform development treatment on the exposed photosensitive resin composition layer. By developing, the unexposed part (non-exposed part) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, developing methods such as spin-on immersion, spraying, dipping, and ultrasonic waves can be employed. Image development is performed using a developing solution. There are no particular limitations on the developer as long as it can remove the unexposed portion (non-exposed portion). It is preferable that the developing solution contains an organic solvent. In the present invention, the developer preferably contains an organic solvent with a ClogP value of -1 to 5, and more preferably contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula with ChemBioDraw (chemical biological drawing). Regarding organic solvents, examples of esters include ethyl acetate, n-butyl acetate, amyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyric acid Ethyl ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (example: methyl alkoxyacetate , ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate esters, etc.), 3-alkoxy propionate alkyl esters (eg: 3-alkoxy propionate methyl ester, 3-alkoxy propionate ethyl ester, etc. (eg, 3-methoxy propionate methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (example: 2 - Methyl 2-methoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and 2 - Ethyl alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate ester, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example, Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol mono Methyl 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 as ketone 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. are suitably mentioned, and dimethylargonide is suitably mentioned as aroxines. In the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. It is preferable that 50 mass % or more of a developer is an organic solvent, it is more preferable that 70 mass % or more is an organic solvent, and it is still more preferable that 90 mass % or more is an organic solvent. In addition, 100% by mass of the developer may be an organic solvent.

作為顯影時間，10秒鐘～5分鐘為較佳。顯影時的顯影液的溫度並無特別限定，但是通常能夠在20～40℃下進行。 於使用了顯影液之處理之後，進而可以進行沖洗。沖洗以與顯影液不同之溶劑進行為較佳。例如，能夠使用感光性樹脂組成物中所含有之溶劑進行沖洗。沖洗時間係5秒鐘～1分鐘為較佳。As developing time, 10 seconds - 5 minutes are preferable. Although the temperature of the developing solution at the time of image development is not specifically limited, Usually, it can carry out at 20-40 degreeC. Rinsing may be further performed after the processing using the developing solution. Rinsing is preferably carried out with a solvent different from that of the developer. For example, rinsing can be performed using a solvent contained in the photosensitive resin composition. The flushing time is preferably 5 seconds to 1 minute.

＜＜加熱步驟＞＞ 本發明之製造方法包括在層形成步驟、乾燥步驟或顯影步驟之後進行加熱之步驟為較佳。加熱步驟中，進行聚合物前驅物的環化反應。又，本發明的組成物可以含有除了聚合物前驅物以外的自由基聚合性化合物，但是亦能夠在該步驟中進行除了未反應的聚合物前驅物以外的自由基聚合性化合物的硬化等。作為加熱步驟中的層的加熱溫度（最高加熱溫度），50～500℃為較佳，50～450℃為更佳，140～400℃為進一步較佳、160～350℃為更進一步較佳。 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，能夠確保生產率的同時防止胺的過度揮發，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。 加熱開始時的溫度係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，將感光性樹脂組成物適用於基板上之後，使其乾燥時，為該乾燥後的層的溫度，例如，從比感光性樹脂組成物中所含有之溶劑的沸點-低30～200℃的溫度逐漸升溫為較佳。 加熱時間（最高加熱溫度下的加熱時間）係10～360分鐘為較佳，20～300分鐘為更佳，30～240分鐘為進一步較佳。 尤其形成多層積層體時，從硬化膜的層間的密接性的觀點考慮，於180～320℃的加熱溫度下進行加熱為較佳，於180～260℃下進行加熱為更佳。其理由雖不確定，但認為其原因如下，亦即藉由設為該溫度，層間的聚合物前驅物的乙炔基彼此進行交聯反應。＜＜Heating step＞＞ The production method of the present invention preferably includes a step of heating after the layer forming step, drying step or developing step. In the heating step, the cyclization reaction of the polymer precursor proceeds. Also, the composition of the present invention may contain a radically polymerizable compound other than the polymer precursor, but curing of the radically polymerizable compound other than the unreacted polymer precursor can also be performed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably from 50 to 500°C, more preferably from 50 to 450°C, still more preferably from 140 to 400°C, and still more preferably from 160 to 350°C. The heating is preferably carried out at a rate of temperature increase from the temperature at the start of heating to the maximum heating temperature at a rate of 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min. By setting the rate of temperature increase to 1° C./minute or more, excessive volatilization of amine can be prevented while ensuring productivity, and residual stress of the cured film can be relaxed by setting the rate of temperature increase to 12° C./minute or less. The temperature at the start of heating is preferably from 20 to 150°C, more preferably from 20 to 130°C, and still more preferably from 25 to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the highest heating temperature. For example, when the photosensitive resin composition is applied to the substrate and dried, the temperature of the dried layer is, for example, 30 to 200°C lower than the boiling point of the solvent contained in the photosensitive resin composition. It is better to increase the temperature gradually. The heating time (heating time at the highest heating temperature) is preferably from 10 to 360 minutes, more preferably from 20 to 300 minutes, and still more preferably from 30 to 240 minutes. In particular, when forming a multilayer laminate, it is preferable to heat at a heating temperature of 180 to 320° C., and more preferably to heat at 180 to 260° C., from the viewpoint of the adhesiveness between layers of a cured film. The reason for this is not certain, but it is considered that by setting this temperature, the acetylene groups of the polymer precursor between the layers undergo a crosslinking reaction.

加熱可以分階段進行。作為例子，可以以3℃/分鐘從25℃升溫至180℃，且於180℃下保持60分鐘，以2℃/分鐘從180℃升溫至200℃，且於200℃下保持120分鐘之前處理步驟。作為前處理步驟之加熱溫度係100～200℃為較佳，110～190℃為更佳，120～185℃為進一步較佳。該前處理步驟中，如美國專利9159547號公報中所記載那樣照射紫外線的同時進行處理亦為較佳。藉由該等前處理步驟能夠提高膜的特性。前處理步驟於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。前處理可以是兩階段以上的步驟，例如可以於100～150℃的範圍下進行前處理步驟1，然後於150～200℃的範圍下進行前處理步驟2。 進而，可以於加熱之後進行冷卻，作為該情況下的冷卻速度，1～5℃/分鐘為較佳。Heating can be done in stages. As an example, you can heat up from 25°C to 180°C at 3°C/min and hold at 180°C for 60 minutes, and heat up from 180°C to 200°C at 2°C/min and hold at 200°C for 120 minutes. . The heating temperature in the pretreatment step is preferably 100 to 200°C, more preferably 110 to 190°C, and still more preferably 120 to 185°C. In this pretreatment step, it is also preferable to perform treatment while irradiating ultraviolet rays as described in US Patent No. 9,159,547. The properties of the film can be improved by these pretreatment steps. The pretreatment step can be carried out within a short period of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be a step of two or more stages. For example, the pretreatment step 1 may be performed at a temperature ranging from 100 to 150°C, and then the pretreatment step 2 may be performed at a temperature ranging from 150 to 200°C. Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5° C./min.

關於加熱步驟，從防止聚合物前驅物的分解的方面考慮，藉由使氮、氦、氬等惰性氣體流過等，於低氧濃度的環境下進行為較佳。氧濃度係50ppm（體積比）以下為較佳，20ppm（體積比）以下為更佳。The heating step is preferably performed in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, from the viewpoint of preventing the decomposition of the polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.

＜＜金屬層形成步驟＞＞ 本發明之製造方法包括在顯影處理後的感光性樹脂組成物層的表面形成金屬層之金屬層形成步驟為較佳。 作為金屬層，無特別限定，能夠使用現有的金屬種類，例示銅、鋁、鎳、釩、鈦、鉻、鈷、金及鎢，銅及鋁為更佳，銅為進一步較佳。 金屬層的形成方法無特別限定，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、印刷及組合該等而成之方法等。更具體而言，可舉出組合濺射、光微影及蝕刻而成之圖案化方法、組合光微影與電解電鍍而成之圖案化方法。 作為金屬層的厚度，於最厚的壁厚部係0.1～50μm為較佳，1～10μm為更佳。＜＜Metal layer formation process＞＞ It is preferable that the manufacturing method of the present invention includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment. The metal layer is not particularly limited, and conventional metals can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is still more preferable. The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining them can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating are mentioned. The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

＜＜積層步驟＞＞ 本發明的製造方法還包括積層步驟為較佳。 積層步驟係包括以上述順序在硬化膜（樹脂層）或金屬層的表面再次進行上述層形成步驟及加熱步驟或者在感光性樹脂組成物進行上述層形成步驟、上述曝光步驟及上述顯影處理步驟之一系列的步驟。當然，積層步驟還可以包括上述乾燥步驟或加熱步驟等。 在積層步驟之後進而進行積層步驟之情況下，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而可以進行表面活性化處理步驟。作為表面活化處理，例示電漿處理。 上述積層步驟進行2～5次為較佳，進行3～5次為更佳。 例如，如樹脂層/金屬層/樹脂層/金屬層/樹脂層/金屬層那樣的樹脂層為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。 亦即，本發明中，尤其在設置金屬層之後，進而以上述順序如覆蓋上述金屬層那樣進行上述感光性樹脂組成物的層形成步驟及加熱步驟或者在感光性樹脂組成物進行上述層形成步驟、上述曝光步驟及上述顯影處理步驟（依據需要還進行加熱步驟）為較佳。藉由交替進行積層感光性樹脂組成物層（樹脂）之積層步驟與金屬層形成步驟，能夠交替積層感光性樹脂組成物層（樹脂層）與金屬層。＜＜Stacking steps＞＞ It is preferable that the manufacturing method of the present invention further includes a layering step. The lamination step includes performing the above-mentioned layer-forming step and heating step again on the surface of the cured film (resin layer) or metal layer in the above-mentioned order, or performing the above-mentioned layer-forming step, the above-mentioned exposure step, and the above-mentioned development treatment step on the photosensitive resin composition. series of steps. Of course, the lamination step may also include the above-mentioned drying step or heating step. When the layering step is performed after the layering step, a surface activation treatment step may be further performed after the above-mentioned heating step, after the above-mentioned exposure step, or after the above-mentioned metal layer forming step. As the surface activation treatment, plasma treatment is exemplified. It is better to carry out the above lamination step 2 to 5 times, more preferably 3 to 5 times. For example, the resin layer structure such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably 3 or more and 7 or less layers, and is more preferably 3 or more and 5 or less layers. That is, in the present invention, especially after the metal layer is provided, the layer forming step and the heating step of the photosensitive resin composition are performed in the above order as if covering the metal layer, or the layer forming step is performed on the photosensitive resin composition. , the above-mentioned exposure step and the above-mentioned development treatment step (if necessary, a heating step) are preferred. By alternately performing the lamination step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated.

本發明中亦揭示具有本發明的硬化膜或積層體之半導體元件。作為對將本發明的感光性樹脂組成物使用在再配線層用層間絕緣膜的形成中之半導體元件的具體例，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，並將該等內容編入本說明書中。 [實施例]In this invention, the semiconductor element which has the cured film or laminated body of this invention is also disclosed. As a specific example of a semiconductor element in which the photosensitive resin composition of the present invention is used in the formation of an interlayer insulating film for a rewiring layer, reference can be made to the description in paragraphs 0213 to 0218 of JP-A-2016-027357 and FIG. 1 records and incorporate them into this manual. [Example]

以下，舉出實施例對本發明進行進一步詳細的說明。以下的實施例中所示出之材料、使用量、比例、處理內容、處理步驟等於不脫離本發明的宗旨之範圍內，能夠適當進行變更。因此，本發明的範圍並不限定於以下所示之具體例。只要沒有特別說明，“份”、“%”係質量基準。Hereinafter, the present invention will be described in more detail with reference to examples. The materials, usage amounts, ratios, processing contents, and processing steps shown in the following examples can be appropriately changed within the scope not departing from the gist 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 quality standards.

＜聚合物前驅物組成物（感光性樹脂組成物）的合成＞ （合成例1） ［聚合物前驅物A-1的合成］ 混合21.2g的4,4’-氧代二鄰苯二甲酸二酐、18.2g的2-羥基乙基甲基丙烯酸酯、11.0g的吡啶及50mL的四氫呋喃，在60℃的溫度下攪拌了4小時。接著，將反應混合物冷卻至-10℃，在-10℃下經60分鐘將在40mL的γ-丁內酯溶解了28.1g的二環己基碳化二醯亞胺之溶液滴加到反應混合物，對混合物攪拌了30分鐘。接著，在-10℃下經30分鐘將在100mL的γ-丁內酯溶解了6.9g的1,4-伸苯基二胺之溶液滴加到反應混合物，對混合物攪拌了1小時之後，加入了6.0g的4-胺基苯磺酸、10mL的乙醇及100mL的γ-丁內酯。藉由過濾去除反應混合物中所生成之沉澱物，從而得到了反應液。向所得到之反應液加入6L的水而使聚醯亞胺前驅物沉澱，以500rpm的速度震蕩水-聚醯亞胺前驅物混合物並攪拌了60分鐘。對聚醯亞胺前驅物的固體進行過濾，減壓下在45℃下乾燥了2天。所得到之聚醯亞胺前驅物中，重量平均分子量係19500、數平均分子量係8100，磺酸基的數係總構成單元的合計數的7.54%。＜Synthesis of polymer precursor composition (photosensitive resin composition)＞ (Synthesis Example 1) [Synthesis of polymer precursor A-1] Mix 21.2g of 4,4'-oxodiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 11.0g of pyridine and 50mL of tetrahydrofuran, and stir at 60°C for 4 Hour. Next, the reaction mixture was cooled to -10°C, and a solution of 28.1 g of dicyclohexylcarbodiimide dissolved in 40 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at -10°C. The mixture was stirred for 30 minutes. Next, a solution of 6.9 g of 1,4-phenylenediamine dissolved in 100 mL of γ-butyrolactone was added dropwise to the reaction mixture over 30 minutes at -10°C, and after stirring the mixture for 1 hour, added 6.0 g of 4-aminobenzenesulfonic acid, 10 mL of ethanol and 100 mL of γ-butyrolactone were prepared. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. 6 L of water was added to the obtained reaction solution to precipitate the polyimide precursor, and the water-polyimide precursor mixture was shaken at a speed of 500 rpm and stirred for 60 minutes. The solid of the polyimide precursor was filtered and dried at 45° C. for 2 days under reduced pressure. In the obtained polyimide precursor, the weight average molecular weight was 19500, the number average molecular weight was 8100, and the number of sulfonic acid groups was 7.54% of the total number of the total structural units.

（合成例2） ［聚合物前驅物A-2的合成］ 混合14.9g的均苯四甲酸二酐、18.2g的2-羥基乙基甲基丙烯酸酯、23.9g的吡啶及100mL的二乙二醇二甲醚，在60℃的溫度下攪拌了4小時。接著，將反應混合物冷卻至-10℃，將溫度保持在-10℃的同時經60分鐘添加了17.0g的SOCl2 。用50mL的N-甲基吡咯啶酮進行稀釋之後，在-5℃下經30分鐘將在100mL的N-甲基吡咯啶酮溶解了20.3g的4,4’-二胺基-2,2’-雙（三氟甲基）聯苯及0.2g的2-磺基苯甲酸酐之溶液滴加到反應混合物，對混合物攪拌了1小時之後，加入了乙醇20mL。向所得到之反應液加入6L的水而使聚醯亞胺前驅物沉澱，對固體進行過濾並溶解於四氫呋喃400mL。向所得到之溶液加入6L的水而使聚醯亞胺前驅物沉澱，以500rpm的速度震蕩水-聚醯亞胺前驅物混合物並攪拌了60分鐘。再次過濾聚醯亞胺前驅物的固體並在減壓下，在45℃下乾燥了2天。所得到之聚醯亞胺前驅物中，重量平均分子量係22400、數平均分子量係8600，磺酸基的數係總構成單元的合計數的0.15%。(Synthesis Example 2) [Synthesis of Polymer Precursor A-2] Mix 14.9 g of pyromellitic dianhydride, 18.2 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 100 mL of diethylene glycol Alcohol dimethyl ether was stirred at a temperature of 60°C for 4 hours. Next, the reaction mixture was cooled to -10°C, and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at -10°C. After dilution with 50 mL of N-methylpyrrolidone, 20.3 g of 4,4'-diamino-2,2 A solution of '-bis(trifluoromethyl)biphenyl and 0.2 g of 2-sulfobenzoic anhydride was added dropwise to the reaction mixture, and after stirring the mixture for 1 hour, 20 mL of ethanol was added. 6 L of water was added to the obtained reaction liquid to precipitate a polyimide precursor, and the solid was filtered and dissolved in 400 mL of tetrahydrofuran. 6 L of water was added to the obtained solution to precipitate the polyimide precursor, and the water-polyimide precursor mixture was shaken at a speed of 500 rpm and stirred for 60 minutes. The solid of the polyimide precursor was filtered again and dried at 45° C. for 2 days under reduced pressure. In the obtained polyimide precursor, the weight average molecular weight was 22400, the number average molecular weight was 8600, and the number of sulfonic acid groups was 0.15% of the total number of the total structural units.

（合成例3） ［聚合物前驅物A-3的合成］ 混合21.2g的4,4’-氧代二鄰苯二甲酸二酐、18.2g的2-羥基乙基甲基丙烯酸酯、23.9g的吡啶及100mL的二乙二醇二甲醚，在60℃的溫度下攪拌了4小時。接著，將反應混合物冷卻至-10℃，將溫度保持在-10℃的同時經60分鐘添加了17.0g的SOCl2 。用50mL的N-甲基吡咯啶酮進行稀釋之後，在-5℃下經30分鐘將在100mL的N-甲基吡咯啶酮溶解了12.7g的4,4’-二胺基二苯基醚之溶液滴加到反應混合物，對混合物攪拌了1小時之後，加入了0.6g的2-胺基苯磺酸及乙醇20mL。向所得到之反應液加入6L的水而使聚醯亞胺前驅物沉澱，對固體進行過濾並溶解於四氫呋喃400mL。向所得到之溶液加入6L的水而使聚醯亞胺前驅物沉澱，以500rpm的速度震蕩水-聚醯亞胺前驅物混合物並攪拌了60分鐘。再次過濾聚醯亞胺前驅物的固體並在減壓下，在45℃下乾燥了2天。所得到之聚醯亞胺前驅物中，重量平均分子量係26400、數平均分子量係9600，磺酸基的數係總構成單元的合計數的1.05%。(Synthesis Example 3) [Synthesis of Polymer Precursor A-3] 21.2 g of 4,4'-oxodiphthalic dianhydride, 18.2 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 100 mL of diethylene glycol dimethyl ether were stirred at a temperature of 60° C. for 4 hours. Next, the reaction mixture was cooled to -10°C, and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at -10°C. After dilution with 50 mL of N-methylpyrrolidone, 12.7 g of 4,4'-diaminodiphenyl ether was dissolved in 100 mL of N-methylpyrrolidone at -5°C for 30 minutes The solution was added dropwise to the reaction mixture, and after stirring the mixture for 1 hour, 0.6 g of 2-aminobenzenesulfonic acid and 20 mL of ethanol were added. 6 L of water was added to the obtained reaction liquid to precipitate a polyimide precursor, and the solid was filtered and dissolved in 400 mL of tetrahydrofuran. 6 L of water was added to the obtained solution to precipitate the polyimide precursor, and the water-polyimide precursor mixture was shaken at a speed of 500 rpm and stirred for 60 minutes. The solid of the polyimide precursor was filtered again and dried at 45° C. for 2 days under reduced pressure. In the obtained polyimide precursor, the weight average molecular weight was 26400, the number average molecular weight was 9600, and the number of sulfonic acid groups was 1.05% of the total number of the total structural units.

（合成例4） ［聚合物前驅物A-4的合成］ 混合21.2g的4,4’-氧代二鄰苯二甲酸二酐、18.2g的2-羥基乙基甲基丙烯酸酯、11.0g的吡啶及50mL的四氫呋喃，在60℃的溫度下攪拌了4小時。接著，將反應混合物冷卻至-10℃，在-10℃下經60分鐘將在40mL的γ-丁內酯溶解了17.2g的二異丙基碳化二醯亞胺之溶液滴加到反應混合物，對混合物攪拌了30分鐘。接著，在-10℃下經30分鐘將在100mL的γ-丁內酯溶解了12.7g的4,4’-二胺基二苯基醚及1.2g的2-磺基苯甲酸酐之溶液滴加到反應混合物，對混合物攪拌了1小時之後，加入了10mL的乙醇及100mL的γ-丁內酯。藉由過濾去除反應混合物中所生成之沉澱物，從而得到了反應液。向所得到之反應液加入6L的水而使聚醯亞胺前驅物沉澱，以500rpm的速度震蕩水-聚醯亞胺前驅物混合物並攪拌了60分鐘。對聚醯亞胺前驅物的固體進行過濾，減壓下在45℃下乾燥了2天。所得到之聚醯亞胺前驅物中，重量平均分子量係20900、數平均分子量係8200，磺酸基的數係總構成單元的合計數的0.44%。(Synthesis Example 4) [Synthesis of polymer precursor A-4] Mix 21.2g of 4,4'-oxodiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 11.0g of pyridine and 50mL of tetrahydrofuran, and stir at 60°C for 4 Hour. Next, the reaction mixture was cooled to -10°C, and a solution in which 17.2 g of diisopropylcarbodiimide was dissolved in 40 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at -10°C, The mixture was stirred for 30 minutes. Next, a solution of 12.7 g of 4,4'-diaminodiphenyl ether and 1.2 g of 2-sulfobenzoic anhydride dissolved in 100 mL of γ-butyrolactone was dropped over a period of 30 minutes at -10°C. The reaction mixture was added, and after the mixture was stirred for 1 hour, 10 mL of ethanol and 100 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. 6 L of water was added to the obtained reaction solution to precipitate the polyimide precursor, and the water-polyimide precursor mixture was shaken at a speed of 500 rpm and stirred for 60 minutes. The solid of the polyimide precursor was filtered and dried at 45° C. for 2 days under reduced pressure. In the obtained polyimide precursor, the weight average molecular weight was 20900, the number average molecular weight was 8200, and the number of sulfonic acid groups was 0.44% of the total number of the total structural units.

（合成例5） ［聚合物前驅物A-5的合成］ 混合21.2g的4,4’-氧代二鄰苯二甲酸二酐、18.2g的2-羥基乙基甲基丙烯酸酯、23.9g的吡啶及100mL的二乙二醇二甲醚，在60℃的溫度下攪拌了4小時。接著，將反應混合物冷卻至-10℃，將溫度保持在-10℃的同時經60分鐘添加了17.0g的SOCl2 。用50mL的N-甲基吡咯啶酮進行稀釋之後，在-5℃下經30分鐘將在100mL的N-甲基吡咯啶酮溶解了20.29g的2,2’-雙（三氟甲基）聯苯胺之溶液滴加到反應混合物，對混合物攪拌了1小時之後，加入了1.0g的2-胺基乙烷磺酸及乙醇20mL。向所得到之反應液加入6L的水而使聚醯亞胺前驅物沉澱，對固體進行過濾並溶解於四氫呋喃400mL。向所得到之溶液加入6L的水而使聚醯亞胺前驅物沉澱，以500rpm的速度震蕩水-聚醯亞胺前驅物混合物並攪拌了60分鐘。再次過濾聚醯亞胺前驅物的固體並在減壓下，在45℃下乾燥了2天。所得到之聚醯亞胺前驅物中，重量平均分子量係27100、數平均分子量係10100，磺酸基的數係總構成單元的合計數的3.21%。(Synthesis Example 5) [Synthesis of Polymer Precursor A-5] 21.2 g of 4,4'-oxodiphthalic dianhydride, 18.2 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 100 mL of diethylene glycol dimethyl ether were stirred at a temperature of 60° C. for 4 hours. Next, the reaction mixture was cooled to -10°C, and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at -10°C. After dilution with 50 mL of N-methylpyrrolidone, 20.29 g of 2,2'-bis(trifluoromethyl) was dissolved in 100 mL of N-methylpyrrolidone at -5°C for 30 minutes The benzidine solution was added dropwise to the reaction mixture, and after stirring the mixture for 1 hour, 1.0 g of 2-aminoethanesulfonic acid and 20 mL of ethanol were added. 6 L of water was added to the obtained reaction liquid to precipitate a polyimide precursor, and the solid was filtered and dissolved in 400 mL of tetrahydrofuran. 6 L of water was added to the obtained solution to precipitate the polyimide precursor, and the water-polyimide precursor mixture was shaken at a speed of 500 rpm and stirred for 60 minutes. The solid of the polyimide precursor was filtered again and dried at 45° C. for 2 days under reduced pressure. In the obtained polyimide precursor, the weight average molecular weight was 27100, the number average molecular weight was 10100, and the number of sulfonic acid groups was 3.21% of the total number of the total structural units.

（合成例6） ［聚合物前驅物A-6的合成］ 混合21.2g的4,4’-氧代二鄰苯二甲酸二酐、18.2g的2-羥基乙基甲基丙烯酸酯、23.9g的吡啶及100mL的二乙二醇二甲醚，在60℃的溫度下攪拌了4小時。接著，將反應混合物冷卻至-10℃，將溫度保持在-10℃的同時經60分鐘添加了17.0g的SOCl2 。用50mL的N-甲基吡咯啶酮進行稀釋之後，在-5℃下經30分鐘將在100mL的N-甲基吡咯啶酮溶解了20.29g的2,2’-雙（三氟甲基）聯苯胺之溶液滴加到反應混合物，對混合物攪拌了1小時之後，加入了0.1g的2-胺基乙烷磺酸及乙醇20mL。向所得到之反應液加入6L的水而使聚醯亞胺前驅物沉澱，對固體進行過濾並溶解於四氫呋喃400mL。向所得到之溶液加入6L的水而使聚醯亞胺前驅物沉澱，以500rpm的速度震蕩水-聚醯亞胺前驅物混合物並攪拌了60分鐘。再次過濾聚醯亞胺前驅物的固體並在減壓下，在45℃下乾燥了2天。所得到之聚醯亞胺前驅物中，重量平均分子量係27500、數平均分子量係9900，磺酸基的數係總構成單元的合計數的0.07%。(Synthesis Example 6) [Synthesis of Polymer Precursor A-6] 21.2 g of 4,4'-oxodiphthalic dianhydride, 18.2 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 100 mL of diethylene glycol dimethyl ether were stirred at a temperature of 60° C. for 4 hours. Next, the reaction mixture was cooled to -10°C, and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at -10°C. After dilution with 50 mL of N-methylpyrrolidone, 20.29 g of 2,2'-bis(trifluoromethyl) was dissolved in 100 mL of N-methylpyrrolidone at -5°C for 30 minutes A solution of benzidine was added dropwise to the reaction mixture, and after stirring the mixture for 1 hour, 0.1 g of 2-aminoethanesulfonic acid and 20 mL of ethanol were added. 6 L of water was added to the obtained reaction liquid to precipitate a polyimide precursor, and the solid was filtered and dissolved in 400 mL of tetrahydrofuran. 6 L of water was added to the obtained solution to precipitate the polyimide precursor, and the water-polyimide precursor mixture was shaken at a speed of 500 rpm and stirred for 60 minutes. The solid of the polyimide precursor was filtered again and dried at 45° C. for 2 days under reduced pressure. In the obtained polyimide precursor, the weight average molecular weight was 27500, the number average molecular weight was 9900, and the number of sulfonic acid groups was 0.07% of the total number of the total structural units.

（合成例7） ［聚合物前驅物A-7的合成］ 將28.0g的2,2’-雙（3-胺基-4-羥基苯基）六氟丙烷在200mL的N-甲基吡咯啶酮中進行了攪拌並溶解。接著，將溫度保持在0～5℃的同時經30分鐘滴加25.0g的4,4’-氧基二苯甲醯氯之後，加入3.0g的3-羥基丙烷磺酸（約80質量%水溶液）持續攪拌了60分鐘。向所得到之反應液加入6L水而使聚苯并㗁唑前驅物沉澱，對固體進行過濾並在減壓下，在45℃下乾燥了2天。所得到之聚苯并㗁唑前驅物中，重量平均分子量係21800、數平均分子量係8300，磺酸基的數係總構成單元的合計數的4.20%。(Synthesis Example 7) [Synthesis of polymer precursor A-7] 28.0 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved in 200 mL of N-methylpyrrolidone. Next, after adding 25.0 g of 4,4'-oxydibenzoyl chloride dropwise over 30 minutes while maintaining the temperature at 0 to 5°C, 3.0 g of 3-hydroxypropanesulfonic acid (about 80% by mass aqueous solution ) was stirred continuously for 60 minutes. 6 L of water was added to the obtained reaction liquid to precipitate a polybenzoxazole precursor, and the solid was filtered and dried at 45° C. for 2 days under reduced pressure. In the obtained polybenzoxazole precursor, the weight average molecular weight was 21800, the number average molecular weight was 8300, and the number of sulfonic acid groups was 4.20% of the total number of the total constituent units.

（合成例8） ［聚合物前驅物A-8的合成］ 將28.0g的2,2’-雙（3-胺基-4-羥基苯基）六氟丙烷在200mL的N-甲基吡咯啶酮中進行了攪拌並溶解。接著，將溫度保持在0～5℃的同時經30分鐘滴加25.0g的4,4’-氧基二苯甲醯氯之後，加入10.0g的2-磺基苯甲酸酐持續攪拌了60分鐘。向所得到之反應液加入6L水而使聚苯并㗁唑前驅物沉澱，對固體進行過濾並在減壓下，在45℃下乾燥了2天。所得到之聚苯并㗁唑前驅物中，重量平均分子量係18800、數平均分子量係7300，磺酸基的數係總構成單元的合計數的12.48%。(Synthesis Example 8) [Synthesis of polymer precursor A-8] 28.0 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved in 200 mL of N-methylpyrrolidone. Next, 25.0 g of 4,4'-oxydibenzoyl chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5°C, and then 10.0 g of 2-sulfobenzoic anhydride was added and stirring was continued for 60 minutes. . 6 L of water was added to the obtained reaction liquid to precipitate a polybenzoxazole precursor, and the solid was filtered and dried at 45° C. for 2 days under reduced pressure. In the obtained polybenzoxazole precursor, the weight average molecular weight was 18800, the number average molecular weight was 7300, and the number of sulfonic acid groups was 12.48% of the total number of the total constituent units.

（合成例9） ［聚合物前驅物A-9的合成］ 混合21.2g的4,4’-氧代二鄰苯二甲酸二酐、18.2g的2-羥基乙基甲基丙烯酸酯、10.0g的4-胺基苯磺酸、23.9g的吡啶及100mL的二乙二醇二甲醚，在60℃的溫度下攪拌了4小時。接著，將反應混合物冷卻至-10℃，將溫度保持在-10℃的同時經60分鐘添加了17.0g的SOCl2 。用50mL的N-甲基吡咯啶酮進行稀釋之後，在-5℃下經30分鐘將在100mL的N-甲基吡咯啶酮溶解了20.29g的2,2’-雙（三氟甲基）聯苯胺之溶液滴加到反應混合物，對混合物攪拌了1小時之後，加入了乙醇20mL。向所得到之反應液加入6L的水而使聚醯亞胺前驅物沉澱，對固體進行過濾並溶解於四氫呋喃400mL。向所得到之溶液加入6L的水而使聚醯亞胺前驅物沉澱，以500rpm的速度震蕩水-聚醯亞胺前驅物混合物並攪拌了60分鐘。再次過濾聚醯亞胺前驅物的固體並在減壓下，在45℃下乾燥了2天。該聚醯亞胺前驅物中，重量平均分子量係24300、數平均分子量係9200，磺酸基的數係總構成單元的合計數的17.20%。(Synthesis Example 9) [Synthesis of Polymer Precursor A-9] 21.2 g of 4,4'-oxodiphthalic dianhydride, 18.2 g of 2-hydroxyethyl methacrylate, 10.0 g of 4-aminobenzenesulfonic acid, 23.9 g of pyridine, and 100 mL of diethylene glycol dimethyl ether were stirred at a temperature of 60° C. for 4 hours. Next, the reaction mixture was cooled to -10°C, and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at -10°C. After dilution with 50 mL of N-methylpyrrolidone, 20.29 g of 2,2'-bis(trifluoromethyl) was dissolved in 100 mL of N-methylpyrrolidone at -5°C for 30 minutes The benzidine solution was added dropwise to the reaction mixture, and after the mixture was stirred for 1 hour, 20 mL of ethanol was added thereto. 6 L of water was added to the obtained reaction liquid to precipitate a polyimide precursor, and the solid was filtered and dissolved in 400 mL of tetrahydrofuran. 6 L of water was added to the obtained solution to precipitate the polyimide precursor, and the water-polyimide precursor mixture was shaken at a speed of 500 rpm and stirred for 60 minutes. The solid of the polyimide precursor was filtered again and dried at 45° C. for 2 days under reduced pressure. In this polyimide precursor, the weight average molecular weight is 24300, the number average molecular weight is 9200, and the number of sulfonic acid groups is 17.20% of the total number of the total structural units.

（合成例10） ［聚合物前驅物A-10的合成］ 混合21.2g的4,4’-氧代二鄰苯二甲酸二酐、18.2g的2-羥基乙基甲基丙烯酸酯、5.0g的4-胺基苯磺酸、23.9g的吡啶及100mL的二乙二醇二甲醚，在60℃的溫度下攪拌了4小時。接著，將反應混合物冷卻至-10℃，將溫度保持在-10℃的同時經60分鐘添加了17.0g的SOCl2 。用50mL的N-甲基吡咯啶酮進行稀釋之後，在-5℃下經30分鐘將在100mL的N-甲基吡咯啶酮溶解了20.29g的2,2’-雙（三氟甲基）聯苯胺之溶液滴加到反應混合物，對混合物攪拌了1小時之後，加入了乙醇20mL。向所得到之反應液加入6L的水而使聚醯亞胺前驅物沉澱，對固體進行過濾並溶解於四氫呋喃400mL。向所得到之溶液加入6L的水而使聚醯亞胺前驅物沉澱，以500rpm的速度震蕩水-聚醯亞胺前驅物混合物並攪拌了60分鐘。再次過濾聚醯亞胺前驅物的固體並在減壓下，在45℃下乾燥了2天。該聚醯亞胺前驅物中，重量平均分子量係22700、數平均分子量係9400，磺酸基的數係總構成單元的合計數的3.21%。(Synthesis Example 10) [Synthesis of Polymer Precursor A-10] 21.2 g of 4,4'-oxodiphthalic dianhydride, 18.2 g of 2-hydroxyethyl methacrylate, 5.0 g of 4-aminobenzenesulfonic acid, 23.9 g of pyridine, and 100 mL of diethylene glycol dimethyl ether were stirred at a temperature of 60° C. for 4 hours. Next, the reaction mixture was cooled to -10°C, and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at -10°C. After dilution with 50 mL of N-methylpyrrolidone, 20.29 g of 2,2'-bis(trifluoromethyl) was dissolved in 100 mL of N-methylpyrrolidone at -5°C for 30 minutes The benzidine solution was added dropwise to the reaction mixture, and after the mixture was stirred for 1 hour, 20 mL of ethanol was added thereto. 6 L of water was added to the obtained reaction liquid to precipitate a polyimide precursor, and the solid was filtered and dissolved in 400 mL of tetrahydrofuran. 6 L of water was added to the obtained solution to precipitate the polyimide precursor, and the water-polyimide precursor mixture was shaken at a speed of 500 rpm and stirred for 60 minutes. The solid of the polyimide precursor was filtered again and dried at 45° C. for 2 days under reduced pressure. In this polyimide precursor, the weight average molecular weight is 22,700, the number average molecular weight is 9,400, and the number of sulfonic acid groups is 3.21% of the total number of the total structural units.

（合成例11） ［聚合物前驅物A-11的合成］ 混合21.2g的4,4’-氧代二鄰苯二甲酸二酐、18.2g的2-羥基乙基甲基丙烯酸酯、3.0g的4-胺基苯磺酸、11.0g的吡啶及50mL的四氫呋喃，在60℃的溫度下攪拌了4小時。接著，將反應混合物冷卻至-10℃，在-10℃下經60分鐘將在40mL的γ-丁內酯溶解了17.2g的二異丙基碳化二醯亞胺之溶液滴加到反應混合物，對混合物攪拌了30分鐘。接著，在-10℃下經30分鐘將在100mL的γ-丁內酯溶解了12.7g的4,4’-二胺基二苯基醚之溶液滴加到反應混合物，對混合物攪拌了1小時之後，加入了10mL的乙醇及100mL的γ-丁內酯。藉由過濾去除反應混合物中所生成之沉澱物，從而得到了反應液。向所得到之反應液加入6L的水而使聚醯亞胺前驅物沉澱，以500rpm的速度震蕩水-聚醯亞胺前驅物混合物並攪拌了60分鐘。對聚醯亞胺前驅物的固體進行過濾，減壓下在45℃下乾燥了2天。該聚醯亞胺前驅物中，重量平均分子量係25100、數平均分子量係9800，磺酸基的數係總構成單元的合計數的4.32%。(Synthesis Example 11) [Synthesis of polymer precursor A-11] Mix 21.2g of 4,4'-oxodiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 3.0g of 4-aminobenzenesulfonic acid, 11.0g of pyridine and 50mL of THF was stirred at 60°C for 4 hours. Next, the reaction mixture was cooled to -10°C, and a solution in which 17.2 g of diisopropylcarbodiimide was dissolved in 40 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at -10°C, The mixture was stirred for 30 minutes. Next, a solution obtained by dissolving 12.7 g of 4,4'-diaminodiphenyl ether in 100 mL of γ-butyrolactone was added dropwise to the reaction mixture over 30 minutes at -10°C, and the mixture was stirred for 1 hour. Thereafter, 10 mL of ethanol and 100 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. 6 L of water was added to the obtained reaction solution to precipitate the polyimide precursor, and the water-polyimide precursor mixture was shaken at a speed of 500 rpm and stirred for 60 minutes. The solid of the polyimide precursor was filtered and dried at 45° C. for 2 days under reduced pressure. In this polyimide precursor, the weight average molecular weight is 25100, the number average molecular weight is 9800, and the number of sulfonic acid groups is 4.32% of the total number of the total structural units.

（合成例12） ［聚合物前驅物A-12的合成］ 混合21.2g的4,4’-氧代二鄰苯二甲酸二酐、18.2g的2-羥基乙基甲基丙烯酸酯、2.0g的3-羥基丙烷磺酸（約80質量%水溶液）、11.0g的吡啶及50mL的四氫呋喃，在60℃的溫度下攪拌了4小時。接著，將反應混合物冷卻至-10℃，在-10℃下經60分鐘將在40mL的γ-丁內酯溶解了28.1g的二環己基碳化二醯亞胺之溶液滴加到反應混合物，對混合物攪拌了30分鐘。接著，在-10℃下經30分鐘將在100mL的γ-丁內酯溶解了12.7g的4,4’-二胺基二苯基醚之溶液滴加到反應混合物，對混合物攪拌了1小時之後，加入了10mL的乙醇及100mL的γ-丁內酯。藉由過濾去除反應混合物中所生成之沉澱物，從而得到了反應液。向所得到之反應液加入6L的水而使聚醯亞胺前驅物沉澱，以500rpm的速度震蕩水-聚醯亞胺前驅物混合物並攪拌了60分鐘。對聚醯亞胺前驅物的固體進行過濾，減壓下在45℃下乾燥了2天。該聚醯亞胺前驅物中，重量平均分子量係18100、數平均分子量係7100，磺酸基的數係總構成單元的合計數的2.20%。(Synthesis Example 12) [Synthesis of polymer precursor A-12] Mix 21.2 g of 4,4'-oxodiphthalic dianhydride, 18.2 g of 2-hydroxyethyl methacrylate, 2.0 g of 3-hydroxypropanesulfonic acid (about 80 mass % aqueous solution), 11.0 g of pyridine and 50 mL of tetrahydrofuran were stirred at a temperature of 60° C. for 4 hours. Next, the reaction mixture was cooled to -10°C, and a solution of 28.1 g of dicyclohexylcarbodiimide dissolved in 40 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at -10°C. The mixture was stirred for 30 minutes. Next, a solution obtained by dissolving 12.7 g of 4,4'-diaminodiphenyl ether in 100 mL of γ-butyrolactone was added dropwise to the reaction mixture over 30 minutes at -10°C, and the mixture was stirred for 1 hour. Thereafter, 10 mL of ethanol and 100 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. 6 L of water was added to the obtained reaction solution to precipitate the polyimide precursor, and the water-polyimide precursor mixture was shaken at a speed of 500 rpm and stirred for 60 minutes. The solid of the polyimide precursor was filtered and dried at 45° C. for 2 days under reduced pressure. In this polyimide precursor, the weight average molecular weight is 18100, the number average molecular weight is 7100, and the number of sulfonic acid groups is 2.20% of the total number of the total structural units.

（合成例13） ［聚合物前驅物A-13的合成］ 混合21.2g的4,4’-氧代二鄰苯二甲酸二酐、18.2g的2-羥基乙基甲基丙烯酸酯、0.2g的2-胺基乙烷磺酸、11.0g的吡啶及50mL的四氫呋喃，在60℃的溫度下攪拌了4小時。接著，將反應混合物冷卻至-10℃，在-10℃下經60分鐘將在40mL的γ-丁內酯溶解了28.1g的二環己基碳化二醯亞胺之溶液滴加到反應混合物，對混合物攪拌了30分鐘。接著，在-10℃下經30分鐘將在100mL的γ-丁內酯溶解了12.7g的4,4’-二胺基二苯基醚之溶液滴加到反應混合物，對混合物攪拌了1小時之後，加入了10mL的乙醇及100mL的γ-丁內酯。藉由過濾去除反應混合物中所生成之沉澱物，從而得到了反應液。向所得到之反應液加入6L的水而使聚醯亞胺前驅物沉澱，以500rpm的速度震蕩水-聚醯亞胺前驅物混合物並攪拌了60分鐘。對聚醯亞胺前驅物的固體進行過濾，減壓下在45℃下乾燥了2天。該聚醯亞胺前驅物中，重量平均分子量係22400、數平均分子量係8900，磺酸基的數係總構成單元的合計數的0.04%。(Synthesis Example 13) [Synthesis of polymer precursor A-13] Mix 21.2g of 4,4'-oxodiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 0.2g of 2-aminoethanesulfonic acid, 11.0g of pyridine and 50mL of THF, stirred at a temperature of 60 °C for 4 hours. Next, the reaction mixture was cooled to -10°C, and a solution of 28.1 g of dicyclohexylcarbodiimide dissolved in 40 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at -10°C. The mixture was stirred for 30 minutes. Next, a solution obtained by dissolving 12.7 g of 4,4'-diaminodiphenyl ether in 100 mL of γ-butyrolactone was added dropwise to the reaction mixture over 30 minutes at -10°C, and the mixture was stirred for 1 hour. Thereafter, 10 mL of ethanol and 100 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. 6 L of water was added to the obtained reaction solution to precipitate the polyimide precursor, and the water-polyimide precursor mixture was shaken at a speed of 500 rpm and stirred for 60 minutes. The solid of the polyimide precursor was filtered and dried at 45° C. for 2 days under reduced pressure. In this polyimide precursor, the weight average molecular weight is 22400, the number average molecular weight is 8900, and the number of sulfonic acid groups is 0.04% of the total number of the total structural units.

（合成例14） ［聚合物前驅物A-14的合成］ 將28.0g的2,2’-雙（3-胺基-4-羥基苯基）六氟丙烷在200mL的N-甲基吡咯啶酮中進行了攪拌並溶解。接著，將溫度保持在0～5℃的同時經30分鐘滴加25.0g的4,4’-氧基二苯甲醯氯之後，加入5.0g的2-磺基乙酸及8.0g的二環己基碳化二醯亞胺並持續攪拌了60分鐘。藉由過濾去除反應混合物中所生成之沉澱物，從而得到了反應液。向所得到之反應液加入6L水而使聚苯并㗁唑前驅物沉澱，對固體進行過濾並在減壓下，在45℃下乾燥了2天。該聚苯并㗁唑前驅物中，重量平均分子量係22800、數平均分子量係8900，磺酸基的數係總構成單元的合計數的6.21%。(Synthesis Example 14) [Synthesis of polymer precursor A-14] 28.0 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved in 200 mL of N-methylpyrrolidone. Next, 25.0 g of 4,4'-oxydibenzoyl chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5°C, and then 5.0 g of 2-sulfoacetic acid and 8.0 g of dicyclohexyl carbodiimide and continued stirring for 60 minutes. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. 6 L of water was added to the obtained reaction liquid to precipitate a polybenzoxazole precursor, and the solid was filtered and dried at 45° C. for 2 days under reduced pressure. In this polybenzoxazole precursor, the weight average molecular weight is 22800, the number average molecular weight is 8900, and the number of sulfonic acid groups is 6.21% of the total number of the total constituent units.

（合成例15） ［聚合物前驅物A-15的合成］ 混合21.2g的4,4’-氧代二鄰苯二甲酸二酐、18.2g的2-羥基乙基甲基丙烯酸酯、11.0g的吡啶及50mL的四氫呋喃，在60℃的溫度下攪拌了4小時。接著，將反應混合物冷卻至-10℃，在-10℃下經60分鐘將在40mL的γ-丁內酯溶解了28.1g的二環己基碳化二醯亞胺之溶液滴加到反應混合物，對混合物攪拌了30分鐘。接著，在-10℃下經30分鐘將在100mL的γ-丁內酯溶解了6.9g的1,4-伸苯基二胺之溶液滴加到反應混合物，對混合物攪拌了1小時之後，加入了10mL的乙醇及100mL的γ-丁內酯。藉由過濾去除反應混合物中所生成之沉澱物，從而得到了反應液。向所得到之反應液加入6L的水而使聚醯亞胺前驅物沉澱，以500rpm的速度震蕩水-聚醯亞胺前驅物混合物並攪拌了60分鐘。對聚醯亞胺前驅物的固體進行過濾，減壓下在45℃下乾燥了2天。該聚醯亞胺前驅物中，重量平均分子量係22800、數平均分子量係9100，不存在磺酸基。(Synthesis Example 15) [Synthesis of polymer precursor A-15] Mix 21.2g of 4,4'-oxodiphthalic dianhydride, 18.2g of 2-hydroxyethyl methacrylate, 11.0g of pyridine and 50mL of tetrahydrofuran, and stir at 60°C for 4 Hour. Next, the reaction mixture was cooled to -10°C, and a solution of 28.1 g of dicyclohexylcarbodiimide dissolved in 40 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at -10°C. The mixture was stirred for 30 minutes. Next, a solution of 6.9 g of 1,4-phenylenediamine dissolved in 100 mL of γ-butyrolactone was added dropwise to the reaction mixture over 30 minutes at -10°C, and after stirring the mixture for 1 hour, added 10mL of ethanol and 100mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. 6 L of water was added to the obtained reaction solution to precipitate the polyimide precursor, and the water-polyimide precursor mixture was shaken at a speed of 500 rpm and stirred for 60 minutes. The solid of the polyimide precursor was filtered and dried at 45° C. for 2 days under reduced pressure. In this polyimide precursor, the weight average molecular weight is 22800, the number average molecular weight is 9100, and there is no sulfonic acid group.

（合成例16） ［聚合物前驅物A-16的合成］ 將28.0g的2,2’-雙（3-胺基-4-羥基苯基）六氟丙烷在200mL的N-甲基吡咯啶酮中進行了攪拌並溶解。接著，將溫度保持在0～5℃的同時經30分鐘滴加25.0g的4,4’-氧二苯甲醯氯之後，持續攪拌了60分鐘。藉由過濾去除反應混合物中所生成之沉澱物，從而得到了反應液。向所得到之反應液加入6L水而使聚苯并㗁唑前驅物沉澱，對固體進行過濾並在減壓下，在45℃下乾燥了2天。該聚苯并㗁唑前驅物中，重量平均分子量係21400、數平均分子量係8500，不存在磺酸基。(Synthesis Example 16) [Synthesis of polymer precursor A-16] 28.0 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was stirred and dissolved in 200 mL of N-methylpyrrolidone. Next, 25.0 g of 4,4'-oxydibenzoyl chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5°C, and stirring was continued for 60 minutes. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid. 6 L of water was added to the obtained reaction liquid to precipitate a polybenzoxazole precursor, and the solid was filtered and dried at 45° C. for 2 days under reduced pressure. In this polybenzoxazole precursor, the weight average molecular weight is 21400, the number average molecular weight is 8500, and there is no sulfonic acid group.

（合成例17） ［聚合物前驅物A-17的合成］ 混合14.9g（68.3mmol）的均苯四甲酸二酐、18.0g的2-羥基乙基甲基丙烯酸酯、23.9g的吡啶、0.10g的水及250mL的二乙二醇二甲醚，在60℃的溫度下攪拌4小時，從而製造了均苯四甲酸及2-羥基乙基甲基丙烯酸酯的二酯。測量了該所得到之反應液的水分量之結果，包含6.9mmol。接著，將反應混合物冷卻至-10℃，將溫度保持在-10±5℃的同時經60分鐘加入了16.9g（142.1mmol）的SOCl2 。用50mL的N-甲基吡咯啶酮進行稀釋之後，在-10±5℃下經60分鐘將在100mL的N-甲基吡咯啶酮溶解了20.1g的4,4’-二胺基-2,2’-雙（三氟甲基）聯苯之溶液滴加到反應混合物，對混合物攪拌了2小時。接著，在6升的水中使聚醯亞胺前驅物沉澱，以5000rpm的速度對水-聚醯亞胺前驅物混合物攪拌了15分鐘。對聚醯亞胺前驅物的固體進行過濾而將其溶解於四氫呋喃380g。關於所得到之溶液，在6升的水中使聚醯亞胺前驅物沉澱，以5000rpm的速度對水-聚醯亞胺前驅物混合物攪拌了15分鐘。再次對聚醯亞胺前驅物的固體進行過濾並在減壓下，在45℃下乾燥了3天。該聚醯亞胺前驅物中，重量平均分子量係26,800、數平均分子量係8400，與除了碳骨架以外鍵結之-SO3 H基的數係總構成單元的合計數的4.52%。(Synthesis Example 17) [Synthesis of Polymer Precursor A-17] 14.9 g (68.3 mmol) of pyromellitic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, 0.10 g of water and 250 mL of diethylene glycol dimethyl ether were stirred at a temperature of 60° C. for 4 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. As a result of measuring the water content of the obtained reaction liquid, it contained 6.9 mmol. Next, the reaction mixture was cooled to -10°C, and 16.9 g (142.1 mmol) of SOCl 2 was added over 60 minutes while maintaining the temperature at -10±5°C. After diluting with 50 mL of N-methylpyrrolidone, 20.1 g of 4,4'-diamino-2 was dissolved in 100 mL of N-methylpyrrolidone at -10±5°C for 60 minutes A solution of 2'-bis(trifluoromethyl)biphenyl was added dropwise to the reaction mixture, and the mixture was stirred for 2 hours. Next, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred at a speed of 5000 rpm for 15 minutes. The solid of the polyimide precursor was filtered and dissolved in 380 g of tetrahydrofuran. Regarding the obtained solution, the polyimide precursor was precipitated in 6 liters of water, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The solid of the polyimide precursor was filtered again and dried at 45° C. for 3 days under reduced pressure. In this polyimide precursor, the weight average molecular weight is 26,800, the number average molecular weight is 8400, and the number of -SO 3 H groups bonded to other than the carbon skeleton is 4.52% of the total number of structural units.

＜重量平均分子量及數平均分子量的測量＞ 聚合物前驅物的重量平均分子量（Mw）及數平均分子量（Mn）係基於凝膠滲透層析法（GPC）測量之聚苯乙烯換算值，藉由以下的方法來進行了測量。 作為測量裝置使用了HLC-8220（TOSOH CORPORATION製），作為管柱使用了保護管柱HZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、TSKgel Super HZ2000（TOSOH CORPORATION製）。又，洗提液使用THF（四氫呋喃），在40℃下以0.35mL/分鐘的流速進行了測量。檢測時使用了紫外線（UV）254nm檢測器。又，測量樣品使用了用THF將含雜環的聚合物前驅物稀釋調整為0.1質量%之樣品。<Measurement of weight average molecular weight and number average molecular weight> The weight average molecular weight (Mw) and the number average molecular weight (Mn) of a polymer precursor are based on the polystyrene conversion value measured by gel permeation chromatography (GPC), and measured by the following method. HLC-8220 (manufactured by TOSOH CORPORATION) was used as the measuring device, and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) were used as the column. Also, the eluent was measured at a flow rate of 0.35 mL/min at 40° C. using THF (tetrahydrofuran). Detection was performed using an ultraviolet (UV) 254nm detector. In addition, as a measurement sample, a sample prepared by diluting the heterocycle-containing polymer precursor with THF to 0.1% by mass was used.

＜實施例及比較例的感光性樹脂組成物的製備＞ 混合下述表1中所記載的各成分，作為均勻的溶液，通過細孔的寬度係0.8μm的聚四氟乙烯（PTFE）過濾器在壓力0.3MPa下進行加壓過濾，藉此得到了各感光性樹脂組成物。<Preparation of Photosensitive Resin Compositions of Examples and Comparative Examples> The components described in the following Table 1 were mixed, and as a uniform solution, pressure filtration was performed at a pressure of 0.3 MPa through a polytetrafluoroethylene (PTFE) filter with a pore width of 0.8 μm, thereby obtaining each Photosensitive resin composition.

＜保存穩定性＞ 將上述感光性樹脂組成物10g放入容器（容器的材質：遮光玻璃、容量：100mL）並密封，於25℃、相對濕度65%的環境下靜置1週。關於經時前後各自的組成物，使用RE-85L（TOKI SANGYO CO.,LTD.製）進行25℃下的黏度測量，計算出了黏度的變化率（ηr=|η2-η1|/η1、ηr：黏度的變化率、η1：經時前的黏度、η2：經時後的黏度）。變化率愈少，感光性樹脂組成物的穩定性愈高，成為較佳的結果。裝置的設定或測量條件等、其他事項以JIS Z 8803：2011為基準。 A：0%以上且小於5% B：5%以上且小於8% C：8%以上且小於10% D：10%以上且小於15% E：15%以上＜Storage stability＞ Put 10 g of the photosensitive resin composition above into a container (container material: light-shielding glass, capacity: 100 mL), seal it, and let it stand at 25° C. and a relative humidity of 65% for 1 week. Regarding the respective compositions before and after time, the viscosity was measured at 25°C using RE-85L (manufactured by TOKI SANGYO CO., LTD.), and the rate of change in viscosity was calculated (ηr=|η2-η1|/η1, ηr : rate of change of viscosity, η1: viscosity before time elapsed, η2: viscosity after time elapsed). The smaller the rate of change, the higher the stability of the photosensitive resin composition, which is a better result. Device settings, measurement conditions, etc., and other items are based on JIS Z 8803:2011. A: More than 0% and less than 5% B: More than 5% and less than 8% C: More than 8% and less than 10% D: More than 10% and less than 15% E: more than 15%

＜銅腐蝕性＞ 將上述感光性樹脂組成物旋壓成形於厚度250μm的銅基板上而適用。 在加熱板上，以100℃對適用了感光性樹脂組成物之銅基板乾燥5分鐘，在銅基板上形成了厚度10μm的膜。接著，在氮環境下，以10℃/分鐘的升溫速度升溫而達到230℃之後，保持了3小時。冷卻之後，用切割機刮掉銅基板上的膜。用肉眼觀察銅基板，並計算出著色成錆色之面積比例，對銅腐蝕性進行了評價。面積比例愈少，銅腐蝕性愈少。 A：5%以下。 B：大於5%且10%以下。 C：大於10%且20%以下。 D：大於20%。＜Copper Corrosion＞ The above-mentioned photosensitive resin composition was applied by spin molding on a copper substrate with a thickness of 250 μm. The copper substrate to which the photosensitive resin composition was applied was dried on a hot plate at 100° C. for 5 minutes to form a film with a thickness of 10 μm on the copper substrate. Next, in a nitrogen atmosphere, the temperature was raised at a rate of 10° C./minute to reach 230° C., and then held for 3 hours. After cooling, the film on the copper substrate was scraped off with a cutter. The copper substrate was observed with the naked eye, and the ratio of the area that was colored into a tinted color was calculated to evaluate the corrosion resistance of copper. The smaller the area ratio, the less corrosive copper is. A: Below 5%. B: More than 5% and 10% or less. C: More than 10% and 20% or less. D: more than 20%.

[表1]

Figure 108102651-A0304-0001
[Table 1]
Figure 108102651-A0304-0001

如示於上述表1之結果，導入了包含磺酸基之部位之樹脂在保存穩定性及銅腐蝕性上均顯示高的性能（實施例1～23）。與此相對，使用了不具有包含磺酸基之部位之樹脂之比較例中，保存穩定性尤其差（比較例1、2）。又，即使具有-SO3 H基，僅有與除了碳骨架以外鍵結之-SO3 H基之情況下，保存穩定性亦較差。實施例中，其中，包含磺酸基之部位的導入比例係中程度的實施例6～10（A-3～A-5）、實施例12（A-7）、實施例16～21（A-10～A-12）中，顯示相對高的性能。 由上述結果，依據本發明，能夠實現保存穩定性。另外，可知能夠實現保存穩定性及銅腐蝕性等的權衡的效果這兩個方面。又，藉由本發明，能夠提供於習知之者不同之新型聚醯亞胺前驅物及聚苯并㗁唑前驅物。As shown in the results in Table 1 above, the resins into which the site containing the sulfonic acid group exhibited high performance in both storage stability and copper corrosion resistance (Examples 1 to 23). On the other hand, in the comparative example which used the resin which does not have the part containing a sulfonic acid group, storage stability was especially inferior (comparative example 1, 2). Also, even if it has a -SO 3 H group, if there is only a -SO 3 H group bonded to other than the carbon skeleton, the storage stability is poor. Among the examples, examples 6 to 10 (A-3 to A-5), example 12 (A-7), examples 16 to 21 (A -10 to A-12), showing relatively high performance. From the above results, according to the present invention, storage stability can be achieved. In addition, it turned out that both aspects of the effect of trade-off, such as storage stability and copper corrosion property, can be achieved. Also, according to the present invention, novel polyimide precursors and polybenzoxazole precursors different from conventional ones can be provided.

（A）聚合物前驅物 A-1～A-16：在合成例1～16中製造之聚合物前驅物(A) Polymer precursor A-1 to A-16: Polymer precursors produced in Synthesis Examples 1 to 16

（B）自由基聚合性化合物 B-1：NK ESTER M-40G（Shin-Nakamura Chemical Co.,Ltd.製） B2：SR-209（Sartomer Company,Inc.製） B-3：NK ESTER A-9300（Shin-Nakamura Chemical Co.,Ltd.製） B-4：A-TMMT（Shin-Nakamura Chemical Co.,Ltd.製） B-5：A-DPH（二新戊四醇六丙烯酸酯、Shin-Nakamura Chemical Co.,Ltd.製）(B) Radical polymerizable compound B-1: NK ESTER M-40G (manufactured by Shin-Nakamura Chemical Co., Ltd.) B2: SR-209 (manufactured by Sartomer Company, Inc.) B-3: NK ESTER A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.) B-4: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) B-5: A-DPH (Di-Neopentylthritol Hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

（C）光自由基聚合起始劑 C-1：IRGACURE OXE 01（BASF公司製） C-2：IRGACURE OXE 02（BASF公司製） C-3：IRGACURE OXE 04（BASF公司製） C-4：IRGACURE-784（BASF公司製） C-5：NCI-831（ADEKA CORPORATION製）(C) Photoradical polymerization initiator C-1: IRGACURE OXE 01 (manufactured by BASF Corporation) C-2: IRGACURE OXE 02 (manufactured by BASF Corporation) C-3: IRGACURE OXE 04 (manufactured by BASF Corporation) C-4: IRGACURE-784 (manufactured by BASF Corporation) C-5: NCI-831 (manufactured by ADEKA CORPORATION)

（D）硬化促進劑（鹼產生劑） D-1：下述化合物 D-2：下述化合物 D-3：下述化合物 [化學式43]

Figure 02_image085
(D) Hardening accelerator (base generator) D-1: the following compound D-2: the following compound D-3: the following compound [Chemical formula 43]
Figure 02_image085

（E）聚合抑制劑 E-1：1,4-對苯醌 E-2：4-甲氧基苯酚(E) Polymerization inhibitors E-1: 1,4-p-benzoquinone E-2: 4-methoxyphenol

（F）添加劑（遷移抑制劑） F-1：1,2,4-三唑 F-2：1H-四唑(F) Additives (migration inhibitors) F-1: 1,2,4-triazole F-2: 1H-tetrazole

（G）矽烷偶合劑（金屬接黏性改良劑） G-1：下述化合物 G-2：下述化合物 G-3：下述化合物 [化學式44]

Figure 02_image087
(G) Silane coupling agent (metal adhesion improver) G-1: the following compound G-2: the following compound G-3: the following compound [Chemical formula 44]
Figure 02_image087

（H）溶劑 H-1：γ-丁內酯 H-2：二甲基亞碸 H-3：N-甲基-2-吡咯啶酮 H-4：乳酸乙酯 關於表1中的溶劑，例如種類的欄成為“H-1/H-2”、質量%的欄成為“48+12”之情況下，係指含有48質量%的H-1、含有12質量%的H-2。(H) solvent H-1: γ-butyrolactone H-2: Dimethylsulfone H-3: N-methyl-2-pyrrolidone H-4: ethyl lactate Regarding the solvents in Table 1, for example, when the column of type is "H-1/H-2" and the column of mass % is "48+12", it means that H-1 is contained in 48 mass%, and H-1 is contained in 12 mass%. % H-2.

＜實施例100＞ 通過細孔的寬度係0.8μm的過濾器對實施例1的感光性樹脂組成物進行加壓過濾之後，藉由旋塗法在矽晶圓上塗佈了感光性樹脂組成物。將塗佈有感光性樹脂組成物層之矽晶圓於加熱板上，在100℃下乾燥5分鐘而於矽晶圓上形成了厚度15μm的均勻的感光性樹脂組成物層。使用步進機（Nikon NSR 2005 i9C），以500mJ/cm2 的曝光能量對矽晶圓上的感光性樹脂組成物層進行曝光，用環戊酮對經曝光之感光性樹脂組成物層（樹脂層）進行60秒鐘的顯影而形成了直徑10μm的孔。接著，在氮環境下，以10℃/分鐘的升溫速度進行升溫而達到250℃之後，在該溫度下維持了3小時。冷卻至室溫之後，以覆蓋上述孔部分之方式，於感光性樹脂組成物層的表面的一部分，藉由蒸鍍法形成了厚度2μm的銅薄層（金屬層）。進而，於金屬層及感光性樹脂組成物層的表面，再次使用種類相同的感光性樹脂組成物，與上述相同地再次實施感光性樹脂組成物的濾過至經圖案化之膜的3小時加熱的步驟而製作了由樹脂層/金屬層/樹脂層構成之積層體。 該樹脂層（再配線層用層間絕緣膜）的絕緣性優異。 又，使用該再配線層用層間絕緣膜製造半導體元件之結果，確認到動作正常。<Example 100> After pressure-filtering the photosensitive resin composition of Example 1 through a filter with a pore width of 0.8 μm, the photosensitive resin composition was coated on a silicon wafer by spin coating . The silicon wafer coated with the photosensitive resin composition layer was dried on a heating plate at 100° C. for 5 minutes to form a uniform photosensitive resin composition layer with a thickness of 15 μm on the silicon wafer. Use a stepper (Nikon NSR 2005 i9C) to expose the photosensitive resin composition layer on the silicon wafer with an exposure energy of 500mJ/ cm2 , and use cyclopentanone to expose the exposed photosensitive resin composition layer (resin layer) was developed for 60 seconds to form holes with a diameter of 10 μm. Next, the temperature was raised to 250° C. at a rate of temperature increase of 10° C./min under a nitrogen atmosphere, and then maintained at that temperature for 3 hours. After cooling to room temperature, a copper thin layer (metal layer) with a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer by a vapor deposition method so as to cover the hole. Furthermore, on the surface of the metal layer and the photosensitive resin composition layer, the photosensitive resin composition of the same type was used again, and the process of filtering the photosensitive resin composition and heating the patterned film for 3 hours was performed again in the same manner as above. The laminated body composed of resin layer/metal layer/resin layer was produced according to the steps. This resin layer (interlayer insulating film for rewiring layer) is excellent in insulation. Also, as a result of manufacturing a semiconductor element using this interlayer insulating film for a rewiring layer, it was confirmed that the operation was normal.

無none

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Claims (18)

一種感光性樹脂組成物，其包含選自聚醯亞胺前驅物及聚苯并
Figure 108102651-A0305-02-0098-7
唑前驅物之聚合物前驅物及光活性化合物，該聚合物前驅物具有包括在由來自於四羧酸、四羧酸衍生物、二羧酸及二羧酸衍生物的至少一種之構成單元、以及來自於二胺的至少一種之構成單元構成之該聚合物前驅物的側鏈經由連接基鍵結之磺酸基以及與該聚合物前驅物的末端鍵結之磺酸基之群組中的至少一種，其中該磺酸基由下述式(Ls)表示：*1-Li-Lt-(SO3H)ns 式(Ls)*1係成為主鏈之結構側的鍵結位置；Li係雜原子或具有雜原子之連接基；Lt係由碳原子及氫原子構成之連接基Lt；該連接基Lt為具有雜原子之連接基Lh，該連接基Lh為氧原子、硫原子、羰基、硫羰基、磺醯基、-NRN-或包括該等組合之連接基，RN係氫原子或有機基；ns係1~4的整數。 A photosensitive resin composition comprising polyimide precursors and polybenzo
Figure 108102651-A0305-02-0098-7
A polymer precursor and a photoactive compound of an azole precursor, the polymer precursor having at least one constituent unit derived from tetracarboxylic acid, tetracarboxylic acid derivative, dicarboxylic acid and dicarboxylic acid derivative, And in the group of the sulfonic acid group bonded to the side chain of the polymer precursor composed of at least one structural unit derived from diamine via a linker and the sulfonic acid group bonded to the terminal of the polymer precursor At least one, wherein the sulfonic acid group is represented by the following formula (Ls): * 1 -Li-Lt-(SO 3 H) ns formula (Ls) * 1 is the bonding position on the structural side of the main chain; Li system A heteroatom or a linking group with a heteroatom; Lt is a linking group Lt composed of a carbon atom and a hydrogen atom; the linking group Lt is a linking group Lh with a heteroatom, and the linking group Lh is an oxygen atom, a sulfur atom, a carbonyl group, Thiocarbonyl, sulfonyl, -NR N - or linking groups including these combinations, R N is a hydrogen atom or an organic group; ns is an integer from 1 to 4. 如申請專利範圍第1項所述之感光性樹脂組成物，其中該聚合物前驅物包含由下述式(1)表示之構成單元或由式(2)表示之構成單元，
Figure 108102651-A0305-02-0098-1
 式(1)中，A1及A2分別獨立地表示氧原子或NH，R111表示2價的有機基，R115表示4價的有機基，R113及R114分別獨立地表示氫原子或1價的有機基，
Figure 108102651-A0305-02-0099-2
 式(2)中，R121表示2價的有機基，R122表示4價的有機基，R123及R124分別獨立地表示氫原子或1價的有機基。 The photosensitive resin composition as described in claim 1, wherein the polymer precursor comprises a structural unit represented by the following formula (1) or a structural unit represented by the formula (2),
Figure 108102651-A0305-02-0098-1
 In formula (1), A 1 and A 2 independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 independently represent a hydrogen atom or 1-valent organic group,
Figure 108102651-A0305-02-0099-2
 In formula (2), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. 如申請專利範圍第2項所述之感光性樹脂組成物，其中該聚合物前驅物包含由式(1)表示之構成單元。 The photosensitive resin composition as described in claim 2, wherein the polymer precursor comprises a structural unit represented by formula (1). 如申請專利範圍第1項或第2項所述之感光性樹脂組成物，其中該聚合物前驅物具有由式(1-1)、式(1-2)、式(1-3)、式(2-1)、式(2-2)及式(2-3)中的任一個所表示之結構，
Figure 108102651-A0305-02-0099-3
 式中，A1及A2分別獨立地表示氧原子或NH，R111表示2價的有機基，R115表示4價的有機基，R113及R114分別獨立地表示氫原子或1價的有機基，X1、X2及X3分別獨立地表示連接基，*表示與聚醯亞胺前驅物的主鏈的鍵結位置，ns表示1~4的整數，
Figure 108102651-A0305-02-0100-4
 式中，R121表示2價的有機基，R122表示4價的有機基，R123及R124分別獨立地表示氫原子或1價的有機基，X4、X5及X6分別獨立地表示連接基，*表示與聚苯并
Figure 108102651-A0305-02-0100-8
唑前驅物的主鏈的鍵結位置，ns表示1~4的整數。 The photosensitive resin composition as described in item 1 or item 2 of the scope of patent application, wherein the polymer precursor has formula (1-1), formula (1-2), formula (1-3), formula (2-1), the structure represented by any one of formula (2-2) and formula (2-3),
Figure 108102651-A0305-02-0099-3
 In the formula, A 1 and A 2 independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 independently represent a hydrogen atom or a monovalent An organic group, X 1 , X 2 and X 3 independently represent a linking group, * represents the bonding position with the main chain of the polyimide precursor, ns represents an integer of 1 to 4,
Figure 108102651-A0305-02-0100-4
 In the formula, R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group, X 4 , X 5 and X 6 independently Indicates linking group, * indicates that it is compatible with polybenzo
Figure 108102651-A0305-02-0100-8
The bonding position of the main chain of the azole precursor, ns represents an integer of 1-4. 如申請專利範圍第1項或第2項所述之感光性樹脂組成物，其中該聚合物前驅物中所含有之磺酸基的合計數係總構成單元的合計數的0.05%以上且15.0%以下。 The photosensitive resin composition as described in item 1 or item 2 of the patent application, wherein the total number of sulfonic acid groups contained in the polymer precursor is 0.05% or more and 15.0% of the total number of the total structural units the following. 如申請專利範圍第1項或第2項所述之感光性樹脂組成物，其還包含自由基聚合性化合物。 The photosensitive resin composition as described in item 1 or item 2 of the patent claims further includes a free radical polymerizable compound. 如申請專利範圍第1項或第2項所述之感光性樹脂組成物，其還包含硬化促進劑。 The photosensitive resin composition as described in claim 1 or claim 2, which further includes a hardening accelerator. 如申請專利範圍第1項或第2項所述之感光性樹脂組成物，其中該光活性化合物包含光自由基聚合起始劑。 The photosensitive resin composition as described in claim 1 or claim 2, wherein the photoactive compound includes a photoradical polymerization initiator. 如申請專利範圍第1項或第2項所述之感光性樹脂組成物，其用於顯影。 The photosensitive resin composition as described in item 1 or item 2 of the patent application, which is used for developing. 如申請專利範圍第1項或第2項所述之感光性樹脂組成物，其用於使用包含有機溶劑之顯影液進行顯影之用途。 The photosensitive resin composition as described in item 1 or item 2 of the patent application, which is used for developing with a developer solution containing an organic solvent. 如申請專利範圍第1項或第2項所述之感光性樹脂組成物，其用於再配線層用層間絕緣膜的形成。 The photosensitive resin composition described in claim 1 or claim 2, which is used for forming an interlayer insulating film for a rewiring layer. 一種樹脂，其包括如申請專利範圍第1項所述之感光性樹脂組 成物之聚合物前驅物之樹脂，其中該聚合物前驅物具有由式(1-1)、式(1-2)、式(1-3)、式(2-1)、式(2-2)或式(2-3)中的任一個所表示之部位，
Figure 108102651-A0305-02-0101-5
 式中，A1及A2分別獨立地表示氧原子或NH，R111表示2價的有機基，R115表示4價的有機基，R113及R114分別獨立地表示氫原子或1價的有機基，X1、X2及X3分別獨立地表示連接基，*表示與聚醯亞胺前驅物的主鏈的鍵結位置，ns表示1~4的整數，
Figure 108102651-A0305-02-0101-6
 式中，R121表示2價的有機基，R122表示4價的有機基，R123及R124分別獨立地表示氫原子或1價的有機基，X4、X5及X6分別獨立地表示連接基，*表示與聚苯并
Figure 108102651-A0305-02-0101-9
唑前驅物的主鏈的鍵結位置，ns表示1~4的整數。 A kind of resin, it comprises the resin of the polymer precursor of the photosensitive resin composition as described in item 1 of the patent scope, wherein the polymer precursor has formula (1-1), formula (1-2), The position represented by any one of formula (1-3), formula (2-1), formula (2-2) or formula (2-3),
Figure 108102651-A0305-02-0101-5
 In the formula, A 1 and A 2 independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 independently represent a hydrogen atom or a monovalent An organic group, X 1 , X 2 and X 3 independently represent a linking group, * represents the bonding position with the main chain of the polyimide precursor, ns represents an integer of 1 to 4,
Figure 108102651-A0305-02-0101-6
 In the formula, R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group, X 4 , X 5 and X 6 independently Indicates linking group, * indicates that it is compatible with polybenzo
Figure 108102651-A0305-02-0101-9
The bonding position of the main chain of the azole precursor, ns represents an integer of 1-4. 一種硬化膜，其將申請專利範圍第1項至第11項中任一項所述之感光性樹脂組成物進行硬化而成。 A cured film, which is formed by curing the photosensitive resin composition described in any one of the first to eleventh claims of the patent application. 一種積層體，其具有2層以上的申請專利範圍第13項所述之硬化膜。 A laminate having two or more layers of the cured film described in claim 13 of the scope of application. 如申請專利範圍第14項所述之積層體，其中在該硬化膜之間具有金屬層。 The laminate according to claim 14, wherein a metal layer is provided between the cured films. 一種硬化膜之製造方法，其包括使用申請專利範圍第1項至第11項中任一項所述之感光性樹脂組成物之步驟。 A method for producing a cured film, which includes the step of using the photosensitive resin composition described in any one of the first to eleventh claims of the patent application. 如申請專利範圍第16項所述之硬化膜之製造方法，其具有：將該感光性樹脂組成物適用於基板而成為層狀之感光性樹脂組成物層形成步驟；對該感光性樹脂組成物層進行曝光之曝光步驟；及對經該曝光之感光性樹脂組成物層進行顯影處理之顯影處理步驟。 The method for producing a cured film as described in claim 16 of the scope of the patent application, which comprises: applying the photosensitive resin composition to a substrate to form a layered photosensitive resin composition layer; an exposure step of exposing the exposed photosensitive resin composition layer; and a development treatment step of performing development treatment on the exposed photosensitive resin composition layer. 一種半導體元件，其具有如申請專利範圍第13項所述之硬化膜、或者如申請專利範圍第14項或第15項所述之積層體。 A semiconductor element having the cured film as described in Claim 13, or the laminate as described in Claim 14 or 15.
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