TWI825626B - Photosensitive resin composition, cured product, laminate, manufacturing method of cured product, and semiconductor element - Google Patents

Photosensitive resin composition, cured product, laminate, manufacturing method of cured product, and semiconductor element Download PDF

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TWI825626B
TWI825626B TW111109965A TW111109965A TWI825626B TW I825626 B TWI825626 B TW I825626B TW 111109965 A TW111109965 A TW 111109965A TW 111109965 A TW111109965 A TW 111109965A TW I825626 B TWI825626 B TW I825626B
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resin composition
group
mass
photosensitive resin
solvent
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TW202244132A (en
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吉田健太
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日商富士軟片股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/145—Polyamides; Polyesteramides; Polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/094—Multilayer resist systems, e.g. planarising layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
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Abstract

本發明提供一種感光性樹脂組成物、硬化上述感光性樹脂組成物而成之硬化物、包含上述硬化物之積層體、上述硬化物的製造方法，及包含上述硬化物或上述積層體之半導體元件，所述感光性樹脂組成物包含：環化樹脂或其前驅物；SP值為21.0（J/cm 3） 0.5以上且小於25.0（J/cm 3） 0.5之溶劑B；SP值小於21.0（J/cm 3） 0.5或為25.0（J/cm 3） 0.5以上且沸點為60℃以上之溶劑C；及感光劑，上述溶劑C的含量相對於感光性樹脂組成物的總質量為1ppm以上且10,000ppm以下。 The present invention provides a photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition, a laminated body containing the cured product, a method for manufacturing the cured product, and a semiconductor element containing the cured product or the laminated body. , the photosensitive resin composition includes: cyclized resin or its precursor; solvent B with an SP value of 21.0 (J/cm 3 ) 0.5 or more and less than 25.0 (J/cm 3 ) 0.5 ; an SP value less than 21.0 (J /cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or more and a solvent C with a boiling point of 60°C or more; and a photosensitive agent, the content of the above solvent C is 1 ppm or more and 10,000 based on the total mass of the photosensitive resin composition ppm or less.

Description

感光性樹脂組成物、硬化物、積層體、硬化物的製造方法及半導體元件Photosensitive resin composition, cured product, laminate, manufacturing method of cured product, and semiconductor element

本發明係有關一種感光性樹脂組成物、硬化物、積層體、硬化物的製造方法及半導體元件。The present invention relates to a photosensitive resin composition, a cured product, a laminated body, a method for manufacturing the cured product, and a semiconductor element.

聚醯亞胺等環化樹脂由於耐熱性及絕緣性等優異，因此可用於各種用途。作為上述用途，並沒有特別限定，若以實際安裝用半導體元件為例，則可以舉出作為絕緣膜、密封材料的素材或保護膜的利用。又，亦可用作可撓性基板的基底膜、覆蓋膜等。Cyclized resins such as polyimide are used in various applications because they have excellent heat resistance and insulation properties. The above-mentioned use is not particularly limited. Taking a semiconductor element for actual mounting as an example, the use as an insulating film, a material for a sealing material, or a protective film can be cited. In addition, it can also be used as a base film, a cover film, etc. of a flexible substrate.

例如，在上述用途中，聚醯亞胺等環化樹脂以包含聚醯亞胺等環化樹脂及環化樹脂的前驅物中的至少1種之樹脂組成物的形態使用。 例如藉由塗佈等將該種樹脂組成物適用於基材上形成感光膜，之後根據需要進行曝光、顯影、加熱等，藉此能夠在基材上形成硬化物。 聚醯亞胺前驅物等上述環化樹脂的前驅物例如藉由加熱被環化而在硬化物中成為聚醯亞胺等環化樹脂。 樹脂組成物能夠藉由公知的塗佈方法等適用，因此，可以說例如所適用之樹脂組成物的適用時的形狀、大小、適用位置等設計自由度高等製造上的適應性優異。從除了聚醯亞胺等環化樹脂所具有之高性能以外，該種製造上的適應性亦優異的觀點考慮，上述樹脂組成物在產業上的應用拓展愈發令人期待。 For example, in the above applications, the cyclized resin such as polyimide is used in the form of a resin composition containing at least one of the cyclized resin such as polyimide and a precursor of the cyclized resin. For example, the resin composition is applied to a base material by coating to form a photosensitive film, and then exposure, development, heating, etc. are performed as necessary to form a cured product on the base material. Precursors of the cyclized resin such as polyimide precursors are cyclized by heating, for example, and become cyclized resins such as polyimide in the cured product. The resin composition can be applied by a known coating method, etc., so it can be said that the applied resin composition has a high degree of freedom in designing the shape, size, application position, etc. at the time of application, and is excellent in manufacturing adaptability. In addition to the high performance of cyclized resins such as polyimide and their excellent manufacturing adaptability, the expansion of industrial applications of the above-mentioned resin compositions is increasingly expected.

例如，在專利文獻1中，記載有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噁唑前驅物之聚合物前驅物、光自由基聚合起始劑及溶劑，聚合物前驅物中所包含之中和點的pH在7.0～12.0的範圍內之酸基的酸值在2.5～34.0mgKOH/g的範圍內，並且上述聚合物前驅物具有自由基聚合性基或者包含除了上述聚合物前驅物以外的自由基聚合性化合物。 在專利文獻2中，記載有一種聚醯亞胺擠出成型用聚醯亞胺前驅物組成物，其包含使芳香族四羧酸二酐或其衍生物（a）與芳香族二胺或其衍生物（b）反應而獲得之聚醯亞胺前驅物（c）30～60重量%、上述聚醯亞胺前驅物的不良溶劑0.1～5重量%及上述聚醯亞胺前驅物的良溶劑35～69.9重量%。 For example, Patent Document 1 describes a photosensitive resin composition including a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a photoradical polymerization initiator, and a solvent. , the polymer precursor contains an acid group with a neutralization point pH in the range of 7.0 to 12.0, an acid value in the range of 2.5 to 34.0 mgKOH/g, and the polymer precursor has a radical polymerizable group Or it contains a radically polymerizable compound other than the above-mentioned polymer precursor. Patent Document 2 describes a polyimide precursor composition for polyimide extrusion molding, which contains an aromatic tetracarboxylic dianhydride or its derivative (a) and an aromatic diamine or its derivative. 30 to 60% by weight of the polyimide precursor (c) obtained by reacting the derivative (b), 0.1 to 5% by weight of the poor solvent for the above-mentioned polyimide precursor, and 0.1 to 5% by weight of the good solvent for the above-mentioned polyimide precursor. 35~69.9% by weight.

[專利文獻1]國際公開第2018/221457號 [專利文獻2]日本特開平08-157598號公報 [Patent Document 1] International Publication No. 2018/221457 [Patent Document 2] Japanese Patent Application Publication No. 08-157598

在用於獲得硬化物的感光性樹脂組成物中，要求所獲得之硬化物的斷裂伸長率優異。In the photosensitive resin composition used to obtain a cured product, it is required that the obtained cured product has excellent elongation at break.

本發明的目的在於提供一種可以獲得斷裂伸長率優異之硬化物之感光性樹脂組成物、硬化上述感光性樹脂組成物而成之硬化物、包含上述硬化物之積層體、上述硬化物的製造方法及包含上述硬化物或上述積層體之半導體元件。An object of the present invention is to provide a photosensitive resin composition capable of obtaining a cured product excellent in elongation at break, a cured product obtained by curing the photosensitive resin composition, a laminate including the cured product, and a method for manufacturing the cured product. And a semiconductor element including the above-mentioned cured product or the above-mentioned laminated body.

以下，示出本發明的代表性實施態樣的例子。 ＜1＞一種感光性樹脂組成物，其係包含：環化樹脂或其前驅物； SP值為21.0（J/cm 3） 0.5以上且小於25.0（J/cm 3） 0.5之溶劑B； SP值小於21.0（J/cm 3） 0.5或為25.0（J/cm 3） 0.5以上且沸點為60℃以上之溶劑C；及 感光劑， 上述溶劑C的含量相對於感光性樹脂組成物的總質量為1ppm以上且10,000ppm以下。 ＜2＞如＜1＞所述之感光性樹脂組成物，其中，上述溶劑C為選自包括乙酸乙酯、乙酸異丙酯、乙酸正丙酯、乙酸丁酯、己烷、庚烷、苯、甲苯、甲醇、乙醇、四氫呋喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二乙醚、丙二醇單甲醚乙酸酯、環戊酮及環己酮之群組中之至少1種。 ＜3＞一種感光性樹脂組成物，其係包含： 環化樹脂或其前驅物； SP值為21.0（J/cm 3） 0.5以上且小於25.0（J/cm 3） 0.5之溶劑B； 作為乙酸乙酯、乙酸異丙酯、乙酸正丙酯、乙酸丁酯、己烷、庚烷、苯、甲苯、甲醇、乙醇、四氫呋喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二乙醚、丙二醇單甲醚乙酸酯、環戊酮或環己酮之溶劑C；及 感光劑， 上述溶劑C的含量相對於感光性樹脂組成物的總質量為1ppm以上且10,000ppm以下。 ＜4＞如＜1＞至＜3＞之任一項所述之感光性樹脂組成物，其中，上述溶劑B包含選自包括γ-丁內酯、二甲基亞碸、N-甲基-2-吡咯啶酮、丙二醇單甲醚及乳酸乙酯之群組中之至少1種。 ＜5＞如＜1＞至＜4＞之任一項所述之感光性樹脂組成物，其中，上述溶劑B的含量相對於感光性樹脂組成物的總質量為40質量%以上且小於90質量%。 ＜6＞如＜1＞至＜5＞之任一項所述之感光性樹脂組成物，其中，上述溶劑B包含γ-丁內酯或N-甲基-2-吡咯啶酮。 ＜7＞如＜1＞至＜6＞之任一項所述之感光性樹脂組成物，其中，上述溶劑C為甲苯、四氫呋喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二乙醚或環戊酮。 ＜8＞如＜1＞至＜7＞之任一項所述之感光性樹脂組成物，其中，上述溶劑C為甲苯、四氫呋喃、1,4-二噁烷或二乙二醇二甲醚。 ＜9＞如＜1＞至＜8＞之任一項所述之感光性樹脂組成物，其中，上述感光劑為光自由基聚合起始劑。 ＜10＞如＜1＞至＜9＞之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。 ＜11＞如＜1＞至＜10＞之任一項所述之感光性樹脂組成物，其還包含矽烷偶合劑。 ＜12＞如＜1＞至＜11＞之任一項所述之感光性樹脂組成物，其用於形成供負型顯影之感光膜。 ＜13＞如＜1＞至＜12＞之任一項所述之感光性樹脂組成物，其用於形成再配線層用層間絕緣膜。 ＜14＞一種硬化物，其係硬化＜1＞至＜13＞之任一項所述之感光性樹脂組成物而成。 ＜15＞一種積層體，其係包含2層以上由＜14＞所述之硬化物構成之層，在由上述硬化物構成之任意層之間包含金屬層。 ＜16＞一種硬化物的製造方法，其係包括在基板上適用＜1＞至＜13＞之任一項所述之感光性樹脂組成物來形成膜之膜形成步驟。 ＜17＞如＜16＞所述之硬化物的製造方法，其包括： 曝光步驟，對上述膜進行曝光；及顯影步驟，對上述膜進行顯影。 ＜18＞如＜16＞或＜17＞所述之硬化物的製造方法，其包括在50～450℃下加熱上述膜之加熱步驟。 ＜19＞一種半導體元件，其係包含＜14＞所述之硬化物或＜15＞所述之積層體。 [發明效果] Examples of representative embodiments of the present invention are shown below. <1> A photosensitive resin composition containing: a cyclized resin or its precursor; a solvent B with an SP value of 21.0 (J/cm 3 ) 0.5 or more and less than 25.0 (J/cm 3 ) 0.5 ; SP value A solvent C that is less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or more and has a boiling point of 60°C or more; and a photosensitive agent. The content of the above solvent C relative to the total mass of the photosensitive resin composition is: 1ppm or more and 10,000ppm or less. <2> The photosensitive resin composition according to <1>, wherein the solvent C is selected from the group consisting of ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, hexane, heptane, and benzene. , toluene, methanol, ethanol, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone and cyclohexanone group At least 1 of them. <3> A photosensitive resin composition containing: cyclized resin or its precursor; solvent B with an SP value of 21.0 (J/cm 3 ) 0.5 or more and less than 25.0 (J/cm 3 ) 0.5 ; as acetic acid Ethyl ester, isopropyl acetate, n-propyl acetate, butyl acetate, hexane, heptane, benzene, toluene, methanol, ethanol, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Solvent C of ethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone or cyclohexanone; and photosensitizer, the content of the above solvent C is 1 ppm or more and 10,000 ppm relative to the total mass of the photosensitive resin composition. the following. <4> The photosensitive resin composition according to any one of <1> to <3>, wherein the solvent B contains γ-butyrolactone, dimethylsulfoxide, N-methyl- At least one of the group consisting of 2-pyrrolidinone, propylene glycol monomethyl ether and ethyl lactate. <5> The photosensitive resin composition according to any one of <1> to <4>, wherein the content of the solvent B is 40 mass % or more and less than 90 mass % with respect to the total mass of the photosensitive resin composition. %. <6> The photosensitive resin composition according to any one of <1> to <5>, wherein the solvent B contains γ-butyrolactone or N-methyl-2-pyrrolidinone. <7> The photosensitive resin composition according to any one of <1> to <6>, wherein the solvent C is toluene, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether or cyclopentanone. <8> The photosensitive resin composition according to any one of <1> to <7>, wherein the solvent C is toluene, tetrahydrofuran, 1,4-dioxane or diglyme. <9> The photosensitive resin composition according to any one of <1> to <8>, wherein the photosensitizer is a photoradical polymerization initiator. <10> The photosensitive resin composition according to any one of <1> to <9>, further containing a radically polymerizable compound. <11> The photosensitive resin composition according to any one of <1> to <10>, further containing a silane coupling agent. <12> The photosensitive resin composition according to any one of <1> to <11>, which is used to form a photosensitive film for negative development. <13> The photosensitive resin composition according to any one of <1> to <12>, which is used to form an interlayer insulating film for a rewiring layer. <14> A cured product obtained by curing the photosensitive resin composition according to any one of <1> to <13>. <15> A laminated body including two or more layers composed of the hardened material described in <14>, and including a metal layer between any layers composed of the hardened material. <16> A method for manufacturing a cured product, which includes a film forming step of forming a film on a substrate by applying the photosensitive resin composition according to any one of <1> to <13>. <17> The method for manufacturing a hardened product according to <16>, which includes: an exposure step of exposing the film; and a development step of developing the film. <18> The method for producing a hardened product according to <16> or <17>, which includes a heating step of heating the film at 50 to 450°C. <19> A semiconductor element including the cured product according to <14> or the laminated body according to <15>. [Effects of the invention]

依據本發明，提供一種可以獲得斷裂伸長率優異之硬化物之感光性樹脂組成物、硬化上述感光性樹脂組成物而成之硬化物、包含上述硬化物之積層體、上述硬化物的製造方法及包含上述硬化物或上述積層體之半導體元件。According to the present invention, there are provided a photosensitive resin composition that can obtain a cured product excellent in elongation at break, a cured product obtained by curing the photosensitive resin composition, a laminate including the cured product, a method for manufacturing the cured product, and A semiconductor element including the above-mentioned cured product or the above-mentioned laminated body.

以下，對本發明的主要實施形態進行說明。然而，本發明並不限定於所明示之實施形態。 本說明書中，利用“～”記號表示之數值範圍係指，將記載於“～”的前後之數值分別作為下限值及上限值包括之範圍。 在本說明書中，“步驟”這一術語係指，不僅包括獨立的步驟，只要能夠達成該步驟的預期作用，則亦包括無法與其他步驟明確區分之步驟。 在本說明書中之基團（原子團）的標記中，未標有經取代及未經取代之標記包括不具有取代基之基團（原子團）的同時亦包括具有取代基之基團（原子團）。例如，“烷基”不僅包括不具有取代基之烷基（未經取代之烷基），亦包括具有取代基之烷基（經取代之烷基）。 在本說明書中，只要沒有特別說明，則“曝光”不僅包括利用光之曝光，亦包括利用電子束、離子束等粒子束之曝光。又，作為用於曝光之光，可以舉出水銀燈的明線光譜、以準分子雷射為代表之遠紫外線、極紫外線（EUV光）、X射線、電子束等活性光線或放射線。 在本說明書中，“（甲基）丙烯酸酯”表示“丙烯酸酯”及“甲基丙烯酸酯”這兩者或其中任一者，“（甲基）丙烯酸”表示“丙烯酸”及“甲基丙烯酸”這兩者或其中任一者，“（甲基）丙烯醯基”表示“丙烯醯基”及“甲基丙烯醯基”這兩者或其中任一者。 在本說明書中，結構式中的Me表示甲基，Et表示乙基，Bu表示丁基，Ph表示苯基。 在本說明書中，總固體成分係指組成物的所有成分中除溶劑之外的成分的總質量。又，在本說明書中，固體成分濃度為除溶劑以外的其他成分相對於組成物的總質量的質量百分率。 在本說明書中，只要沒有特別說明，重量平均分子量（Mw）及數量平均分子量（Mn）為利用凝膠滲透層析（GPC）法測定之值，定義為聚苯乙烯換算值。在本說明書中，例如，利用HLC-8220GPC（TOSOH CORPORATION製），將保護管柱HZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000及TSKgel Super HZ2000（以上為TOSOH CORPORATION製）串聯而用作管柱，藉此能夠求出重量平均分子量（Mw）及數量平均分子量（Mn）。只要沒有特別說明，該等分子量使用THF（四氫呋喃）作為洗提液進行測定。其中，溶解性較低的情況等，在THF不適合作為溶離液的情況下，亦能夠使用NMP（N-甲基-2-吡咯啶酮）。又，只要沒有特別說明，GPC測定中的檢測使用波長254nm的UV射線（紫外線）檢測器。 在本說明書中，關於構成積層體之各層的位置關係，記載為“上”或“下”時，只要在所關注的複數層中成為基準之層的上側或下側存在其他層即可。亦即，在成為基準之層與上述其他層之間可進一步夾有第3層或第3元素，成為基準之層與上述其他層無需接觸。又，只要沒有特別說明，將對基材堆疊層之方向稱為“上”，或在存在樹脂組成物層的情況下，將從基材朝向樹脂組成物層的方向稱為“上”，將其相反方向稱為“下”。此外，該等上下方向的設定係為了便於說明本說明書，在實際態樣中，本說明書中的“上”方向亦可以與鉛垂上朝向不同。 在本說明書中，只要沒有特別說明，作為組成物中所包含之各成分，組成物亦可以包含對應於該成分之2種以上的化合物。又，只要沒有特別說明，組成物中的各成分的含量係指對應於該成分之所有化合物的合計含量。 在本說明書中，只要沒有特別說明，溫度為23℃，氣壓為101,325Pa（1氣壓），相對濕度為50%RH。 在本說明書中，較佳態樣的組合為更佳態樣。 Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the illustrated embodiments. In this specification, the numerical range represented by the "～" mark means a range including the numerical values before and after "～" as the lower limit and the upper limit respectively. In this specification, the term "step" refers to not only independent steps, but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved. Among the labels for groups (atomic groups) in this specification, the labels indicating unsubstituted and unsubstituted include groups (atomic groups) without substituents as well as groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of the light used for exposure include the bright line spectrum of a mercury lamp, active rays or radiation such as far ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, and electron beams represented by excimer lasers. In this specification, "(meth)acrylate" means both or any one of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid". "Both or either of them, "(meth)acrylyl" means both or either of "acrylyl" and "methacrylyl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of all components of the composition except the solvent. In addition, in this specification, the solid content concentration is the mass percentage of other components except a solvent with respect to the total mass of a composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) and are defined as polystyrene-converted values. In this specification, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) is used, and the protection column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (the above are manufactured by TOSOH CORPORATION) are connected in series. When used as a column, the weight average molecular weight (Mw) and number average molecular weight (Mn) can be determined. Unless otherwise stated, the molecular weights are measured using THF (tetrahydrofuran) as the eluent. Among them, NMP (N-methyl-2-pyrrolidone) can also be used when the solubility is low and THF is not suitable as the eluent. In addition, unless otherwise specified, a UV ray (ultraviolet) detector with a wavelength of 254 nm is used for detection in GPC measurement. In this specification, when the positional relationship between the layers constituting the laminated body is described as "upper" or "lower", it suffices that there is another layer above or below the reference layer among the plurality of layers in question. That is, a third layer or a third element may be sandwiched between the base layer and the other layers, and the base layer does not need to be in contact with the other layers. In addition, unless otherwise specified, the direction in which the layers are stacked on the base material is called "upper", or when a resin composition layer is present, the direction from the base material toward the resin composition layer is called "upper". Its opposite direction is called "down". In addition, the setting of the up and down directions is for the convenience of explaining this specification. In actual aspects, the "up" direction in this specification may also be different from the vertical upward direction. In this specification, unless otherwise stated, as each component contained in the composition, the composition may contain two or more compounds corresponding to the component. In addition, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to the component. In this manual, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325Pa (1 atmosphere), and the relative humidity is 50%RH. In this specification, the combination of preferred aspects is a more preferred aspect.

（感光性樹脂組成物） 本發明的第1態樣的感光性樹脂組成物包含：環化樹脂或其前驅物；SP值為21.0（J/cm 3） 0.5以上且小於25.0（J/cm 3） 0.5之溶劑B；SP值小於21.0（J/cm 3） 0.5或為25.0（J/cm 3） 0.5以上且沸點為60℃以上之溶劑C；及感光劑，上述溶劑C的含量相對於感光性樹脂組成物的總質量為1ppm以上且10,000ppm以下。 本發明的第2態樣的感光性樹脂組成物包含：環化樹脂或其前驅物；SP值為21.0（J/cm 3） 0.5以上且小於25.0（J/cm 3） 0.5之溶劑B；作為乙酸乙酯、乙酸異丙酯、乙酸正丙酯、乙酸丁酯、己烷、庚烷、苯、甲苯、甲醇、乙醇、四氫呋喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二乙醚、丙二醇單甲醚乙酸酯、環戊酮或環己酮之溶劑C；及感光劑，上述溶劑C的含量相對於感光性樹脂組成物的總質量為1ppm以上且10,000ppm以下。 以下，簡單記載為“感光性樹脂組成物”或“樹脂組成物”的情況下，是指上述的第1態樣的感光性樹脂組成物及第2態樣的感光性樹脂組成物這兩者。 又，亦將上述的環化樹脂或其前驅物稱為“特定樹脂”。 (Photosensitive resin composition) The photosensitive resin composition according to the first aspect of the present invention contains: a cyclized resin or a precursor thereof; an SP value of 21.0 (J/cm 3 ) 0.5 or more and less than 25.0 (J/cm 3 ) ) 0.5 solvent B; solvent C with an SP value less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or above and a boiling point of 60°C or above; and photosensitizer, the content of the above solvent C relative to the photosensitive The total mass of the flexible resin composition is 1 ppm or more and 10,000 ppm or less. The photosensitive resin composition of the second aspect of the present invention contains: a cyclized resin or a precursor thereof; a solvent B with an SP value of 21.0 (J/cm 3 ) 0.5 or more and less than 25.0 (J/cm 3 ) 0.5 ; as Ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, hexane, heptane, benzene, toluene, methanol, ethanol, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, Solvent C of diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone or cyclohexanone; and photosensitizer, the content of the above solvent C relative to the total mass of the photosensitive resin composition is 1 ppm or more and 10,000 ppm or less. Hereinafter, when simply described as "photosensitive resin composition" or "resin composition", it refers to both the photosensitive resin composition of the above-mentioned first aspect and the photosensitive resin composition of the second aspect. . Moreover, the above-mentioned cyclized resin or its precursor is also called "specific resin".

在此，在本發明中，ppm為質量基準，上述溶劑C的含量相對於感光性樹脂組成物的總質量為下述式所表示之值。 上述溶劑C的含量相對於感光性樹脂組成物的總質量（ppm）=溶劑C的含有質量/感光性樹脂組成物的總質量×1,000,000 又，在本發明中，SP值係指，使用漢森溶解度參數亦即藉由Hansen Solubility Parameter in Practice（HSPiP）Ver.5.1.02計算之δD、δP、δH，並根據下述式求出之HSP值。 HSP值=（δD 2+δP 2+δH 2） 0.5 Here, in the present invention, ppm is a mass basis, and the content of the solvent C is a value represented by the following formula relative to the total mass of the photosensitive resin composition. The content of the above-mentioned solvent C relative to the total mass of the photosensitive resin composition (ppm) = mass of the solvent C/total mass of the photosensitive resin composition × 1,000,000 In addition, in the present invention, the SP value refers to the use of Hansen The solubility parameters are δD, δP, and δH calculated by Hansen Solubility Parameter in Practice (HSPiP) Ver.5.1.02, and the HSP value is calculated according to the following formula. HSP value = (δD 2 +δP 2 +δH 2 ) 0.5

本發明的樹脂組成物用於形成供曝光及顯影之感光膜為較佳，用於形成供曝光及使用包含有機溶劑之顯影液之顯影之膜為更佳。 本發明的樹脂組成物例如能夠用於形成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，用於形成再配線層用層間絕緣膜為較佳。 又，本發明的樹脂組成物可以用於形成供正型顯影之感光膜，亦可以用於形成供負型顯影之感光膜，但用於形成供負型顯影之感光膜為較佳。 在本發明中，在曝光及顯影中，負型顯影係指藉由顯影去除非曝光部之顯影，正型顯影係指藉由顯影去除曝光部之顯影。 作為上述曝光方法、上述顯影液及上述顯影方法，例如，可以使用在後述之硬化物的製造方法的說明中的曝光步驟中所說明之曝光方法、在顯影步驟中所說明之顯影液及顯影方法。 The resin composition of the present invention is preferably used to form a photosensitive film for exposure and development, and is more preferably used for forming a film for exposure and development using a developer containing an organic solvent. The resin composition of the present invention can be used to form, for example, an insulating film of a semiconductor element, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a rewiring layer. In addition, the resin composition of the present invention can be used to form a photosensitive film for positive development, or can be used to form a photosensitive film for negative development, but it is preferably used to form a photosensitive film for negative development. In the present invention, among exposure and development, negative development refers to development in which non-exposed parts are removed by development, and positive development refers to development in which exposed parts are removed by development. As the above-mentioned exposure method, the above-mentioned developer, and the above-mentioned development method, for example, the exposure method described in the exposure step in the description of the manufacturing method of the cured product described later, the developer described in the development step, and the development method can be used. .

依據本發明的樹脂組成物，可以獲得斷裂伸長率優異之硬化物。 以往，在各種領域中使用包含環化樹脂或其前驅物、溶劑及感光劑之感光性樹脂組成物。 本發明人等深入研究的結果，發現藉由使用第1態樣的感光性樹脂組成物或第2態樣的感光性樹脂組成物，從感光性樹脂組成物獲得之硬化物的斷裂伸長率提高。 推測這是因為，感光性樹脂組成物包含SP值小於21.0（J/cm 3） 0.5或為25.0（J/cm 3） 0.5以上且沸點為60℃以上之溶劑C，藉此溶劑C殘留在硬化前的膜中，在硬化時促進相對於該溶劑C溶解度低之環化樹脂或其前驅物的凝集。 又，若溶劑C的含量在上述範圍內，則能夠在維持感光性樹脂組成物的塗佈性的狀態下提高斷裂伸長率。亦即，推測本發明的感光性樹脂組成物在適用於基材等時的膜厚均勻性亦優異。 此外，推測若溶劑C的含量在上述範圍內，則感光劑在膜中均勻地分散，並且在曝光部效率良好地進行交聯反應，因此曝光部的顯影前後的膜厚變化率變小。 According to the resin composition of the present invention, a cured product excellent in elongation at break can be obtained. Conventionally, photosensitive resin compositions containing cyclized resins or their precursors, solvents, and photosensitizers have been used in various fields. As a result of intensive research, the present inventors found that by using the photosensitive resin composition of the first aspect or the photosensitive resin composition of the second aspect, the elongation at break of the cured product obtained from the photosensitive resin composition is improved. . This is presumably because the photosensitive resin composition contains solvent C with an SP value of less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or more and a boiling point of 60°C or more, so that the solvent C remains in the hardened film. In the former film, the aggregation of the cyclized resin or its precursor having low solubility with respect to the solvent C is promoted during curing. Moreover, if the content of the solvent C is within the above range, the elongation at break can be increased while maintaining the coatability of the photosensitive resin composition. That is, it is estimated that the photosensitive resin composition of the present invention also has excellent film thickness uniformity when applied to a base material or the like. Furthermore, it is presumed that when the content of solvent C is within the above range, the photosensitive agent is uniformly dispersed in the film and the crosslinking reaction proceeds efficiently in the exposed portion, so that the film thickness change rate before and after development of the exposed portion becomes small.

在此，在專利文獻1及專利文獻2中，未記載有以特定的量包含溶劑C之內容。Here, Patent Document 1 and Patent Document 2 do not describe that the solvent C is contained in a specific amount.

以下，對本發明的樹脂組成物中所包含之成分進行詳細說明。Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

＜特定樹脂＞ 本發明的樹脂組成物包含選自包括環化樹脂及其前驅物之群組中之至少1種樹脂（特定樹脂）。 環化樹脂係在主鏈結構中包含醯亞胺環結構或噁唑環結構之樹脂為較佳。 在本發明中，主鏈係指樹脂分子中相對最長的鍵結鏈。 作為環化樹脂，可以舉出聚醯亞胺、聚苯并噁唑、聚醯胺醯亞胺等。 環化樹脂的前驅物係指化學結構藉由外部刺激發生變化而成為環化樹脂之樹脂，化學結構藉由熱發生變化而成為環化樹脂之樹脂為較佳，藉由利用熱產生閉環反應而形成環結構來成為環化樹脂之樹脂為更佳。 作為環化樹脂的前驅物，可以舉出聚醯亞胺前驅物、聚苯并噁唑前驅物、聚醯胺醯亞胺前驅物等。 亦即，本發明的樹脂組成物包含選自包括聚醯亞胺、聚醯亞胺前驅物、聚苯并噁唑、聚苯并噁唑前驅物、聚醯胺醯亞胺及聚醯胺醯亞胺前驅物之群組中之至少1種樹脂（特定樹脂）作為特定樹脂為較佳。 本發明的樹脂組成物包含聚醯亞胺或聚醯亞胺前驅物作為特定樹脂為較佳。 又，從容易獲得斷裂伸長率提高這一效果之觀點而言，包含環化樹脂的前驅物作為特定樹脂為較佳，包含聚醯亞胺前驅物為較佳。 又，特定樹脂具有聚合性基為較佳，包含自由基聚合性基為更佳。 在特定樹脂具有自由基聚合性基的情況下，本發明的樹脂組成物包含後述自由基聚合起始劑為較佳，包含後述之自由基聚合起始劑且包含後述之自由基交聯劑為更佳。能夠根據需要進一步包含後述之增感劑。例如，由該等本發明的樹脂組成物可以形成負型感光膜。 又，特定樹脂可以具有酸分解性基等極性轉換基。 在特定樹脂具有酸分解性基的情況下，本發明的樹脂組成物包含後述之光酸產生劑為較佳。例如，由該等本發明的樹脂組成物可以形成作為化學增幅型的正型感光膜或負型感光膜。 ＜Specific resin＞ The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof. The cyclized resin is preferably a resin containing an imine ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain refers to the relatively longest bonding chain in the resin molecules. Examples of the cyclized resin include polyamide imide, polybenzoxazole, polyamide imide, and the like. The precursor of cyclized resin refers to a resin whose chemical structure changes through external stimulation and becomes a cyclized resin. The resin whose chemical structure changes through heat and becomes a cyclized resin is better. It is produced by using heat to produce a ring-closing reaction. It is more preferable to form a ring structure to become a cyclized resin. Examples of the precursors of the cyclized resin include polyamideimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is, the resin composition of the present invention contains polyamide imide, polyamide imide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide imide and polyamide imide. It is preferable that at least one kind of resin (specific resin) in the group of imine precursors is used as the specific resin. The resin composition of the present invention preferably contains polyimide or polyimide precursor as the specific resin. In addition, from the viewpoint of easily obtaining the effect of increasing the elongation at break, the specific resin preferably contains a precursor of a cyclized resin, and more preferably contains a polyimide precursor. Moreover, it is preferable that the specific resin has a polymerizable group, and it is more preferable that it contains a radical polymerizable group. When a specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains the radical polymerization initiator described below, and the resin composition of the present invention preferably contains the radical polymerization initiator described below and the radical cross-linking agent described below. Better. If necessary, a sensitizer described below can be further included. For example, a negative photosensitive film can be formed from the resin composition of the present invention. Furthermore, the specific resin may have a polar converting group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator described below. For example, a chemically amplified positive photosensitive film or a negative photosensitive film can be formed from the resin composition of the present invention.

〔聚醯亞胺前驅物〕 在本發明中所使用之聚醯亞胺前驅物並不特別限定其種類等，但包含下述式（2）所表示之重複單元為較佳。 [化學式1] 式（2）中，A 1及A 2分別獨立地表示氧原子或-NH-，R 111表示2價有機基團，R 115表示4價有機基團，R 113及R 114分別獨立地表示氫原子或1價有機基團。 [Polyimide Precursor] The type of the polyimide precursor used in the present invention is not particularly limited, but it is preferred that it contains a repeating unit represented by the following formula (2). [Chemical formula 1] In formula (2), 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, and R 113 and R 114 each independently represent hydrogen. Atom or 1-valent organic group.

式（2）中的A 1及A 2分別獨立地表示氧原子或-NH-，氧原子為較佳。 式（2）中的R 111表示2價有機基團。作為2價有機基團，可以例示出直鏈或支鏈的脂肪族基、環狀的脂肪族基及包含芳香族基之基團，碳數2～20的直鏈或支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數3～20的芳香族基或由該等的組合構成之基團為較佳，包含碳數6～20的芳香族基之基團為更佳。上述直鏈或支鏈的脂肪族基的鏈中的烴基可以被含雜原子之基團取代，上述環狀的脂肪族基及芳香族基的員環的烴基可以被含雜原子之基團取代。作為本發明的較佳之實施形態，可以例示出-Ar-及-Ar-L-Ar-所表示之基團，特佳為-Ar-L-Ar-所表示之基團。其中，Ar分別獨立地為芳香族基，L為單鍵或可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO 2-或-NHCO-、或者由上述2個以上的組合構成之基團。該等的較佳範圍如上所述。 A 1 and A 2 in the formula (2) each independently represent an oxygen atom or -NH-, with an oxygen atom being preferred. R 111 in formula (2) represents a divalent organic group. Examples of the divalent organic group include linear or branched aliphatic groups, cyclic aliphatic groups, and groups containing aromatic groups, and linear or branched aliphatic groups having 2 to 20 carbon atoms. , a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group including an aromatic group having 6 to 20 carbon atoms is preferred. For the better. The hydrocarbon groups in the linear or branched aliphatic group may be substituted by heteroatom-containing groups, and the hydrocarbon groups in the cyclic aliphatic and aromatic groups may be substituted by heteroatom-containing groups. . As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, and a group represented by -Ar-L-Ar- is particularly preferred. Among them, Ar is independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO 2 -or- NHCO-, or a group consisting of a combination of two or more of the above. The preferred ranges are as described above.

R 111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，可以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1種，亦可以使用2種以上。 具體而言，包含碳數2～20的直鏈或支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數3～20的芳香族基或由該等的組合構成之基團之二胺為較佳，包含碳數6～20的芳香族基之二胺為更佳。上述直鏈或支鏈的脂肪族基的鏈中的烴基可以被含雜原子之基團取代，上述環狀的脂肪族基及芳香族基的員環的烴基亦可以被含雜原子之基團取代。作為包含芳香族基之基團的例子，可以舉出下述基團。 R 111 is preferably derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, it includes a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof. A diamine having a group is preferred, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferred. The hydrocarbon groups in the chain of the above-mentioned linear or branched aliphatic groups may be substituted by heteroatom-containing groups. The hydrocarbon groups of the above-mentioned cyclic aliphatic groups and aromatic groups may also be substituted by heteroatom-containing groups. replace. Examples of the group containing an aromatic group include the following groups.

[化學式2] 式中，A表示單鍵或2價的連結基，單鍵或選自可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO 2-、-NHCO-或該等的組合之基團為較佳，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-或-SO 2-之基團為更佳，-CH 2-、-O-、-S-、-SO 2-、-C（CF 3） 2-或-C（CH 3） 2-為進一步較佳。 式中，*表示與其他結構的鍵結部位。 [Chemical formula 2] In the formula, A represents a single bond or a divalent linking group, and the single bond or aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -C(=O)-, -S- , -SO 2 -, -NHCO- or a combination of these groups is preferred, a single bond or an alkylene group with 1 to 3 carbon atoms that can be substituted by a fluorine atom, -O-, -C (= O)-, -S- or -SO 2 - groups are more preferred, -CH 2 -, -O-, -S-, -SO 2 -, -C (CF 3 ) 2 - or -C (CH 3 ) 2- is further preferred. In the formula, * represents the bonding site with other structures.

作為二胺，具體而言，可以舉出國際公開第2021/045126號的0078～0088段中所記載之化合物等。Specific examples of the diamine include compounds described in paragraphs 0078 to 0088 of International Publication No. 2021/045126, and the like.

從所獲得之有機膜的柔軟性的觀點考慮，R 111由-Ar-L-Ar-表示為較佳。其中，Ar分別獨立地為芳香族基，L為可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO 2-或-NHCO-、或者由上述2個以上的組合構成之基團。Ar為伸苯基為較佳，L為可以被氟原子取代之碳數1或2的脂肪族烴基、-O-、-CO-、-S-或-SO 2-為較佳。此處的脂肪族烴基為伸烷基為較佳。 From the viewpoint of flexibility of the obtained organic film, R 111 is preferably represented by -Ar-L-Ar-. Wherein, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO 2 - or -NHCO-, Or a group composed of a combination of two or more of the above. Ar is preferably a phenylene group, and L is an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- or -SO 2 -. The aliphatic hydrocarbon group here is preferably an alkylene group.

又，從i射線透射率的觀點考慮，R 111係下述式（51）或式（61）所表示之2價有機基團為較佳。尤其，從i射線透射率、易獲得性的觀點考慮，係式（61）所表示之2價有機基團為更佳。 式（51） [化學式3] 在式（51）中，R 50～R 57分別獨立地為氫原子、氟原子或1價有機基團，R 50～R 57中的至少1個為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為R 50～R 57的1價有機基團，可以舉出碳數1～10（較佳為碳數1～6）的未經取代之烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式4] 式（61）中，R 58及R 59分別獨立地為氟原子、甲基或三氟甲基，*分別獨立地表示與式（2）中的氮原子的鍵結部位。 作為賦予式（51）或（61）的結構之二胺，可以舉出2,2'-二甲基對聯苯胺、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。該等可以使用1種或組合使用2種以上。 Furthermore, 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, from the viewpoint of i-ray transmittance and easy availability, a divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 3] In formula (51), 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, a methyl group or a trifluoromethyl group, * Each independently represents the bonding site with the nitrogen atom in formula (2). Examples of the monovalent organic groups of R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). 1 to 6) fluorinated alkyl groups, etc. [Chemical formula 4] In the formula (61), R 58 and R 59 are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site with a nitrogen atom in the formula (2). Examples of the diamine that provides the structure of formula (51) or (61) include 2,2'-dimethyl p-benzidine and 2,2'-bis(trifluoromethyl)-4,4'-diamine. biphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used 1 type or in combination of 2 or more types.

式（2）中的R 115表示4價有機基團。作為4價有機基團，包含芳香環之4價有機基團為較佳，下述式（5）或式（6）所表示之基團為更佳。 式（5）或式（6）中，*分別獨立地表示與其他結構的鍵結部位。 [化學式5] 式（5）中，R 112為單鍵或2價連結基，單鍵或選自可以被氟原子取代之碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO 2-及-NHCO-、以及該等的組合之基團為較佳，單鍵、選自可以被氟原子取代之碳數1～3的伸烷基、-O-、-CO-、-S-及-SO 2-中之基團為更佳，選自包括-CH 2-、-C（CF 3） 2-、-C（CH 3） 2-、-O-、-CO-、-S-及-SO 2-之群組中之2價基團為進一步較佳。 R 115 in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In Formula (5) or Formula (6), * independently represents the bonding site with other structures. [Chemical formula 5] In formula (5), R 112 is a single bond or a divalent linking group, and the single bond or aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO 2 - and -NHCO-, and groups of combinations thereof are preferred. Single bonds are selected from alkylene groups with 1 to 3 carbon atoms that may be substituted by fluorine atoms, -O-, -CO-, The groups in -S- and -SO 2 - are more preferred, and are selected from the group consisting of -CH 2 -, -C (CF 3 ) 2 -, -C (CH 3 ) 2 -, -O-, -CO-, Bivalent groups in the group of -S- and -SO 2 - are further preferred.

具體而言，R 115可以舉出從四羧酸二酐去除酸酐基之後而殘留之四羧酸殘基等。作為對應於R 115之結構，聚醯亞胺前驅物可以僅包含1種四羧酸二酐殘基，亦可以包含2種以上。 四羧酸二酐係下述式（O）所表示為較佳。 [化學式6] 在式（O）中，R 115表示4價有機基團。R 115與式（2）中的R 115的含義相同，較佳範圍亦相同。 Specifically, examples of R 115 include the tetracarboxylic acid residue remaining after removing the acid anhydride group from tetracarboxylic dianhydride. As a structure corresponding to R 115 , the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical formula 6] In formula (O), R 115 represents a tetravalent organic group. R 115 has the same meaning as R 115 in formula (2), and the preferred range is also the same.

作為四羧酸二酐的具體例，可以舉出國際公開第2021/045126號的0029～0031段中所記載之化合物等。Specific examples of tetracarboxylic dianhydride include compounds described in paragraphs 0029 to 0031 of International Publication No. 2021/045126.

在式（2）中，亦可以為R 111及R 115中的至少1個具有OH基。更具體而言，作為R 111，可以舉出雙胺基苯酚衍生物的殘基。 In formula (2), at least one of R 111 and R 115 may have an OH group. More specifically, examples of R 111 include residues of bisaminophenol derivatives.

式（2）中的R 113及R 114分別獨立地表示氫原子或1價有機基團。作為1價有機基團，包含直鏈或支鏈的烷基、環狀烷基、芳香族基或聚伸烷氧基為較佳。又，R 113及R 114中的至少1個包含聚合性基為較佳，兩者均包含聚合性基為更佳。R 113及R 114中的至少1個包含2個以上的聚合性基亦為較佳。作為聚合性基，係能夠藉由熱、自由基等的作用進行交聯反應之基團，自由基聚合性基為較佳。作為聚合性基的具體例，可以舉出具有乙烯性不飽和鍵之基團、烷氧基甲基、羥基甲基、醯氧基甲基、環氧基、氧雜環丁基、苯并噁唑基、封端異氰酸酯基、胺基。作為聚醯亞胺前驅物所具有之自由基聚合性基，具有乙烯性不飽和鍵之基團為較佳。 作為具有乙烯性不飽和鍵之基團，可以舉出乙烯基、烯丙基、異烯丙基、2-甲基烯丙基、具有與乙烯基直接鍵結之芳香環之基團（例如，乙烯基苯基等）、（甲基）丙烯醯胺基、（甲基）丙烯醯氧基、下述式（III）所表示之基團等，下述式（III）所表示之基團為較佳。 R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Furthermore, it is preferred that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferred that both R 113 and R 114 contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups. The polymerizable group is a group that can undergo a cross-linking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, a hydroxymethyl group, an epoxy group, an oxetanyl group, and a benzoxane group. Azole group, blocked isocyanate group, amine group. As the radically polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, and a group having an aromatic ring directly bonded to a vinyl group (for example, Vinyl phenyl, etc.), (meth)acrylamide group, (meth)acryloxy group, a group represented by the following formula (III), etc. The group represented by the following formula (III) is Better.

[化學式7] [Chemical Formula 7]

在式（III）中，R 200表示氫原子、甲基、乙基或羥甲基，氫原子或甲基為較佳。 在式（III）中，*表示與其他結構的鍵結部位。 在式（III）中，R 201表示碳數2～12的伸烷基、-CH 2CH（OH）CH 2-、伸環烷基或聚伸烷氧基。 在本發明中，聚伸烷氧基係指2個以上的伸烷氧基直接鍵結之基團。聚伸烷氧基中所包含之複數個伸烷氧基中的伸烷基分別可以相同或不同。 聚伸烷氧基包含伸烷基不同之複數種伸烷氧基的情況下，聚伸烷氧基中的伸烷氧基的排列可以為隨機排列，可以為具有嵌段之排列，亦可以為具有交替等圖案之排列。 上述伸烷基的碳數（伸烷基具有取代基的情況下，包括取代基的碳數）為2以上為較佳，2～10為更佳，2～6為更佳，2～5為進一步較佳，2～4為更進一步較佳，2或3為特佳，2為最佳。 又，上述伸烷基可以具有取代基。作為較佳之取代基，可以舉出烷基、芳基、鹵素原子等。 又，聚伸烷氧基中所包含之伸烷氧基的數量（聚伸烷氧基的重複數）係2～20為較佳，2～10為更佳，2～6為進一步較佳。 作為聚伸烷氧基，從溶劑溶解性及耐溶劑性的觀點考慮，聚乙烯氧基、聚丙烯氧基、聚三亞甲氧基、聚四亞甲氧基或複數個乙烯氧基與複數個丙烯氧基鍵結之基團為較佳，聚乙烯氧基或聚丙烯氧基為更佳，聚乙烯氧基為進一步較佳。在上述複數個乙烯氧基與複數個丙烯氧基鍵結之基團中，乙烯氧基和丙烯氧基可以隨機排列，可以形成嵌段而排列，亦可以排列成交替等圖案狀。該等基團中的乙烯氧基等的重複數之較佳態樣如上所述。 In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with other structures. In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, a cycloalkylene group or a polyalkyleneoxy group. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains a plurality of alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be random, may be a block arrangement, or may be Arrangements with alternating patterns. The carbon number of the above-mentioned alkylene group (when the alkylene group has a substituent, the number of carbon atoms of the substituent is included) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, and 2 to 5. More preferably, 2 to 4 are even better, 2 or 3 is particularly good, and 2 is the best. Moreover, the above-mentioned alkylene group may have a substituent. Preferable substituents include alkyl groups, aryl groups, halogen atoms, and the like. In addition, the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and further preferably 2 to 6. As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy or a plurality of ethyleneoxy groups and a plurality of A propyleneoxy bonded group is preferred, polyethyleneoxy or polypropyleneoxy is more preferred, and polyvinyloxy is even more preferred. Among the groups in which a plurality of vinyloxy groups are bonded to a plurality of propyleneoxy groups, the vinyloxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. The preferred repeating numbers of vinyloxy groups and the like in these groups are as described above.

在式（2）中，在R 113為氫原子的情況或R 114為氫原子的情況下，聚醯亞胺前驅物可以與具有乙烯性不飽和鍵之三級胺化合物形成共軛鹽。作為該種具有乙烯性不飽和鍵之三級胺化合物的例子，可以舉出N,N-二甲胺基丙基甲基丙烯酸酯。 In the formula (2), when R 113 is a hydrogen atom or when R 114 is a hydrogen atom, the polyimide precursor may form a conjugated salt with a tertiary amine compound having an ethylenically unsaturated bond. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N,N-dimethylaminopropyl methacrylate.

在式（2）中，R 113及R 114中的至少1個可以為酸分解性基等極性轉換基。作為酸分解性基，只要藉由酸的作用分解並產生酚性羥基、羧基等鹼可溶性基，則並沒有特別限定，縮醛基、縮酮基、矽基、矽基醚基、三級烷基酯基等為較佳，從曝光靈敏度的觀點考慮，縮醛基或縮酮基為更佳。 In formula (2), at least one of R 113 and R 114 may be a polar converting group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. Acetal group, ketal group, silicon group, silicon ether group, tertiary alkyl group An ester group is preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity.

又，聚醯亞胺前驅物在結構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，又，20質量%以下為更佳。In addition, it is also preferred that the polyimide precursor has a fluorine atom in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

又，以提高與基板的密接性為目的，聚醯亞胺前驅物可以與具有矽氧烷結構之脂肪族基共聚。具體而言，作為二胺，可以舉出使用雙（3-胺基丙基）四甲基二矽氧烷、雙（對胺基苯基）八甲基五矽氧烷等之態樣。In addition, for the purpose of improving the adhesiveness with the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

式（2）所表示之重複單元係式（2-A）所表示之重複單元為較佳。亦即，在本發明中所使用之聚醯亞胺前驅物中的至少1種係具有式（2-A）所表示之重複單元之前驅物為較佳。藉由聚醯亞胺前驅物包含式（2-A）所表示之重複單元，能夠進一步增加曝光寬容度的幅度。 式（2-A） [化學式8] 式（2-A）中，A 1及A 2表示氧原子，R 111及R 112分別獨立地表示2價有機基團，R 113及R 114分別獨立地表示氫原子或1價有機基團，R 113及R 114中的至少1個為包含聚合性基之基團，兩者均為包含聚合性基之基團為較佳。 The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention has a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, the exposure latitude can be further increased. Formula (2-A) [Chemical Formula 8] In the formula (2-A), A 1 and A 2 represent oxygen atoms, R 111 and R 112 each independently represent a divalent organic group, R 113 and R 114 respectively independently represent a hydrogen atom or a monovalent organic group, At least one of R 113 and R 114 is a group containing a polymerizable group, and both of them are preferably groups containing a polymerizable group.

A 1、A 2、R 111、R 113及R 114分別獨立地與式（2）中的A 1、A 2、R 111、R 113及R 114的含義相同，較佳範圍亦相同。 R 112與式（5）中的R 112的含義相同，較佳範圍亦相同。 A 1 , A 2 , R 111 , R 113 and R 114 each independently have the same meaning as A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and the preferred ranges are also the same. R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.

聚醯亞胺前驅物可以包含1種式（2）所表示之重複單元，亦可以包含2種以上。又，可以包含式（2）所表示之重複單元的結構異構物。又，除上述式（2）的重複單元以外，聚醯亞胺前驅物顯然亦可以包含其他種類的重複單元。The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. Moreover, it may contain the structural isomer of the repeating unit represented by formula (2). In addition, in addition to the repeating units of the above formula (2), the polyimide precursor may obviously also contain other types of repeating units.

作為本發明中的聚醯亞胺前驅物的一實施形態，可以舉出式（2）所表示之重複單元的含量為所有重複單元的50莫耳%以上之態樣。上述合計含量係70莫耳%以上為更佳，90莫耳%以上為進一步較佳，大於90莫耳%為特佳。上述合計含量的上限並沒有特別限定，除了末端以外的聚醯亞胺前驅物中的所有重複單元可以為式（2）所表示之重複單元。As an embodiment of the polyimide precursor in the present invention, there is an aspect in which the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, more preferably 90 mol% or more, and more than 90 mol% is particularly preferred. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except the terminals may be repeating units represented by formula (2).

聚醯亞胺前驅物的重量平均分子量（Mw）較佳為5,000～100,000，更佳為10,000～50,000，進一步較佳為15,000～40,000。又，數量平均分子量（Mn）較佳為2,000～40,000，更佳為3,000～30,000，進一步較佳為4,000～20,000。 上述聚醯亞胺前驅物的分子量的分散度係1.5以上為較佳，1.8以上為更佳，2.0以上為進一步較佳。聚醯亞胺前驅物的分子量的分散度的上限值並沒有特別限定，例如，7.0以下為較佳，6.5以下為更佳，6.0以下為進一步較佳。 在本說明書中，分子量的分散度為藉由重量平均分子量/數量平均分子量計算出之值。 又，樹脂組成物包含複數種聚醯亞胺前驅物作為特定樹脂的情況下，至少1種聚醯亞胺前驅物的重量平均分子量、數量平均分子量及分散度在上述範圍為較佳。又，將上述複數種聚醯亞胺前驅物作為1種樹脂所計算出之重量平均分子量、數量平均分子量及分散度分別在上述範圍內亦為較佳。 The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, further preferably 15,000 to 40,000. Moreover, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and still more preferably 4,000 to 20,000. The molecular weight dispersion of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less. In this specification, the dispersion of molecular weight is a value calculated by weight average molecular weight/number average molecular weight. When the resin composition contains a plurality of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight and dispersion of at least one polyimide precursor are within the above ranges. In addition, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersion calculated by using the plurality of polyimide precursors as one resin are within the above ranges.

〔聚醯亞胺〕 用於本發明之聚醯亞胺可以為鹼可溶性聚醯亞胺，亦可以為在以有機溶劑為主成分之顯影液中可溶解之聚醯亞胺。 本說明書中，鹼可溶性聚醯亞胺係指在23℃下、在100g的2.38質量%四甲基銨水溶液中溶解0.1g以上的聚醯亞胺，從圖案形成性的觀點考慮，溶解0.5g以上的聚醯亞胺為較佳，溶解1.0g以上的聚醯亞胺為進一步較佳。上述溶解量的上限並沒有特別限定，100g以下為較佳。 又，從所獲得之有機膜的膜強度及絕緣性的觀點考慮，聚醯亞胺為在主鏈具有複數個醯亞胺結構之聚醯亞胺為較佳。 本說明書中，“主鏈”表示在構成樹脂之高分子化合物的分子中相對最長的鍵結鏈，“側鏈”表示除其以外的鍵結鏈。 〔Polyimide〕 The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer containing an organic solvent as the main component. In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves 0.1g or more in 100g of a 2.38 mass% tetramethylammonium aqueous solution at 23°C. From the viewpoint of pattern formation, 0.5g is dissolved The above-mentioned polyimide is preferred, and a polyimide in which 1.0 g or more is dissolved is further preferred. The upper limit of the above-mentioned dissolved amount is not particularly limited, but is preferably 100 g or less. Furthermore, from the viewpoint of film strength and insulation properties of the obtained organic film, it is preferable that the polyimide has a plurality of amide structures in the main chain. In this specification, the "main chain" means the relatively longest bonding chain among the molecules of the polymer compound constituting the resin, and the "side chain" means the bonding chains other than this.

-氟原子- 從所獲得之有機膜的膜強度的觀點考慮，聚醯亞胺具有氟原子亦為較佳。 氟原子例如包含於後述式（4）所表示之重複單元中的R 132或後述式（4）所表示之重複單元中的R 131為較佳，作為氟化烷基而包含於在後述式（4）所表示之重複單元中的R 132或後述式（4）所表示之重複單元中的R 131為更佳。 相對於聚醯亞胺的總質量之氟原子的量為5質量%以上為較佳，又，20質量%以下為較佳。 -Fluorine atom- From the viewpoint of film strength of the obtained organic film, it is also preferred that the polyimide has fluorine atoms. The fluorine atom is preferably contained in R 132 in the repeating unit represented by the following formula (4), or R 131 in the repeating unit represented by the following formula (4), and is contained as a fluorinated alkyl group in the following formula ( 4) R 132 in the repeating unit represented by the formula (4) or R 131 in the repeating unit represented by the following formula (4) are more preferred. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and more preferably 20% by mass or less.

-矽原子- 從所獲得之有機膜的膜強度的觀點考慮，聚醯亞胺具有矽原子亦為較佳。 矽原子例如包含於後述式（4）所表示之重複單元中的R 131為較佳，作為後述有機改質（聚）矽氧烷結構而包含於後述式（4）所表示之重複單元中的R 131為更佳。 又，上述矽原子或上述有機改質（聚）矽氧烷結構可以包含於聚醯亞胺的側鏈中，但包含於聚醯亞胺的主鏈中為較佳。 相對於聚醯亞胺的總質量之矽原子的量為1質量%以上為較佳，20質量%以下為更佳。 -Silicon atoms- From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide has silicon atoms. For example, the silicon atom is preferably R 131 contained in the repeating unit represented by the following formula (4), and R 131 is contained in the repeating unit represented by the following formula (4) as the organic modified (poly)siloxane structure described later. R 131 is better. Furthermore, the silicon atom or the organically modified (poly)siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

-乙烯性不飽和鍵- 從所獲得之有機膜的膜強度的觀點考慮，聚醯亞胺具有乙烯性不飽和鍵為較佳。 聚醯亞胺可以在主鏈末端具有乙烯性不飽和鍵，亦可以在側鏈具有乙烯性不飽和鍵，在側鏈具有為較佳。 上述乙烯性不飽和鍵具有自由基聚合性為較佳。 乙烯性不飽和鍵包含於後述式（4）所表示之重複單元中的R 132或後述式（4）所表示之重複單元中的R 131為較佳，作為具有乙烯性不飽和鍵之基團而包含於後述式（4）所表示之重複單元中的R 132或後述式（4）所表示之重複單元中的R 131為更佳。 在該等之中，乙烯性不飽和鍵包含於後述式（4）所表示之重複單元中的R 131為較佳，作為具有乙烯性不飽和鍵之基團而包含於後述式（4）所表示之重複單元中的R 131為更佳。 作為具有乙烯性不飽和鍵之基團，可以舉出乙烯基、烯丙基、乙烯基苯基等具有直接鍵結於芳香環之可以被取代的乙烯基之基團、（甲基）丙烯醯胺基、（甲基）丙烯醯氧基、下述式（IV）所表示之基團等。 -Ethylenically unsaturated bond- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has an ethylenically unsaturated bond. The polyimide may have an ethylenically unsaturated bond at the end of the main chain, or may have an ethylenically unsaturated bond at the side chain, and preferably it has an ethylenically unsaturated bond at the side chain. It is preferred that the ethylenically unsaturated bond has radical polymerizability. It is preferable that the ethylenically unsaturated bond is contained in R 132 in the repeating unit represented by the following formula (4) or R 131 in the repeating unit represented by the following formula (4) as the group having an ethylenically unsaturated bond. More preferably, R 132 contained in the repeating unit represented by the following formula (4) or R 131 contained in the repeating unit represented by the following formula (4). Among these, R 131 in which an ethylenically unsaturated bond is contained in the repeating unit represented by formula (4) to be described later is preferred, and R 131 is a group having an ethylenically unsaturated bond and is contained in the repeating unit represented by formula (4) to be described later. R 131 in the repeating unit is more preferred. Examples of the group having an ethylenically unsaturated bond include groups having an optionally substituted vinyl group directly bonded to an aromatic ring, such as vinyl, allyl, vinylphenyl, and (meth)acrylyl. Amino group, (meth)acryloxy group, group represented by the following formula (IV), etc.

[化學式9] [Chemical formula 9]

在式（IV）中，R 200表示氫原子、甲基、乙基或羥甲基，氫原子或甲基為較佳。 In formula (IV), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group.

在式（IV）中，R 21表示碳數2～12的伸烷基、-O-CH 2CH（OH）CH 2-、-C（=O）O-、-O（C=O）NH-、碳數2～30的（聚）伸烷氧基（伸烷基的碳數為2～12為較佳，2～6為更佳，2或3為特佳；重複數為1～12為較佳，1～6為更佳，1～3為特佳）或將該等組合2個以上而成之基團。 又，作為上述碳數2～12的伸烷基，可以為直鏈狀、支鏈狀、環狀或由該等的組合表示之伸烷基的任一種。 作為上述碳數2～12的伸烷基，碳數2～8的伸烷基為較佳，碳數2～4的伸烷基為更佳。 In formula (IV), R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -C(=O)O-, -O(C=O)NH -, (poly)alkyleneoxy group having 2 to 30 carbon atoms (the carbon number of the alkylene group is preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 or 3; the repeat number is 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is particularly preferred) or a group formed by combining two or more of these. In addition, the alkylene group having 2 to 12 carbon atoms may be any of linear, branched, cyclic, or a combination thereof. As the alkylene group having 2 to 12 carbon atoms, an alkylene group having 2 to 8 carbon atoms is preferred, and an alkylene group having 2 to 4 carbon atoms is more preferred.

在該等之中，R 21為由下述式（R1）～式（R3）中的任一個表示之基團為較佳，式（R1）所表示之基團為更佳。 [化學式10] 式（R1）～（R3）中，L表示單鍵或碳數2～12的伸烷基、碳數2～30的（聚）伸烷氧基或將該等鍵結2個以上而成之基團，X表示氧原子或硫原子，*表示與其他結構的鍵結部位，●表示與式（IV）中的R 21所鍵結之氧原子的鍵結部位。 在式（R1）～（R3）中，L中的碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣與上述R 21中的碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣相同。 在式（R1）中，X為氧原子為較佳。 式（R1）～（R3）中，*與式（IV）中的*的含義相同，較佳態樣亦相同。 式（R1）所表示之結構例如可藉由使酚性羥基等具有羥基之聚醯亞胺與具有異氰酸基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-異氰酸基乙酯等）進行反應來獲得。 式（R2）所表示之結構例如可藉由使具有羧基之聚醯亞胺與具有羥基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-羥乙酯等）進行反應來獲得。 式（R3）所表示之結構例如可藉由使酚性羥基等具有羥基之聚醯亞胺與具有環氧丙基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸環氧丙酯等）進行反應來獲得。 Among these, R 21 is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1). [Chemical formula 10] In formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or two or more of these bonds. In the group , In the formulas (R1) to (R3), the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the same as the carbon number in the above-mentioned R 21 Preferable aspects of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms are the same. In formula (R1), X is preferably an oxygen atom. In the formulas (R1) to (R3), * has the same meaning as * in the formula (IV), and the preferred aspects are also the same. The structure represented by the formula (R1) can be obtained by, for example, combining a polyimide having a hydroxyl group such as a phenolic hydroxyl group and a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatomethacrylate group Ethyl ester, etc.) are obtained by reaction. The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group and a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.). The structure represented by formula (R3) can be obtained by, for example, combining a polyimide having a hydroxyl group such as a phenolic hydroxyl group and a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.) Get the reaction.

在式（IV）中，*表示與其他結構的鍵結部位，與聚醯亞胺的主鏈的鍵結部位為較佳。In the formula (IV), * represents a bonding site with other structures, preferably a bonding site with the main chain of polyimide.

相對於聚醯亞胺的總質量之乙烯性不飽和鍵的量為0.0001～0.1mol/g為較佳，0.0005～0.05mol/g為更佳。The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.

-具有乙烯性不飽和鍵之基團以外的聚合性基- 聚醯亞胺可以包含除了具有乙烯性不飽和鍵之基團以外的聚合性基。 作為具有乙烯性不飽和鍵之基團以外的聚合性基，可以舉出環氧基、氧雜環丁基等環狀醚基、甲氧基甲基等的烷氧基甲基、羥甲基等。 例如，除具有乙烯性不飽和鍵之基團以外的聚合性基包含於後述式（4）所表示之重複單元中的R 131為較佳。 相對於聚醯亞胺的總質量之除了具有乙烯性不飽和鍵之基團以外的聚合性基的量為0.0001～0.1mol/g為較佳，0.001～0.05mol/g為更佳。 -Polymerizable group other than the group having an ethylenically unsaturated bond- The polyimide may contain a polymerizable group other than the group having an ethylenically unsaturated bond. Examples of polymerizable groups other than groups having an ethylenically unsaturated bond include cyclic ether groups such as epoxy groups and oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups. wait. For example, it is preferable that a polymerizable group other than a group having an ethylenically unsaturated bond is included in R 131 in the repeating unit represented by the formula (4) described below. The amount of polymerizable groups other than the group having an ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

-極性轉換基- 聚醯亞胺可以具有酸分解性基等極性轉換基。聚醯亞胺中的酸分解性基與在上述式（2）的R 113及R 114中說明的酸分解性基相同，較佳態樣亦相同。 極性轉換基例如包含於後述式（4）所表示之重複單元中的R 131、R 132、聚醯亞胺的末端等中。 -Polar converting group- The polyimide may have a polar converting group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group explained for R 113 and R 114 in the above formula (2), and the preferred aspects are also the same. The polar converting group is contained, for example, in R 131 and R 132 in the repeating unit represented by the formula (4) described below, the terminal of the polyimide, and the like.

-酸值- 將聚醯亞胺用於鹼顯影的情況下，從提高顯影性的觀點考慮，聚醯亞胺的酸值為30mgKOH/g以上為較佳，50mgKOH/g以上為更佳，70mgKOH/g以上為進一步較佳。 又，上述酸值為500mgKOH/g以下為較佳，400mgKOH/g以下為更佳，200mgKOH/g以下為進一步較佳。 又，在使用以有機溶劑為主成分之顯影液之顯影（例如，後述“溶劑顯影”）中使用聚醯亞胺的情況下，聚醯亞胺的酸值為1～35mgKOH/g為較佳，2～30mgKOH/g為更佳，5～20mgKOH/g為進一步較佳。 上述酸值藉由公知的方法測定，例如，藉由記載於JIS K 0070:1992中的方法測定。 又，作為包含在聚醯亞胺中的酸基，從兼顧保存穩定性及顯影性的觀點考慮，pKa為0～10的酸基為較佳，3～8的酸基為更佳。 pKa係考慮由酸釋放氫離子之解離反應而藉由其負常用對數pKa來表示其平衡常數Ka者。本說明書中，只要沒有特別說明，則將pKa設為基於ACD/ChemSketch（註冊商標）之計算值。或者，可以參考日本化學會編“改訂5版 化學便覽 基礎篇”中所記載之值。 又，酸基例如為磷酸等多元酸的情況下，上述pKa為第一解離常數。 作為該種酸基，聚醯亞胺包含選自包括羧基及酚性羥基之群組中之至少1種為較佳，包含酚性羥基為更佳。 -acid value- When polyimide is used for alkali development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and 70 mgKOH/g or more. Better still. Moreover, the above-mentioned acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and still more preferably 200 mgKOH/g or less. Furthermore, when polyimide is used for development using a developer containing an organic solvent as the main component (for example, "solvent development" described below), the acid value of the polyimide is preferably 1 to 35 mgKOH/g. , 2 to 30 mgKOH/g is more preferred, and 5 to 20 mgKOH/g is still more preferred. The acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. In addition, as the acid group contained in the polyimide, from the viewpoint of balancing storage stability and developability, those having a pKa of 0 to 10 are preferred, and those having a pKa of 3 to 8 are more preferred. pKa takes into account the dissociation reaction of releasing hydrogen ions from acid and expresses its equilibrium constant Ka by its negative common logarithm pKa. In this manual, unless otherwise stated, pKa is a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, you can refer to the values recorded in "Chemistry Handbook, Basics, Revised 5th Edition" compiled by the Chemical Society of Japan. When the acid group is a polybasic acid such as phosphoric acid, the pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

-酚性羥基- 從使基於鹼顯影液之顯影速度適當的觀點考慮，聚醯亞胺具有酚性羥基為較佳。 聚醯亞胺可以在主鏈末端具有酚性羥基，亦可以在側鏈具有酚性羥基。 酚性羥基例如包含於後述式（4）所表示之重複單元中的R 132或後述式（4）所表示之重複單元中的R 131為較佳。 相對於聚醯亞胺的總質量之酚性羥基的量為0.1～30mol/g為較佳，1～20mol/g為更佳。 -Phenolic hydroxyl group- From the viewpoint of appropriate development speed using an alkali developer, it is preferred that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain or a phenolic hydroxyl group in the side chain. The phenolic hydroxyl group is preferably contained in R 132 in the repeating unit represented by the following formula (4) or R 131 in the repeating unit represented by the following formula (4), for example. The amount of phenolic hydroxyl groups relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

作為本發明中所使用之聚醯亞胺，只要為具有醯亞胺結構之高分子化合物，則並沒有特別限定，包含下述式（4）所表示之重複單元為較佳。 [化學式11] 在式（4）中，R 131表示2價有機基團，R 132表示4價有機基團。 具有聚合性基的情況下，聚合性基可以位於R 131及R 132中的至少1個上，亦可以如下述式（4-1）或式（4-2）所示，位於聚醯亞胺的末端。 式（4-1） [化學式12] 式（4-1）中，R 133為聚合性基，其他基團與式（4）的含義相同。 式（4-2） [化學式13] R 134及R 135中的至少1個為聚合性基，不是聚合性基的情況下為有機基團，其他基團與式（4）的含義相同。 The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imine structure, but it is preferably a polyimide containing a repeating unit represented by the following formula (4). [Chemical formula 11] In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group. When a polymerizable group is present, the polymerizable group may be located on at least one of R 131 and R 132 , or may be located on the polyimide as shown in the following formula (4-1) or formula (4-2). end. Formula (4-1) [Chemical Formula 12] In formula (4-1), R 133 is a polymerizable group, and other groups have the same meanings as in formula (4). Formula (4-2) [Chemical Formula 13] At least one of R 134 and R 135 is a polymerizable group. If not, it is an organic group. The other groups have the same meaning as in formula (4).

作為聚合性基，可以舉出包含上述乙烯性不飽和鍵之基團或包含上述乙烯性不飽和鍵之基團以外的交聯性基。 R 131表示2價有機基團。作為2價有機基團，可以例示出與式（2）中的R 111相同者，較佳範圍亦相同。 又，作為R 131，可以舉出去除二胺的胺基後殘留之二胺殘基。作為二胺，可以舉出脂肪族、環式脂肪族或芳香族二胺等。作為具體例，可以舉出聚醯亞胺前驅物的式（2）中的R 111的例子。 Examples of the polymerizable group include the group containing the above-mentioned ethylenically unsaturated bond or a crosslinkable group other than the group containing the above-mentioned ethylenically unsaturated bond. R 131 represents a divalent organic group. Examples of the divalent organic group include the same ones as R 111 in formula (2), and the preferred ranges are also the same. Moreover, examples of R 131 include the diamine residue remaining after removing the amine group of the diamine. Examples of diamines include aliphatic, cycloaliphatic or aromatic diamines. As a specific example, R 111 in the formula (2) of the polyimide precursor can be cited.

從更有效地抑制燒成時產生翹曲的觀點考慮，R 131為在主鏈具有至少2個伸烷基二醇單元之二胺殘基為較佳。更佳為在一分子中共計包含2個以上的乙二醇鏈、丙二醇鏈中的任一個或兩者之二胺、進一步較佳為上述二胺且不包含芳香環之二胺殘基。 From the viewpoint of more effectively suppressing warpage during firing, R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain. More preferably, it is a diamine containing a total of two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and still more preferably, it is a diamine residue in which the above-mentioned diamine does not contain an aromatic ring.

作為在一分子中共計包含2個以上的乙二醇鏈、丙二醇鏈中的任一個或兩者之二胺，可以舉出JEFFAMINE（註冊商標）KH-511、ED-600、ED-900、ED-2003、EDR-148、EDR-176、D-200、D-400、D-2000、D-4000（以上為商品名，Huntsman Corporation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。Examples of diamines containing a total of two or more ethylene glycol chains or propylene glycol chains or both in one molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED -2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (the above are trade names, manufactured by Huntsman Corporation), 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 are not limited to these.

R 132表示4價有機基團。作為4價有機基團，可以例示出與式（2）中的R 115相同者，較佳範圍亦相同。 例如，作為R 115例示之4價有機基團的4個鍵結鍵與上述式（4）中的4個-C（=O）-的部分鍵結而形成縮合環。 R 132 represents a tetravalent organic group. Examples of the tetravalent organic group include the same ones as R 115 in formula (2), and the preferred ranges are also the same. For example, four bonds of the tetravalent organic group exemplified as R 115 are bonded to four -C (=O)- portions in the above formula (4) to form a condensed ring.

又，R 132可以舉出從四羧酸二酐去除酸酐基之後殘留之四羧酸殘基等。作為具體例，可以舉出聚醯亞胺前驅物的式（2）中的R 115的例子。從有機膜的強度的觀點考慮，R 132為具有1～4個芳香環之芳香族二胺殘基為較佳。 Moreover, examples of R 132 include the tetracarboxylic acid residue remaining after removing the acid anhydride group from tetracarboxylic dianhydride. As a specific example, R 115 in the formula (2) of the polyimide precursor can be cited. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

在R 131和R 132中的至少1個上具有OH基亦為較佳。更具體而言，作為R 131，可以舉出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、上述（DA-1）～（DA-18）作為較佳例，作為R 132，可以舉出上述（DAA-1）～（DAA-5）作為更佳例。 It is also preferred that at least one of R 131 and R 132 has an OH group. More specifically, examples of R 131 include 2,2-bis(3-hydroxy-4-aminophenyl)propane and 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoro Propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, the above (DA-1) ~ ( DA-18) As a preferred example, as R 132 , the above-mentioned (DAA-1) to (DAA-5) can be cited as more preferred examples.

又，聚醯亞胺在結構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，又，20質量%以下為較佳。In addition, it is also preferable that the polyimide has a fluorine atom in the structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

又，以提高與基板的密接性為目的，聚醯亞胺可以與具有矽氧烷結構之脂肪族基共聚。具體而言，作為二胺成分，可以舉出雙（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。In addition, for the purpose of improving the adhesiveness with the substrate, polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

又，為了提高樹脂組成物的保存穩定性，聚醯亞胺的主鏈末端被單胺、酸酐、單羧酸、單醯氯化合物、活性單酯化合物等封端劑密封為較佳。作為封端劑，可以舉出國際公開第2021/045126號的0090段中所記載之封端劑等。In addition, in order to improve the storage stability of the resin composition, it is preferable that the main chain end of the polyimide is sealed with an end-capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monochloride compound, or an active monoester compound. Examples of the blocking agent include those described in paragraph 0090 of International Publication No. 2021/045126.

-醯亞胺化率（閉環率）- 從所獲得之有機膜的膜強度、絕緣性等觀點考慮，聚醯亞胺的醯亞胺化率（亦稱為“閉環率”）為70%以上為較佳，80%以上為更佳，90%以上為更佳。 上述醯亞胺化率的上限並沒有特別限定，100%以下即可。 例如可藉由下述方法測定上述醯亞胺化率。 測定聚醯亞胺的紅外吸收光譜，求出源自醯亞胺結構之吸收峰亦即1377cm -1附近的峰強度P1。接著，將該聚醯亞胺在350℃下熱處理1小時之後，再次測定紅外吸收光譜，求出1377cm -1附近的峰強度P2。利用所獲得之峰強度P1、P2，根據下述式，能夠求出聚醯亞胺的醯亞胺化率。 醯亞胺化率（%）=（峰強度P1/峰強度P2）×100 -Imination rate (loop closure rate)- From the viewpoint of the film strength and insulation properties of the obtained organic film, the imidization rate (also called "loop closure rate") of polyimide is 70% or more It is better, more than 80% is better, and more than 90% is even better. The upper limit of the above-mentioned imidization rate is not particularly limited, and may be 100% or less. For example, the above-mentioned acyl imidization rate can be measured by the following method. The infrared absorption spectrum of the polyimide was measured to determine the peak intensity P1 near 1377 cm -1 which is the absorption peak derived from the imide structure. Next, the polyimide was heat-treated at 350° C. for 1 hour, and then the infrared absorption spectrum was measured again to determine the peak intensity P2 near 1377 cm −1 . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be determined according to the following formula. Ethylene imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

聚醯亞胺可以全部包含含有1種R 131或R 132之上述式（4）所表示之重複單元，亦可以包含含有2個以上不同種類的R 131或R 132之上述式（4）所表示之重複單元。又，聚醯亞胺除了包含上述式（4）所表示之重複單元以外，亦可以包含其他種類的重複單。作為其他種類的重複單元，例如，可以舉出上述式（2）所表示之重複單元等。 The polyimide may contain all of the repeating units represented by the above formula (4) containing one type of R 131 or R 132 , or may contain two or more different types of R 131 or R 132 represented by the above formula (4). of repeating units. In addition, the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Examples of other types of repeating units include repeating units represented by the above formula (2).

例如，聚醯亞胺能夠利用在低溫中使四羧酸二酐與二胺（將一部分取代為單胺亦即封端劑）反應之方法、在低溫中使四羧酸二酐（將一部分取代為酸酐或單醯氯化合物或活性單酯化合物亦即封端劑）與二胺反應之方法、藉由四羧酸二酐及醇獲得二酯之後使其在二胺（將一部分取代為單胺亦即封端劑）及縮合劑的存在下反應之方法、藉由四羧酸二酐及醇獲得二酯之後醯氯化剩餘的二羧酸並使其與二胺（將一部分取代為單胺亦即封端劑）反應之方法等方法獲得聚醯亞胺前驅物，並利用藉由以往之醯亞胺化反應法將其完全醯亞胺化之方法、或者中途停止醯亞胺化反應並導入一部分醯亞胺結構之方法，藉由進一步混合完全醯亞胺化之聚合物及其聚醯亞胺前驅物來導入一部分醯亞胺結構之方法合成。又，亦能夠適用其他公知的聚醯亞胺的合成方法。For example, polyimide can use a method of reacting tetracarboxylic dianhydride with diamine (part of which is replaced by monoamine, that is, a blocking agent) at low temperature, and making tetracarboxylic dianhydride (part of it substituted with monoamine, that is, a blocking agent) at low temperature. It is a method of reacting an acid anhydride or a monochloride compound or an active monoester compound (i.e., a blocking agent) with a diamine. After obtaining the diester from tetracarboxylic dianhydride and alcohol, it is replaced with the diamine (part of which is replaced by a monoamine). A method of reacting in the presence of a capping agent) and a condensing agent, obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then chlorinating the remaining dicarboxylic acid with a diamine (part of which is replaced by a monoamine (i.e. end-capping agent) reaction method to obtain the polyimide precursor, and use the method of completely imidizing it by the conventional imidization reaction method, or stop the imidization reaction midway and The method of introducing a part of the amide imine structure is synthesized by further mixing a fully imidized polymer and its polyimide precursor to introduce a part of the amide imine structure. In addition, other known polyimide synthesis methods can also be applied.

聚醯亞胺的重量平均分子量（Mw）較佳為5,000～100,000，更佳為10,000～50,000，進一步較佳為15,000～40,000。藉由將重量平均分子量設為5,000以上，能夠提高硬化後的膜的耐折彎性。為了獲得機械特性（例如，斷裂伸長率）優異之有機膜，重量平均分子量為15,000以上為特佳。 又，聚醯亞胺的數平均分子量（Mn）較佳為2,000～40,000，更佳為3,000～30,000，進一步較佳為4,000～20,000。 上述聚醯亞胺的分子量的分散度為1.5以上為較佳，1.8以上為更佳，2.0以上為進一步較佳。聚醯亞胺前驅物的分子量的分散度的上限值並沒有特別限定，例如，7.0以下為較佳，6.5以下為更佳，6.0以下為進一步較佳。 又，樹脂組成物包含複數種聚醯亞胺作為特定樹脂的情況下，至少1種聚醯亞胺的重量平均分子量、數量平均分子量及分散度在上述範圍為較佳。又，將上述複數種聚醯亞胺作為1種樹脂而計算出之重量平均分子量、數量平均分子量及分散度分別在上述範圍內亦為較佳。 The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, further preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (for example, elongation at break), a weight average molecular weight of 15,000 or more is particularly preferred. Moreover, the number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000. The molecular weight dispersion of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and still more preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and further preferably 6.0 or less. When the resin composition contains a plurality of polyimides as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyimide fall within the above ranges. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the dispersion degree calculated using the plurality of polyimides mentioned above as one resin are within the above ranges.

〔聚苯并噁唑前驅物〕 關於在本發明中所使用之聚苯并噁唑前驅物，對其結構並沒有特別限定，較佳為包含下述式（3）所表示之重複單元。 [化學式14] 在式（3）中，R 121表示2價有機基團，R 122表示4價有機基團，R 123及R 124分別獨立地表示氫原子或1價有機基團。 [Polybenzoxazole Precursor] The structure of the polybenzoxazole precursor used in the present invention is not particularly limited, but it preferably contains a repeating unit represented by the following formula (3). [Chemical formula 14] In the formula (3), 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.

在式（3）中，R 123及R 124分別與式（2）中的R 113的含義相同，較佳範圍亦相同。亦即，至少1個為聚合性基為較佳。 式（3）中，R 121表示2價有機基團。作為2價有機基團，包含脂肪族基及芳香族基中的至少1個之基團為較佳。作為脂肪族基，直鏈脂肪族基為較佳。R 121為二羧酸殘基為較佳。二羧酸殘基可以僅使用1種，亦可以使用2種以上。 In the formula (3), R 123 and R 124 have the same meaning as R 113 in the formula (2), and the preferred ranges are also the same. That is, it is preferable that at least one is a polymerizable group. In formula (3), R 121 represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferred. As the aliphatic group, a linear aliphatic group is preferred. R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

〔聚醯胺醯亞胺前驅物〕 聚醯胺醯亞胺前驅物包含下述式（PAI-2）所表示之重複單元為較佳。 [化學式15] 在式（PAI-2）中，R 117表示3價有機基團，R 111表示2價有機基團，A 2表示氧原子或-NH-，R 113表示氫原子或1價有機基團。 [Polyamide imine precursor] The polyamide imine precursor preferably contains a repeating unit represented by the following formula (PAI-2). [Chemical formula 15] In the formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NH-, and R 113 represents a hydrogen atom or a monovalent organic group.

〔聚醯亞胺前驅物等的製造方法〕 例如，聚醯亞胺前驅物等能夠利用如下方法獲得：在低溫中使四羧酸二酐與二胺反應之方法、在低溫中使四羧酸二酐與二胺反應來獲得聚醯胺酸並用縮合劑或烷基化劑酯化之方法、藉由四羧酸二酐及醇獲得二酯之後使其在二胺及縮合劑的存在下反應之方法、藉由四羧酸二酐及醇獲得二酯之後用鹵化劑鹵化剩餘的二羧酸並使其與二胺反應之方法等。上述製造方法中，藉由四羧酸二酐與醇獲得二酯之後用鹵化劑鹵化剩餘的二羧酸並使其與二胺反應之方法為更佳。 作為上述縮合劑，例如可以舉出二環己碳二亞胺、二異丙基碳二亞胺、1-乙氧基羰基-2-乙氧基-1,2-二氫喹啉、1,1-羰基二氧基-二-1,2,3-苯并三唑、N,N’-二琥珀醯亞胺碳酸酯、三氟乙酸酐等。 作為上述烷基化劑，可以舉出N,N-二甲基甲醯胺二甲基縮醛、N,N-二甲基甲醯胺二乙基縮醛、N,N-二烷基甲醯胺二烷基縮醛、原甲酸三甲酯、原甲酸三乙酯等。 作為上述鹵化劑，可以舉出亞硫醯氯、草醯氯、磷醯氯等。 在聚醯亞胺前驅物等的製造方法中，在進行反應時，使用有機溶劑為較佳。有機溶劑可以為1種，亦可以為2種以上。 作為有機溶劑，能夠根據原料而適當確定，可以例示出吡啶、二乙二醇二甲醚（二甘二甲醚）、N-甲基吡咯啶酮、N-乙基吡咯啶酮、丙酸乙酯、二甲基乙醯胺、二甲基甲醯胺、四氫呋喃、γ-丁內酯等。 在聚醯亞胺前驅物等的製造方法中，在進行反應時，添加鹼性化合物為較佳。鹼性化合物可以為1種，亦可以為2種以上。 鹼性化合物能夠根據原料而適當確定，可以例示出三乙胺、二異丙基乙胺、吡啶、1,8-二吖雙環[5.4.0]十一-7-烯、N,N-二甲基-4-胺吡啶等。 [Production method of polyimide precursor, etc.] For example, polyimide precursors and the like can be obtained by the following methods: reacting tetracarboxylic dianhydride and diamine at low temperature, and obtaining polyimide by reacting tetracarboxylic dianhydride and diamine at low temperature. The method of esterification using a condensing agent or an alkylating agent together, the method of obtaining the diester from tetracarboxylic dianhydride and alcohol and then reacting it in the presence of diamine and condensing agent, the method of using tetracarboxylic dianhydride and alcohol After obtaining the diester, the remaining dicarboxylic acid is halogenated with a halogenating agent and reacted with the diamine, etc. Among the above-mentioned production methods, the method of obtaining the diester from tetracarboxylic dianhydride and alcohol and then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with the diamine is more preferred. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, and 1, 1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimide carbonate, trifluoroacetic anhydride, etc. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, and N,N-dialkylmethane. Amide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus chloride, and the like. In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent during the reaction. The organic solvent may be one type or two or more types. The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diglyme, N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl propionate. Ester, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the method of producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The number of basic compounds may be one type or two or more types. The basic compound can be appropriately determined depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-dioxabicyclo[5.4.0]undec-7-ene, and N,N-di Methyl-4-aminepyridine, etc.

-封端劑- 在製造聚醯亞胺前驅物等時，為了進一步提高保存穩定性，密封殘留在聚醯亞胺前驅物等樹脂末端之羧酸酐、酸酐衍生物或胺基為較佳。密封殘留於樹脂末端之羧酸酐及酸酐衍生物時，作為封端劑，可以舉出單醇、苯酚、硫醇、苯硫酚、單胺等，從反應性、膜的穩定性考慮，使用單醇、酚類或單胺為更佳。作為單醇的較佳之化合物，可以舉出甲醇、乙醇、丙醇、丁醇、己醇、辛醇、十二醇、苯甲醇、2-苯基乙醇、2-甲氧基乙醇、2-氯甲醇、糠醇等一級醇、異丙醇、2-丁醇、環己醇、環戊醇、1-甲氧基-2-丙醇等二級醇、三級丁醇、金剛烷醇等三級醇。作為酚類的較佳之化合物，可以舉出苯酚、甲氧基苯酚、甲基苯酚、萘-1-醇、萘-2-醇、羥基苯乙烯等酚類等。又，作為單胺的較佳之化合物，可以舉出苯胺、2-乙炔基苯胺、3-乙炔基苯胺、4-乙炔基苯胺、5-胺基-8-羥喹啉、1-羥基-7-胺萘、1-羥基-6-胺萘、1-羥基-5-胺萘、1-羥基-4-胺萘、2-羥基-7-胺萘、2-羥基-6-胺萘、2-羥基-5-胺萘、1-羧基-7-胺萘、1-羧基-6-胺萘、1-羧基-5-胺萘、2-羧基-7-胺萘、2-羧基-6-胺萘、2-羧基-5-胺萘、2-胺基苯甲酸、3-胺基苯甲酸、4-胺基苯甲酸、4-胺基水楊酸、5-胺基水楊酸、6-胺基水楊酸、2-胺基苯磺酸、3-胺基苯磺酸、4-胺基苯磺酸、3-胺基-4,6-二羥基嘧啶、2-胺基苯酚、3-胺基苯酚、4-胺基苯酚、2-胺基苯硫酚、3-胺基苯硫酚、4-胺基苯硫酚等。該等可以使用2種以上，亦可以藉由使複數種封端劑反應而導入複數種不同之末端基。 又，在密封樹脂末端的胺基時，能夠用具有可與胺基反應的官能基之化合物進行密封。對胺基較佳之封端劑係羧酸酐、羧酸氯化物、羧酸溴化物、磺酸氯化物、磺酸酐、磺酸羧酸酐等為較佳，羧酸酐、羧酸氯化物為更佳。作為羧酸酐的較佳之化合物，可以舉出乙酸酐、丙酸酐、草酸酐、琥珀酸酐、順丁烯二酸酐、鄰苯二甲酸酐、苯甲酸酐、5-降莰烯-2,3-二羧酸酐等。又，作為羧酸氯化物的較佳之化合物，可以舉出乙醯氯、丙烯醯氯、丙醯氯、甲基丙烯醯氯、新戊醯氯、環己烷甲醯氯、2-乙基己醯氯、桂皮醯氯、1-金剛烷甲醯氯、七氟丁醯氯、硬脂醯氯、苯甲醯氯等。 -Capping agent- When producing a polyimide precursor, etc., in order to further improve storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative or amine group remaining at the terminal end of the resin such as the polyimide precursor. When sealing carboxylic acid anhydrides and acid anhydride derivatives remaining at the end of the resin, examples of end-capping agents include monoalcohols, phenols, mercaptans, thiophenols, monoamines, etc. In terms of reactivity and film stability, use of monoalcohols is recommended. Alcohols, phenols or monoamines are more preferred. Preferred compounds of monoalcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, and 2-chloro Primary alcohols such as methanol and furfuryl alcohol, secondary alcohols such as isopropyl alcohol, 2-butanol, cyclohexanol, cyclopentanol, and 1-methoxy-2-propanol, tertiary alcohols such as tertiary butanol, and adamantanol alcohol. Preferred compounds of phenols include phenols such as phenol, methoxyphenol, tolylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Preferred compounds of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7- Aminonaphthalene, 1-hydroxy-6-aminenaphthalene, 1-hydroxy-5-aminenaphthalene, 1-hydroxy-4-aminenaphthalene, 2-hydroxy-7-aminenaphthalene, 2-hydroxy-6-aminenaphthalene, 2- Hydroxy-5-aminenaphthalene, 1-carboxy-7-aminenaphthalene, 1-carboxy-6-aminenaphthalene, 1-carboxy-5-aminenaphthalene, 2-carboxy-7-aminenaphthalene, 2-carboxy-6-amine Naphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6- Aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3 -Aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more types of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents. When sealing the amine group at the end of the resin, a compound having a functional group capable of reacting with the amine group can be used for sealing. Preferred end-capping agents for amine groups are carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride, etc. Carboxylic acid anhydride and carboxylic acid chloride are even more preferred. Preferred compounds of carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-di. Carboxylic anhydride, etc. Preferable compounds of carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propyl chloride, methacrylic acid chloride, neopentyl chloride, cyclohexanecarboxylic acid chloride, and 2-ethylhexyl chloride. Cinnamon chloride, cinnamon chloride, 1-adamantane methyl chloride, heptafluorobutyl chloride, stearyl chloride, benzyl chloride, etc.

-固體析出- 在製造聚醯亞胺前驅物等時，可以包括固體析出步驟。具體而言，根據需要過濾出反應液中共存之脫水縮合劑的吸水副產物之後，在水、脂肪族低級醇或其混合液等不良溶劑中投入所獲得之聚合物成分並析出聚合物成分，藉此以固體析出並使其乾燥從而能夠獲得聚醯亞胺前驅物等。為了提高純化度，可以對聚醯亞胺前驅物等反覆進行再溶解、再沉澱析出、乾燥等操作。亦可以進一步包括使用離子交換樹脂去除離子性雜質之步驟。 -Solid precipitation- When producing a polyimide precursor or the like, a solid precipitation step may be included. Specifically, after filtering out the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution as necessary, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohol or a mixture thereof, and the polymer component is precipitated. Thereby, a polyimide precursor etc. can be obtained by precipitating a solid and drying it. In order to improve the degree of purification, the polyimide precursor and the like can be repeatedly redissolved, reprecipitated, and dried. It may further include the step of using an ion exchange resin to remove ionic impurities.

〔含量〕 特定樹脂在本發明的樹脂組成物中的含量相對於樹脂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。又，本發明的樹脂組成物中的樹脂的含量相對於樹脂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%以下為再進一步較佳。 本發明的樹脂組成物可以僅包含1種特定樹脂，亦可以包含2種以上。在包含2種以上的情況下，合計量在上述範圍內為較佳。 〔content〕 The content of the specific resin in the resin composition of the present invention is preferably 20 mass% or more, more preferably 30 mass% or more, more preferably 40 mass% or more, and 50 mass% or more relative to the total solid content of the resin composition. The above is further better. In addition, the resin content in the resin composition of the present invention is preferably 99.5 mass% or less, more preferably 99 mass% or less, further preferably 98 mass% or less, and 97 mass% or less relative to the total solid content of the resin composition. % or less is more preferably, and 95 mass % or less is still more preferably. The resin composition of the present invention may contain only one specific resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

又，本發明的樹脂組成物包含至少2種樹脂亦為較佳。 具體而言，本發明的樹脂組成物可以將特定樹脂和後述之其他樹脂合計包含2種以上，亦可以包含2種以上的特定樹脂，包含2種以上特定樹脂為較佳。 在本發明的樹脂組成物包含2種以上的特定樹脂的情況下，例如包含源自二酐的結構（上述式（2）中的R 115）不同之2種以上的聚醯亞胺前驅物為較佳。 Furthermore, the resin composition of the present invention preferably contains at least two kinds of resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described below, or may contain two or more specific resins, and preferably contains two or more specific resins. When the resin composition of the present invention contains two or more specific resins, for example, it contains two or more polyimide precursors with different structures derived from dianhydrides (R 115 in the above formula (2)). Better.

＜其他樹脂＞ 本發明的樹脂組成物可以包含上述特定樹脂及與特定樹脂不同之其他樹脂（以下，亦簡稱為“其他樹脂”）。 作為其他樹脂，可以舉出酚樹脂、聚醯胺、環氧樹脂、聚矽氧烷、包含矽氧烷結構之樹脂、（甲基）丙烯酸樹脂、（甲基）丙烯醯胺樹脂、胺基甲酸酯樹脂、丁醛樹脂、苯乙烯樹脂、聚醚樹脂、聚酯樹脂等。 例如，藉由進一步添加（甲基）丙烯酸樹脂，可以獲得塗佈性優異之樹脂組成物，又，可以獲得耐溶劑性優異之圖案（硬化物）。 例如，藉由代替後述之聚合性化合物或者除了後述之聚合性化合物以外，將重量平均分子量為20,000以下的聚合性基值高（例如，樹脂1g中聚合性基的含有莫耳量為1×10 -3莫耳/g以上）的（甲基）丙烯酸樹脂添加於樹脂組成物中，能夠提高樹脂組成物的塗佈性、圖案（硬化物）的耐溶劑性等。 <Other resins> The resin composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also referred to as "other resins"). Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, and aminomethane resins. Acid ester resin, butyral resin, styrene resin, polyether resin, polyester resin, etc. For example, by further adding (meth)acrylic resin, a resin composition excellent in coatability can be obtained, and a pattern (cured product) excellent in solvent resistance can be obtained. For example, by replacing or in addition to the polymerizable compound described below, a polymerizable group having a weight average molecular weight of 20,000 or less has a high polymerizable group value (for example, the molar content of the polymerizable group in 1 g of the resin is 1×10 -3 mol/g or more) (meth)acrylic resin is added to the resin composition to improve the coating properties of the resin composition, the solvent resistance of the pattern (cured product), etc.

在本發明的樹脂組成物包含其他樹脂的情況下，其他樹脂的含量相對於樹脂組成物的總固體成分係0.01質量%以上為較佳，0.05質量%以上為更佳，1質量%以上為進一步較佳，2質量%以上為進一步較佳，5質量%以上為更進一步較佳，10質量%以上為再進一步較佳。 又，本發明的樹脂組成物中的其他樹脂的含量相對於樹脂組成物的總固體成分係80質量%以下為較佳，75質量%以下為更佳，70質量%以下為進一步較佳，60質量%以下為更進一步較佳，50質量%以下為再進一步較佳。 又，作為本發明的樹脂組成物的較佳之一態樣，亦能夠設為其他樹脂的含量為低含量的態樣。在上述態樣中，其他樹脂的含量相對於樹脂組成物的總固體成分係20質量%以下為較佳，15質量%以下為更佳，10質量%以下為進一步較佳，5質量%以下為更進一步較佳，1質量%以下為再進一步較佳。上述含量的下限並沒有特別限定，0質量%以上即可。 本發明的樹脂組成物可以僅包含1種其他樹脂，亦可以包含2種以上。在包含2種以上的情況下，合計量在上述範圍內為較佳。 When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01 mass % or more, more preferably 0.05 mass % or more, and further 1 mass % or more relative to the total solid content of the resin composition. Preferably, it is more preferably 2 mass % or more, still more preferably 5 mass % or more, and still more preferably 10 mass % or more. In addition, the content of other resins in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, and further preferably 70 mass% or less, based on the total solid content of the resin composition. 60 mass% or less is more preferred. It is more preferable that it is 50 mass % or less, and it is more preferable that it is 50 mass % or less. In addition, as a preferred aspect of the resin composition of the present invention, the content of other resins can also be set to a low content. In the above aspect, the content of other resins relative to the total solid content of the resin composition is preferably 20 mass% or less, more preferably 15 mass% or less, further preferably 10 mass% or less, and 5 mass% or less. More preferably, it is 1% by mass or less. The lower limit of the above content is not particularly limited, but it may be 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

＜溶劑B＞ 本發明的樹脂組成物包含SP值為21.0（J/cm 3） 0.5以上且小於25.0（J/cm 3） 0.5之溶劑B。 溶劑B係有機溶劑為較佳。 溶劑B的SP值係21.5（J/cm 3） 0.5以上為較佳，22.0（J/cm 3） 0.5以上為更佳。又，24.0（J/cm 3） 0.5以下為較佳，23.0（J/cm 3） 0.5以下為更佳。 <Solvent B> The resin composition of the present invention contains solvent B having an SP value of 21.0 (J/cm 3 ) 0.5 or more and less than 25.0 (J/cm 3 ) 0.5 . Solvent B is an organic solvent and is preferred. The SP value of solvent B is preferably 21.5 (J/cm 3 ) 0.5 or more, and more preferably 22.0 (J/cm 3 ) 0.5 or more. Moreover, it is more preferable that it is 24.0 (J/ cm3 ) 0.5 or less, and it is more preferable that it is 23.0 (J/ cm3 ) 0.5 or less.

相對於25℃、100g的溶劑B，特定樹脂對溶劑B的溶解度係5g/100g以上為較佳，10g/100g以上為更佳，20g/100g以上為進一步較佳。 在本發明的感光性樹脂組成物包含複數種特定樹脂或溶劑B中的任一個或兩個的情況下，至少1種特定樹脂與至少1種溶劑B的各自的組合中的溶解度在上述範圍內即可。 The solubility of the specific resin in solvent B relative to 100 g of solvent B at 25° C. is preferably 5 g/100g or more, more preferably 10 g/100g or more, and still more preferably 20 g/100g or more. When the photosensitive resin composition of the present invention contains any one or two of a plurality of specific resins or solvents B, the solubility in each combination of at least one specific resin and at least one solvent B is within the above range. That’s it.

溶劑B包含選自包括γ-丁內酯（GBL）、二甲基亞碸（DMSO）、N-甲基-2-吡咯啶酮（NMP）、3-甲氧基-N,N-二甲基丙醯胺、1,3-二甲基-2-咪唑啶酮（DMI）、四甲基（TMU）、丙二醇單甲醚（PGME）及乳酸乙酯之群組中之至少1種為較佳。 又，從所獲得之硬化物的斷裂伸長率及適用於基材時的樹脂組成物的膜厚均勻性的觀點而言，溶劑B可以混合使用2種以上溶劑。 該等之中，作為溶劑B，包含GBL、3-甲氧基-N,N-二甲基丙醯胺、DMI或NMP為較佳，下述（B1）～（B10）所示之組合中的任一種為更佳。又，從適用於基材時的樹脂組成物的膜厚均勻性的觀點而言，（B1）或（B3）所示之組合中的任一種為較佳。 （B1）包含NMP及乳酸乙酯 （B2）包含NMP及PGME （B3）包含GBL及DMSO （B4）包含GBL及NMP （B5）包含GBL及3-甲氧基-N,N-二甲基丙醯胺 （B6）包含GBL及DMI （B7）包含3-甲氧基-N,N-二甲基丙醯胺及乳酸乙酯 （B8）包含3-甲氧基-N,N-二甲基丙醯胺及PGME （B9）包含DMI及乳酸乙酯 （B10）包含DMI及PGME 在上述（B1）～（B10）中，還可以包含對應於其他溶劑B之溶劑，但將對應於其他溶劑B之溶劑的含量相對於溶劑B的總質量設為5質量%以下（較佳為1質量%以下，更佳為0.1質量%以下）之態樣亦為本發明的較佳之態樣之一。 在上述（B1）中，將NMP的含量設為100質量份時的乳酸乙酯的含量係5～50質量份為較佳，10～40質量份為更佳。 在上述（B2）中，將NMP的含量設為100質量份時的PGME的含量係5～50質量份為較佳，10～40質量份為更佳。 在上述（B3）中，將GBL的含量設為100質量份時的DMSO的含量係5～50質量份為較佳，10～40質量份為更佳。 在上述（B4）中，將GBL的含量設為100質量份時的NMP的含量係5～50質量份為較佳，10～40質量份為更佳。 在上述（B5）中，將GBL的含量設為100質量份時的3-甲氧基-N,N-二甲基丙醯胺的含量係5～50質量份為較佳，10～40質量份為更佳。 在上述（B6）中，將GBL的含量設為100質量份時的DMI的含量係5～50質量份為較佳，10～40質量份為更佳。 在上述（B7）中，將3-甲氧基-N,N-二甲基丙醯胺的含量設為100質量份時的乳酸乙酯的含量係5～50質量份為較佳，10～40質量份為更佳。 在上述（B8）中，將3-甲氧基-N,N-二甲基丙醯胺的含量設為100質量份時的PGME的含量係5～50質量份為較佳，10～40質量份為更佳。 在上述（B9）中，將DMI的含量設為100質量份時的乳酸乙酯的含量係5～50質量份為較佳，10～40質量份為更佳。 在上述（B10）中，將DMI的含量設為100質量份時的PGME的含量係5～50質量份為較佳，10～40質量份為更佳。 Solvent B contains gamma-butyrolactone (GBL), dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), 3-methoxy-N,N-dimethyl At least one of the group consisting of 1,3-dimethyl-2-imidazolidinone (DMI), tetramethyl (TMU), propylene glycol monomethyl ether (PGME) and ethyl lactate is a relatively good. In addition, from the viewpoint of the elongation at break of the obtained cured product and the film thickness uniformity of the resin composition when applied to a base material, two or more solvents may be mixed and used in the solvent B. Among them, as the solvent B, it is preferable to include GBL, 3-methoxy-N,N-dimethylpropylamide, DMI or NMP, among the combinations shown in the following (B1) to (B10) Any one is better. In addition, from the viewpoint of film thickness uniformity of the resin composition when applied to a base material, any one of the combinations represented by (B1) or (B3) is preferable. (B1) Contains NMP and ethyl lactate (B2) Includes NMP and PGME (B3) Includes GBL and DMSO (B4) Includes GBL and NMP (B5) Contains GBL and 3-methoxy-N,N-dimethylpropylamine (B6) Includes GBL and DMI (B7) Contains 3-methoxy-N,N-dimethylpropamide and ethyl lactate (B8) Contains 3-methoxy-N,N-dimethylpropylamine and PGME (B9) Contains DMI and ethyl lactate (B10) Includes DMI and PGME In the above (B1) to (B10), a solvent corresponding to other solvent B may also be included, but the content of the solvent corresponding to other solvent B is set to 5 mass % or less (preferably 1 mass% or less, more preferably 0.1 mass% or less) is also one of the preferred aspects of the present invention. In the above (B1), when the content of NMP is 100 parts by mass, the content of ethyl lactate is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass. In the above (B2), when the content of NMP is 100 parts by mass, the content of PGME is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass. In the above (B3), when the content of GBL is 100 parts by mass, the content of DMSO is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass. In the above (B4), when the content of GBL is 100 parts by mass, the content of NMP is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass. In the above (B5), when the content of GBL is 100 parts by mass, the content of 3-methoxy-N,N-dimethylpropylamine is preferably 5 to 50 parts by mass, and 10 to 40 parts by mass. portion is better. In the above (B6), when the content of GBL is 100 parts by mass, the content of DMI is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass. In the above (B7), when the content of 3-methoxy-N,N-dimethylpropylamine is 100 parts by mass, the content of ethyl lactate is preferably 5 to 50 parts by mass, and 10 to 100 parts by mass. 40 parts by mass is more preferred. In the above (B8), when the content of 3-methoxy-N,N-dimethylpropylamine is 100 parts by mass, the content of PGME is preferably 5 to 50 parts by mass, and 10 to 40 parts by mass. portion is better. In the above (B9), when the content of DMI is 100 parts by mass, the content of ethyl lactate is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass. In the above (B10), when the content of DMI is 100 parts by mass, the content of PGME is preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass.

上述溶劑B的含量相對於感光性樹脂組成物的總質量係40質量%以上且小於90質量%為較佳，50～80質量%為更佳，55～75質量%為更佳。The content of the above-mentioned solvent B is preferably 40 mass % or more and less than 90 mass % with respect to the total mass of the photosensitive resin composition, more preferably 50 to 80 mass %, and even more preferably 55 to 75 mass %.

＜溶劑C＞ 本發明的感光性樹脂組成物包含溶劑C。 ＜Solvent C＞ The photosensitive resin composition of the present invention contains solvent C.

在本發明的第1態樣的感光性樹脂組成物中，溶劑C係SP值小於21.0（J/cm 3） 0.5或為25.0（J/cm 3） 0.5以上且沸點為60℃以上之溶劑。 上述沸點係1氣壓（101,325Pa）下的值。 在本發明的第1態樣的感光性樹脂組成物中，溶劑C係選自包括乙酸乙酯、乙酸異丙酯、乙酸正丙酯、乙酸丁酯、己烷、庚烷、苯、甲苯、甲醇、乙醇、四氫呋喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二乙醚、丙二醇單甲醚乙酸酯、環戊酮及環己酮之群組中之至少1種為較佳。 在本發明的第2態樣的感光性樹脂組成物中，溶劑C係乙酸乙酯、乙酸異丙酯、乙酸正丙酯、乙酸丁酯、己烷、庚烷、苯、甲苯、甲醇、乙醇、四氫呋喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二乙醚、丙二醇單甲醚乙酸酯、環戊酮或環己酮。 在本發明的第2態樣的感光性樹脂組成物中的上述溶劑C均係SP值小於21.0（J/cm 3） 0.5或為25.0（J/cm 3） 0.5以上且沸點為60℃以上之溶劑。 In the photosensitive resin composition of the first aspect of the present invention, the solvent C is a solvent with an SP value of less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or more and a boiling point of 60° C. or more. The above boiling point is the value at 1 atmosphere (101,325Pa). In the photosensitive resin composition of the first aspect of the present invention, the solvent C is selected from the group consisting of ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, hexane, heptane, benzene, toluene, At least one of the group consisting of methanol, ethanol, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone and cyclohexanone 1 type is better. In the photosensitive resin composition of the second aspect of the present invention, the solvent C is ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, hexane, heptane, benzene, toluene, methanol, ethanol , tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone or cyclohexanone. The above-mentioned solvent C in the photosensitive resin composition of the second aspect of the present invention all has an SP value of less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or more and a boiling point of 60°C or more. Solvent.

從所獲得之硬化物的斷裂伸長率，及適用於基材時的樹脂組成物的膜厚均勻性的觀點而言，本發明的感光性樹脂組成物中所包含之溶劑C係甲苯、四氫呋喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二乙醚或環戊酮為較佳，甲苯、四氫呋喃、1,4-二噁烷或二乙二醇二甲醚為更佳。From the viewpoint of the elongation at break of the obtained cured product and the film thickness uniformity of the resin composition when applied to a base material, the solvent C contained in the photosensitive resin composition of the present invention is toluene, tetrahydrofuran, 1,4-dioxane, diglyme, diglyme or cyclopentanone are preferred, toluene, tetrahydrofuran, 1,4-dioxane or diglyme are preferred. Better.

上述溶劑C的含量相對於感光性樹脂組成物的總質量係1ppm以上且10,000ppm以下。 從所獲得之硬化物的斷裂伸長率的觀點而言，上述含量係5ppm以上為較佳，10ppm以上為更佳，20ppm以上為進一步較佳。 從適用於基材時的樹脂組成物的膜厚均勻性的觀點而言，上述含量係5,000ppm以下為較佳，2,000ppm以下為更佳，500ppm以下為進一步較佳。 The content of the solvent C is 1 ppm or more and 10,000 ppm or less relative to the total mass of the photosensitive resin composition. From the viewpoint of the elongation at break of the obtained hardened material, the content is preferably 5 ppm or more, more preferably 10 ppm or more, and still more preferably 20 ppm or more. From the viewpoint of film thickness uniformity of the resin composition when applied to a base material, the content is preferably 5,000 ppm or less, more preferably 2,000 ppm or less, and further preferably 500 ppm or less.

本發明的感光性樹脂組成物中的相對於特定樹脂100質量份之溶劑C的含量係0.0003～3.5為較佳，0.002～2為更佳，0.005～0.3為進一步較佳。 本發明的感光性樹脂組成物中的相對於聚合性化合物100質量份之溶劑C的含量係0.001～50為較佳，0.004～5為更佳，0.01～3為進一步較佳。 本發明的感光性樹脂組成物中的相對於聚合抑制劑100質量份之溶劑C的含量係0.5～10000為較佳，1～5000為更佳，10～500為進一步較佳。 本發明的感光性樹脂組成物中的相對於金屬密接性改良劑100質量份之溶劑C的含量係0.01～300為較佳，0.02～200為更佳，0.2～100為進一步較佳。 本發明的感光性樹脂組成物中的相對於遷移抑制劑100質量份之溶劑C的含量係1～20000為較佳，2～15000為更佳，10～10000為進一步較佳。 本發明的感光性樹脂組成物中的相對於酸化防止劑100質量份之溶劑C的含量係0.02～300為較佳，0.03～200為更佳，0.1～100為進一步較佳。 The content of solvent C in the photosensitive resin composition of the present invention based on 100 parts by mass of the specific resin is preferably 0.0003 to 3.5, more preferably 0.002 to 2, and further preferably 0.005 to 0.3. The content of solvent C in the photosensitive resin composition of the present invention relative to 100 parts by mass of the polymerizable compound is preferably 0.001 to 50, more preferably 0.004 to 5, and further preferably 0.01 to 3. The content of solvent C in the photosensitive resin composition of the present invention relative to 100 parts by mass of the polymerization inhibitor is preferably 0.5 to 10,000, more preferably 1 to 5,000, and further preferably 10 to 500. The content of solvent C in the photosensitive resin composition of the present invention based on 100 parts by mass of the metal adhesion improving agent is preferably 0.01 to 300, more preferably 0.02 to 200, and further preferably 0.2 to 100. The content of solvent C in the photosensitive resin composition of the present invention is preferably 1 to 20,000 parts by mass relative to 100 parts by mass of the migration inhibitor, more preferably 2 to 15,000, and further preferably 10 to 10,000. The content of solvent C in the photosensitive resin composition of the present invention relative to 100 parts by mass of the acidification inhibitor is preferably 0.02 to 300, more preferably 0.03 to 200, and further preferably 0.1 to 100.

本發明的感光性樹脂組成物中所包含之溶劑C的SP值小於21.0（J/cm 3） 0.5或為25.0（J/cm 3） 0.5以上，17.0（J/cm 3） 0.5以上且小於21.0（J/cm 3） 0.5、或25.0（J/cm 3） 0.5以上且小於27.0（J/cm 3） 0.5為較佳，18.0（J/cm 3） 0.5以上且小於21.0（J/cm 3） 0.5為更佳。 The SP value of the solvent C contained in the photosensitive resin composition of the present invention is less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or more, and 17.0 (J/cm 3 ) 0.5 or more and less than 21.0 (J/cm 3 ) 0.5 , or 25.0 (J/cm 3 ) 0.5 or more and less than 27.0 (J/cm 3 ) 0.5 is better, 18.0 (J/cm 3 ) 0.5 or more but less than 21.0 (J/cm 3 ) 0.5 is better.

本發明的感光性樹脂組成物中所包含之溶劑C的沸點為60℃以上，65℃以上為較佳，70℃以上為更佳。上述沸點的上限係250℃以下為較佳。 認為若沸點為上述下限以上，則例如在加熱時等，溶劑C的揮發獲得抑制，從而更容易獲得硬化物的斷裂伸長率提高這一效果。 The boiling point of the solvent C contained in the photosensitive resin composition of the present invention is 60°C or higher, preferably 65°C or higher, and more preferably 70°C or higher. The upper limit of the boiling point is preferably 250°C or less. It is considered that if the boiling point is equal to or higher than the above lower limit, volatilization of the solvent C is suppressed during heating, for example, and the effect of improving the elongation at break of the cured product is more likely to be obtained.

相對於25℃、100g的溶劑C，特定樹脂對溶劑C之溶解度小於20g/100g為較佳，小於10g/100g為更佳，小於5g/100g為進一步較佳。上述溶解度的下限沒有特別限定，例如，0.1g/100g以上為較佳。 在本發明的感光性樹脂組成物包含複數種特定樹脂或溶劑C中的任一個或兩個的情況下，至少1種特定樹脂與至少1種溶劑C的組合中的溶解度在上述範圍內即可。 Relative to 100g of solvent C at 25°C, the solubility of the specific resin in solvent C is preferably less than 20g/100g, more preferably less than 10g/100g, and still more preferably less than 5g/100g. The lower limit of the above-mentioned solubility is not particularly limited, but for example, it is preferably 0.1 g/100 g or more. When the photosensitive resin composition of the present invention contains any one or two of a plurality of specific resins or solvents C, it is sufficient that the solubility in a combination of at least one specific resin and at least one solvent C is within the above range. .

＜感光劑＞ 本發明的感光性樹脂組成物包含感光劑。 作為感光劑，可以舉出光聚合起始劑、光酸產生劑等，包含光聚合起始劑為較佳，包含光自由基聚合起始劑為更佳。 ＜Photosensitizer＞ The photosensitive resin composition of the present invention contains a photosensitizer. Examples of the photosensitizer include photopolymerization initiators, photoacid generators, and the like. It is preferable to include a photopolymerization initiator, and more preferably to include a photoradical polymerization initiator.

〔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。作為光自由基聚合起始劑，並沒有特別限制，能夠適當選自公知的光自由基聚合起始劑。例如，對紫外線區域至可見區域的光線具有感光性之光自由基聚合起始劑為較佳。又，可以為與被光激發之增感劑產生一些作用並生成活性自由基之活性劑。 [Photopolymerization initiator] The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet range to the visible range is preferred. In addition, it may be an active agent that interacts with the sensitizer excited by light and generates active free radicals.

光自由基聚合起始劑至少含有1種在波長約240～800nm（較佳為330～500nm）的範圍內至少具有約50L•mol -1•cm -1莫耳吸光係數之化合物為較佳。化合物的莫耳吸光係數能夠利用公知的方法測定。例如，藉由紫外可見分光光度計（Varian公司製Cary-5 spectrophotometer），使用乙酸乙酯溶劑，在0.01g/L的濃度下進行測定為較佳。 The photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50L·mol -1 •cm -1 in the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

作為光自由基聚合起始劑，能夠任意使用公知的化合物。例如，可以舉出鹵化烴衍生物（例如具有三口井骨架之化合物、具有噁二唑骨架之化合物、具有三鹵甲基之化合物等）、醯基氧化膦等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮等α-胺基酮化合物、羥基苯乙酮等α-羥基酮化合物、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，能夠參考日本特開2016-027357號公報的0165～0182段、國際公開第2015/199219號的0138～0151段的記載，該內容編入本說明書中。又，可以舉出日本特開2014-130173號公報的0065～0111段、日本專利第6301489號公報中所記載之化合物、MATERIAL STAGE 37～60p，vol.19，No.3,2019中所記載之過氧化物系光聚合起始劑、國際公開第2018/221177號中所記載之光聚合起始劑、國際公開第2018/110179號中所記載之光聚合起始劑、日本特開2019-043864號公報中所記載之光聚合起始劑、日本特開2019-044030號公報中所記載之光聚合起始劑、日本特開2019-167313號公報中所記載之過氧化物系起始劑，該等內容編入本說明書中。As the photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (for example, compounds having a three-well skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbis Oxime compounds such as imidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone and other α-aminoketone compounds, hydroxyacetophenone and other α-hydroxyl groups Ketone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic hydrocarbon complexes, etc. Regarding these details, reference can be made to the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, and these contents are incorporated into this specification. Examples include compounds described in paragraphs 0065 to 0111 of Japanese Patent Application Laid-Open No. 2014-130173, compounds described in Japanese Patent No. 6301489, and MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019. Peroxide-based photopolymerization initiator, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, Japanese Patent Application Laid-Open No. 2019-043864 The photopolymerization initiator described in Japanese Patent Application Publication No. 2019-044030, the peroxide-based initiator described in Japanese Patent Application Publication No. 2019-167313, These contents are incorporated into this manual.

作為酮化合物，例如，可以例示出日本特開2015-087611號公報的0087段中所記載之化合物，該內容編入本說明書中。在市售品中，亦可較佳地使用KAYACURE DETX-S（Nippon Kayaku Co.,Ltd.製）。Examples of the ketone compound include compounds described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611, which content is incorporated into this specification. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can be preferably used.

在本發明的一實施態樣中，作為光自由基聚合起始劑，能夠較佳地使用羥基苯乙酮化合物、胺基苯乙酮化合物及醯基膦化合物。更具體而言，例如，能夠使用日本特開平10-291969號公報中所記載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，該內容編入本說明書中。In one embodiment of the present invention, as the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a acylphosphine compound can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used. The contents are incorporated into this manual.

作為α-羥基酮系起始劑，能夠使用Omnirad 184、Omnirad 1173、Omnirad 2959、Omnirad 127（以上為IGM Resins B.V.製）、IRGACURE 184（IRGACURE為註冊商標）、DAROCUR 1173、IRGACURE 500、IRGACURE-2959、IRGACURE 127（商品名：均為BASF公司製）。As α-hydroxyketone starters, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (the above are manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, and IRGACURE-2959 , IRGACURE 127 (trade name: both manufactured by BASF).

作為α-胺基酮系起始劑，能夠使用Omnirad 907、Omnirad 369、Omnirad 369E、Omnirad 379EG（以上為IGM Resins B.V.製）、IRGACURE 907、IRGACURE 369及IRGACURE 379（商品名：均為BASF公司製）。As α-aminoketone starters, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (the above are manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade names: all manufactured by BASF) ).

作為胺基苯乙酮系起始劑，亦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，該內容編入本說明書中。As the aminoacetophenone-based initiator, compounds described in Japanese Patent Application Laid-Open No. 2009-191179 whose maximum absorption wavelength matches a light source of wavelengths such as 365 nm or 405 nm can also be used, and this content is incorporated into this specification.

作為醯基氧化膦系起始劑，可以舉出2,4,6-三甲基苯甲醯基-二苯基-氧化膦等。又，能夠使用Omnirad 819、Omnirad TPO（以上為IGM Resins B.V.製）、IRGACURE-819、IRGACURE-TPO（商品名：均為BASF公司製）。Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. In addition, Omnirad 819, Omnirad TPO (the above manufactured by IGM Resins B.V.), IRGACURE-819, and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

作為茂金屬化合物，可以例示出IRGACURE-784、IRGACURE-784EG（均為BASF公司製）、Keycure VIS 813（King Brother Chem Co.,Ltd.製）等。Examples of the metallocene compound include IRGACURE-784, IRGACURE-784EG (all manufactured by BASF), Keycure VIS 813 (King Brother Chem Co., Ltd.), and the like.

作為光自由基聚合起始劑，可更佳地舉出肟化合物。藉由使用肟化合物，能夠進一步有效地提高曝光寬容度。肟化合物的曝光寬容度（曝光餘裕）較廣且亦起到作為光硬化促進劑的作用，因此特佳。As a photoradical polymerization initiator, an oxime compound is more preferable. By using oxime compounds, the exposure latitude can be further effectively increased. Oxime compounds are particularly suitable because they have a wide exposure latitude (exposure margin) and also function as a photohardening accelerator.

作為肟化合物的具體例，可以舉出日本特開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、J.C.S.Perkin II（1979年，第1653-1660頁）中所記載之化合物、J.C.S.Perkin II（1979年，第156-162頁）中所記載之化合物、Journal of Photopolymer Science and Technology（1995年，第202-232頁）中所記載之化合物、日本特開2000-066385號公報中所記載之化合物、日本特表2004-534797號公報中所記載之化合物、日本特開2017-019766號公報中所記載之化合物、日本專利第6065596號公報中所記載之化合物、國際公開第2015/152153號中所記載之化合物、國際公開第2017/051680號中所記載之化合物、日本特開2017-198865號公報中所記載之化合物、國際公開第2017/164127號的0025～0038段中所記載之化合物、國際公開第2013/167515號中所記載之化合物等，該內容編入本說明書中。Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166. Compounds, Compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), Compounds described in J.C.S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, Compounds described in Japanese Patent Application Publication No. 202-232), compounds described in Japanese Patent Application Publication No. 2000-066385, compounds described in Japanese Patent Application Publication No. 2004-534797, and compounds described in Japanese Patent Application Publication No. 2017-019766 Compounds described, compounds described in Japanese Patent Publication No. 6065596, compounds described in International Publication No. 2015/152153, compounds described in International Publication No. 2017/051680, Japanese Patent Publication No. 2017-198865 The compounds described in , the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, the compounds described in International Publication No. 2013/167515, etc. are incorporated into this specification.

作為較佳之肟化合物，例如可以舉出下述結構的化合物、3-（苯甲醯氧基（亞胺基））丁-2-酮、3-（乙醯氧基（亞胺基））丁-2-酮、3-（丙醯氧基（亞胺基））丁-2-酮、2-（乙醯氧基（亞胺基））戊-3-酮、2-（乙醯氧基（亞胺基））-1-苯基丙-1-酮、2-（苯甲醯氧基（亞胺基））-1-苯基丙-1-酮、3-（（）4-甲苯磺醯氧基）（亞胺基）丁-2-酮以及2-（乙氧基羰氧基（亞胺基））-1-苯基丙-1-酮等。在本發明的樹脂組成物中，使用肟化合物（肟系光自由基聚合起始劑）來作為光自由基聚合起始劑為特佳。肟系光自由基聚合起始劑在分子內具有連結基＞C=N-O-C（=O）-。Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, and 3-(acetyloxy(imino))butan -2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetyloxy(imino))pentan-3-one, 2-(acetyloxy(imino)) (imino))-1-phenylpropan-1-one, 2-(benzyloxy(imino))-1-phenylpropan-1-one, 3-(()4-toluene Sulfonyloxy)(imino)butan-2-one and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc. In the resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime-based photoradical polymerization initiator has a linking group >C=N-O-C (=O)- in the molecule.

[化學式16] [Chemical formula 16]

在市售品中，亦可較佳地使用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，亦能夠使用TR-PBG-304、TR-PBG-305（Changzhou Tronly New Electronic Materials CO.,LTD.製）、ADEKA ARKLS NCI-730、NCI-831及ADEKA ARKLS NCI-930（ADEKA CORPORATION製）。又，能夠使用DFI-091（Daito Chemix Corporation製）、SpeedCure PDO（SARTOMER ARKEMA製）。又，亦能夠使用下述結構的肟化合物。 [化學式17] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (the above are manufactured by BASF Corporation), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, Japan Patent Publication No. 2012- Photoradical polymerization initiator 2) described in Publication No. 014052. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Trolly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. . In addition, DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Moreover, the oxime compound of the following structure can also be used. [Chemical formula 17]

作為光自由基聚合起始劑，亦能夠使用具有茀環之肟化合物。作為具有茀環之肟化合物的具體例，可以舉出日本特開2014-137466號公報中所記載之化合物、日本專利06636081號中所記載之化合物，該內容編入本說明書中。As a photoradical polymerization initiator, an oxime compound having a fluorine ring can also be used. Specific examples of the oxime compound having a fluorine ring include the compounds described in Japanese Patent Application Laid-Open No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, the contents of which are incorporated in this specification.

作為光自由基聚合起始劑，亦能夠使用具有咔唑環的至少1個苯環成為萘環之骨架之肟化合物。作為該種肟化合物的具體例，可以舉出國際公開第2013/083505號中所記載之化合物，該內容編入本說明書中。As the photoradical polymerization initiator, an oxime compound in which at least one benzene ring of a carbazole ring serves as the skeleton of a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505, the contents of which are incorporated into this specification.

亦能夠使用具有氟原子之肟化合物。作為該種肟化合物的具體例，可以舉出日本特開2010-262028號公報中所記載之化合物、日本特表2014-500852號公報的0345段中所記載之化合物24、36～40、日本特開2013-164471號公報的0101段中所記載之化合物（C-3）等，該內容編入本說明書中。Oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and Japanese Patent Application Publication No. 2014-500852. Compound (C-3), etc. described in paragraph 0101 of Japanese Patent Application No. 2013-164471, the content of which is incorporated into this specification.

作為光聚合起始劑，能夠使用具有硝基之肟化合物。具有硝基之肟化合物設為二聚物亦為較佳。作為具有硝基之肟化合物的具體例，可以舉出日本特開2013-114249號公報的0031～0047段、日本特開2014-137466號公報的0008～0012、0070～0079段中所記載之化合物、日本專利4223071號公報的0007～0025段中所記載之化合物，該內容編入本說明書中。又，作為具有硝基之肟化合物，亦可以舉出ADEKA ARKLS NCI-831（ADEKA CORPORATION製）。As the photopolymerization initiator, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Laid-Open No. 2013-114249 and paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Application Laid-Open No. 2014-137466. , the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, the content of which is incorporated into this specification. Also, examples of the oxime compound having a nitro group include ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

作為光自由基聚合起始劑，亦能夠使用具有苯并呋喃骨架之肟化合物。作為具體例，可以舉出國際公開第2015/036910號中所記載之OE-01～OE-75。As the photoradical polymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

作為光自由基聚合起始劑，亦能夠使用在咔唑骨架上鍵結有具有羥基之取代基之肟化合物。作為該種光聚合起始劑，可以舉出國際公開第2019/088055號中所記載之化合物等，該內容編入本說明書中。As the photoradical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019/088055, the contents of which are incorporated into this specification.

作為光聚合起始劑，亦能夠使用具有對芳香族環導入了拉電子基團之芳香族環基Ar OX1之肟化合物（以下，亦稱為肟化合物OX）。作為上述芳香族環基Ar OX1所具有之拉電子基團，可以舉出醯基、硝基、三氟甲基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、氰基，醯基及硝基為較佳，從容易形成耐光性優異之膜的理由考慮，醯基為更佳，苯甲醯基為進一步較佳。 As the photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic ring group Ar OX1 having an electron-withdrawing group introduced into the aromatic ring can also be used. Examples of the electron-withdrawing group of the aromatic ring group Ar OX1 include a hydroxyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, and an alkylsulfinyl group. Arylsulfonyl group, cyano group, acyl group and nitro group are preferred, and acyl group is more preferred since it is easy to form a film with excellent light resistance, and benzyl group is further preferred.

肟化合物OX為選自式（OX1）所表示之化合物及式（OX2）所表示之化合物中之至少1種為較佳，式（OX2）所表示之化合物為更佳。 [化學式18] 式中，R X1表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基氫硫基、芳基氫硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯基、醯氧基、胺基、膦醯基、胺甲醯基或胺磺醯基， R X2表示烷基、烯基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烷基氫硫基、芳基氫硫基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、醯氧基或胺基， R X3～R X14分別獨立地表示氫原子或取代基； 其中，R X10～R X14中的至少1個為拉電子基團。 It is preferable that the oxime compound OX is at least one selected from the compound represented by formula (OX1) and the compound represented by formula (OX2), and the compound represented by formula (OX2) is more preferable. [Chemical formula 18] In the formula, R , arylsulfenyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amine group, phosphinoyl group, aminoformyl group or aminesulfonyl group, R X2 represents an alkyl group, Alkenyl, alkoxy, aryl, aryloxy, heterocyclyl, heterocyclicoxy, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkyl sulfonyl group , arylsulfonyl group , acyloxy group or amine group , R .

上述式中，R X12為拉電子基團，R X10、R X11、R X13、R X14為氫原子為較佳。 In the above formula, R X12 is an electron withdrawing group, and R X10 , R X11 , R X13 , and R X14 are preferably hydrogen atoms.

作為肟化合物OX的具體例，可以舉出日本專利第4600600號公報的0083～0105段中所記載之化合物，該內容編入本說明書中。Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated in this specification.

作為最佳之肟化合物，可以舉出日本特開2007-269779號公報中示出之具有特定取代基之肟化合物、日本特開2009-191061號公報中示出之具有硫芳基之肟化合物等，該內容編入本說明書中。Preferred oxime compounds include oxime compounds having specific substituents shown in Japanese Patent Application Laid-Open No. 2007-269779, oxime compounds having a thioaryl group shown in Japanese Patent Application Laid-Open No. 2009-191061, and the like. , this content is incorporated into this manual.

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口井化合物、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、三芳基咪唑二聚物、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、鹵甲基噁二唑化合物、3-芳基取代香豆素化合物之群組中之化合物為較佳。From the perspective of exposure sensitivity, the photoradical polymerization initiator is selected from the group consisting of trihalomethyl three well compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acyl groups. Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole 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, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

更佳之光自由基聚合起始劑為三鹵甲基三口井化合物、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口井化合物、α-胺基酮化合物、茂金屬化合物、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1種化合物為更進一步較佳，使用茂金屬化合物或肟化合物為再進一步較佳。Better photoradical polymerization initiators are trihalomethyl three-well compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salts Compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyl three-well compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds It is further more preferred to use at least one compound in the group, and it is still more preferred to use a metallocene compound or an oxime compound.

又，光自由基聚合起始劑亦能夠使用二苯甲酮、N,N’-四甲基-4,4’-二胺基二苯甲酮（米其勒酮（Michler’s ketone））等N,N’-四烷基-4,4’-二胺基二苯甲酮，2-苄基-2-二甲胺基-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之醌類、安息香烷基醚等安息香醚化合物、安息香、烷基安息香等安息香化合物、苄基二甲基縮酮等苄基衍生物等。又，亦能夠使用下述式（I）所表示之化合物。In addition, as the photoradical polymerization initiator, benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), etc. can also be used. ,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-terminal lylinylphenyl)-butanone-1 , 2-methyl-1-[4-(methylthio)phenyl]-2-ethyl-acetone-1 and other aromatic ketones, alkylanthraquinones, etc., are quinones formed by ring condensation with aromatic rings Benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. Moreover, the compound represented by the following formula (I) can also be used.

[化學式19] [Chemical formula 19]

在式（I）中，R I00為碳數1～20的烷基、被1個以上的氧原子中斷之碳數2～20的烷基、碳數1～12的烷氧基、苯基、或者碳數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、由被1個以上的氧原子中斷之碳數2～18的烷基及碳數1～4的烷基中的至少1個取代之苯基或聯苯基，R I01為式（II）所表示之基團或者與R I00相同的基團，R I02～R I04各自獨立地為碳數1～12的烷基、碳數1～12的烷氧基或鹵素原子。 In formula (I), R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, or a phenyl group, Or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, or a carbon group interrupted by one or more oxygen atoms. At least one substituted phenyl group or biphenyl group among alkyl groups with 2 to 18 carbon atoms and alkyl groups with 1 to 4 carbon atoms, R I01 is a group represented by formula (II) or a group identical to R I00 , R I02 to R I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[化學式20] [Chemical formula 20]

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

又，光自由基聚合起始劑亦能夠使用國際公開第2015/125469號的0048～0055段中所記載之化合物，該內容編入本說明書中。In addition, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used as the photoradical polymerization initiator, and this content is incorporated into this specification.

作為光自由基聚合起始劑，可以使用2官能或3官能以上的光自由基起始劑。藉由使用該種光自由基聚合起始劑，從光自由基聚合起始劑的1個分子產生2個以上的自由基，因此可以獲得良好的靈敏度。又，在使用了非對稱結構的化合物的情況下，結晶性下降而在溶劑等中的溶解性變高，隨時間的經過變得不易析出，藉此能夠提高樹脂組成物的經時穩定性。作為2官能或3官能以上的光自由基聚合起始劑的具體例，可以舉出日本特表2010-527339號公報、日本特表2011-524436號公報、國際公開第2015/004565號、日本特表2016-532675號公報的0407～0412段、國際公開第2017/033680號的0039～0055段中所記載之肟化合物的二聚物、日本特表2013-522445號公報中所記載之化合物（E）及化合物（G）、國際公開第2016/034963號中所記載之Cmpd1～7、日本特表2017-523465號公報的0007段中所記載之肟酯類光起始劑、日本特開2017-167399號公報的0020～0033段中所記載之光起始劑、日本特開2017-151342號公報的0017～0026段中所記載之光聚合起始劑（A）、日本專利第6469669號公報中所記載之肟酯光起始劑等，該內容編入本說明書中。As the photoradical polymerization initiator, a bifunctional or trifunctional or higher photoradical initiator can be used. By using this type of photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity can be obtained. Furthermore, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in a solvent or the like increases, making it less likely to precipitate over time, thereby improving the stability of the resin composition over time. Specific examples of the bifunctional or trifunctional or higher-functional photoradical polymerization initiator include Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Application Publication No. 2015/004565. The dimer of the oxime compound described in Paragraphs 0407 to 0412 of Table 2016-532675, Paragraphs 0039 to 0055 of International Publication No. 2017/033680, and the compound (E) described in Japanese Patent Publication No. 2013-522445 ) and compound (G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Application Publication No. 2017-523465, Japanese Patent Application Publication No. 2017- The photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, and the photopolymerization initiator (A) described in Japanese Patent Publication No. 6469669 The described oxime ester photoinitiator, etc. are incorporated into this specification.

在包含光聚合起始劑的情況下，其含量相對於本發明的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含有1種，亦可以含有2種以上。在含有2種以上光聚合起始劑的情況下，合計量在上述範圍內為較佳。 此外，有時光聚合起始劑亦會作為熱聚合起始劑而發揮作用，因此有時藉由烘箱、加熱板等的加熱會進一步促進基於光聚合起始劑之交聯。 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 30% by mass relative to the total solid content of the resin composition of the present invention. 15% by mass, more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one type or two or more types. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, sometimes the photopolymerization initiator also functions as a thermal polymerization initiator, so the cross-linking based on the photopolymerization initiator may be further accelerated by heating in an oven, a hot plate, etc.

〔增感劑〕 樹脂組成物可以包含增感劑。增感劑吸收特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劑與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，熱自由基聚合起始劑、光自由基聚合起始劑引起化學變化而分解，並生成自由基、酸或鹼。 作為可使用之增感劑，可以舉出國際公開第2021/045126號的0269段中所記載之化合物等。 [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. The sensitizer in the electronically excited state comes into contact with the thermal radical polymerization initiator, photo radical polymerization initiator, etc. to produce electron transfer, energy transfer, heat generation and other effects. Thereby, the thermal radical polymerization initiator and the photo radical polymerization initiator cause chemical changes to decompose, and generate radicals, acids, or bases. Examples of sensitizers that can be used include compounds described in paragraph 0269 of International Publication No. 2021/045126.

在樹脂組成物包含增感劑的情況下，增感劑的含量相對於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。增感劑可以單獨使用1種，亦可以並用2種以上。When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and 0.5 to 10 mass% relative to the total solid content of the resin composition. For further improvement. One type of sensitizer may be used alone, or two or more types may be used in combination.

〔鏈轉移劑〕 本發明的樹脂組成物可以含有鏈轉移劑。鏈轉移劑例如在高分子詞典第三版（高分子學會（The Society of Polymer Science，Japan）編，2005年）683-684頁中有定義。作為鏈轉移劑，例如，可以使用在分子內具有-S-S-、-SO 2-S-、-N-O-、SH、PH、SiH及GeH之化合物群、用於RAFT（Reversible Addition Fragmentation chain Transfer：可逆加成碎斷鏈轉移）聚合之具有硫代羰基硫基之二硫苯甲酸酯、三硫碳酸酯、二硫胺甲酸酯、黃原酸酯化合物等。該等向低活性自由基供給氫而生成自由基，或者可藉由在氧化之後去質子而生成自由基。尤其，能夠較佳地使用硫醇化合物。 [Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined in, for example, Polymer Dictionary 3rd Edition (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having -SS-, -SO 2 -S-, -NO-, SH, PH, SiH and GeH in the molecule can be used, which is used for RAFT (Reversible Addition Fragmentation chain Transfer: reversible Disulfide benzoate, trisulfide carbonate, disulfide carbamate, xanthate compounds, etc. with thiocarbonylthio group polymerized by addition fragment chain transfer). These generate free radicals by donating hydrogen to low-activity free radicals, or may generate free radicals by deprotonation after oxidation. In particular, thiol compounds can be preferably used.

又，鏈轉移劑亦能夠使用國際公開第2015/199219號的0152～0153段中所記載之化合物，該內容編入本說明書中。In addition, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used as the chain transfer agent, and this content is incorporated into this specification.

在本發明的樹脂組成物具有鏈轉移劑的情況下，鏈轉移劑的含量相對於本發明的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，0.1～10質量份為更佳，0.5～5質量份為進一步較佳。鏈轉移劑可以為僅1種，亦可以為2種以上。在鏈轉移劑為2種以上的情況下，其合計在上述範圍內為較佳。When the 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 resin composition of the present invention, and is preferably 0.1 to 10 parts by mass. More preferably, 0.5 to 5 parts by mass is still more preferably. There may be only one type of chain transfer agent, or two or more types of chain transfer agents. When there are two or more types of chain transfer agents, the total amount is preferably within the above range.

〔光酸產生劑〕 作為光酸產生劑，醌二疊氮化合物為較佳。又，除此以外，還可以使用在感光性樹脂組成物的領域中公知的光酸產生劑。 [Photoacid generator] As the photoacid generator, a quinonediazide compound is preferred. In addition, photoacid generators known in the field of photosensitive resin compositions can also be used.

作為醌二疊氮化合物，可以舉出醌二疊氮的磺酸與羥基化合物酯鍵結者、醌二疊氮的磺酸藉由磺醯胺基與多胺基化合物鍵結者、醌二疊氮的磺酸與多羥基多胺基化合物酯鍵結和/或藉由磺醯胺基鍵結者等。 該等多羥基化合物、多胺基化合物、多羥基多胺基化合物的所有官能基可以不被醌二疊氮取代，但以平均計官能基整體的40莫耳%以上被醌二疊氮取代為較佳。藉由含有該種醌二疊氮化合物，能夠獲得對i射線（波長365nm）、h射線（波長405nm）、g射線（波長436nm）感光之正型的感光性樹脂組成物。 Examples of the quinonediazide compound include those in which the sulfonic acid of quinonediazide is ester-bonded to a hydroxy compound, those in which the sulfonic acid of quinonediazide is bonded to a polyamine-based compound via a sulfonamide group, and quinonediazide Nitrogen sulfonic acid is bonded with a polyhydroxypolyamine compound through an ester bond and/or through a sulfonamide group bond. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted by quinonediazide, but on average, more than 40 mol% of the total functional groups are substituted by quinonediazide. Better. By containing this quinonediazide compound, a positive-type photosensitive resin composition sensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) can be obtained.

本發明的感光性樹脂組成物所含有之醌二疊氮化合物的含量相對於感光性樹脂組成物中的全部樹脂100質量份，1質量份以上為較佳，10質量份以上為更佳，50質量份以下為較佳，40質量份以下為較佳。藉由將醌二疊氮化合物的含量設為該範圍，曝光部和未曝光部對顯影液之溶解速度之差變高，從而能夠設為更高靈敏度，並且含量多時所產生之殘渣減少，因此較佳。另外，根據需要可以添加增感劑等。The content of the quinonediazide compound contained in the photosensitive resin composition of the present invention is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and 50 parts by mass relative to 100 parts by mass of all resins in the photosensitive resin composition. It is preferably not more than 40 parts by mass, and preferably not more than 40 parts by mass. By setting the content of the quinonediazide compound within this range, the difference in the dissolution rate of the exposed part and the unexposed part to the developer increases, thereby enabling higher sensitivity, and the residue generated when the content is high is reduced. Therefore it is better. In addition, a sensitizer and the like may be added as necessary.

＜聚合性化合物＞ 本發明的樹脂組成物包含聚合性化合物為較佳。 作為聚合性化合物，可以舉出自由基聚合性化合物（自由基交聯劑）或其他交聯劑。 該等之中，本發明的樹脂組成物進一步包含自由基聚合性化合物（自由基交聯劑）為較佳。 ＜Polymerizable compound＞ The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include radically polymerizable compounds (radical crosslinking agents) and other crosslinking agents. Among these, it is preferable that the resin composition of the present invention further contains a radically polymerizable compound (radical crosslinking agent).

〔自由基交聯劑〕 本發明的樹脂組成物包含自由基交聯劑為較佳。 自由基交聯劑係具有自由基聚合性基之化合物。作為自由基聚合性基，包含乙烯性不飽和鍵之基團為較佳。作為包含上述乙烯性不飽和鍵之基團，可以舉出乙烯基、烯丙基、乙烯基苯基、（甲基）丙烯醯基、順丁烯二醯亞胺基、（甲基）丙烯醯胺基等具有乙烯性不飽和鍵之基團。 在該等之中，作為包含上述乙烯性不飽和鍵之基團，（甲基）丙烯醯基、（甲基）丙烯醯胺基、乙烯基苯基為較佳，從反應性的觀點考慮，（甲基）丙烯醯基為更佳。 [Free radical cross-linking agent] The resin composition of the present invention preferably contains a radical crosslinking agent. A radical cross-linking agent is a compound having a radical polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferred. Examples of the group containing the ethylenically unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acrylyl, maleimide, and (meth)acrylyl. Amino groups and other groups with ethylenically unsaturated bonds. Among these, as the group containing the above-mentioned ethylenically unsaturated bond, (meth)acrylyl group, (meth)acrylamide group, and vinylphenyl group are preferred, and from the viewpoint of reactivity, A (meth)acrylyl group is more preferred.

自由基交聯劑係具有1個以上乙烯性不飽和鍵之化合物為較佳，具有2個以上乙烯性不飽和鍵之化合物為更佳。自由基交聯劑可以具有3個以上乙烯性不飽和鍵。 作為具有2個以上的上述乙烯性不飽和鍵之化合物，具有2～15個乙烯性不飽和鍵之化合物為較佳，具有2～10個乙烯性不飽和鍵之化合物為更佳，具有2～6個乙烯性不飽和鍵之化合物為進一步較佳。 又，從所獲得之圖案（硬化物）的膜強度的觀點考慮，本發明的樹脂組成物包含具有2個乙烯性不飽和鍵之化合物和具有3個以上的上述乙烯性不飽和鍵之化合物亦為較佳。 The radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 10 ethylenically unsaturated bonds is more preferred. Compounds with 6 ethylenically unsaturated bonds are further preferred. Furthermore, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention includes a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. For better.

自由基交聯劑的分子量係2,000以下為較佳，1,500以下為更佳，900以下為進一步較佳。自由基交聯劑的分子量的下限為100以上為較佳。 作為自由基交聯劑的具體例，可以舉出國際公開第2021/045126號的0143～0154段中所記載之化合物等。 The molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more. Specific examples of the radical cross-linking agent include compounds described in paragraphs 0143 to 0154 of International Publication No. 2021/045126, and the like.

從圖案的解析度和膜的伸縮性的觀點考慮，樹脂組成物使用2官能甲基丙烯酸酯或丙烯酸酯為較佳。 作為具體的化合物，可以舉出國際公開第2021/045126號的0155段中所記載之化合物等。 From the viewpoint of pattern resolution and film stretchability, it is preferable to use bifunctional methacrylate or acrylate as the resin composition. Specific compounds include compounds described in paragraph 0155 of International Publication No. 2021/045126, and the like.

在含有自由基交聯劑的情況下，其含量相對於本發明的樹脂組成物的總固體成分，大於0質量%且60質量%以下為較佳。下限為5質量%以上為更佳。上限為50質量%以下為更佳，30質量%以下為進一步較佳。When a radical crosslinking agent is contained, its content is preferably greater than 0% by mass and not more than 60% by mass relative to the total solid content of the resin composition of the present invention. It is more preferable that the lower limit is 5 mass % or more. It is more preferable that the upper limit is 50 mass % or less, and it is further more preferable that it is 30 mass % or less.

自由基交聯劑可以單獨使用1種，亦可以混合使用2種以上。在並用2種以上的情況下，其合計量在上述範圍內為較佳。A radical cross-linking agent may be used individually by 1 type, and may be used in mixture of 2 or more types. When two or more types are used in combination, the total amount is preferably within the above range.

〔其他交聯劑〕 本發明的樹脂組成物包含與上述自由基交聯劑不同之其他交聯劑亦為較佳。 [Other cross-linking agents] It is also preferable that the resin composition of the present invention contains other cross-linking agents different from the above-mentioned radical cross-linking agents.

＜鹼產生劑＞ 本發明的樹脂組成物可以包含鹼產生劑。在此，鹼產生劑係指能夠藉由物理作用或化學作用產生鹼之化合物。作為對本發明的樹脂組成物較佳之鹼產生劑，可以舉出熱鹼產生劑及光鹼產生劑。 尤其，在樹脂組成物包含環化樹脂的前驅物的情況下，樹脂組成物包含鹼產生劑為較佳。藉由樹脂組成物含有熱鹼產生劑，例如能夠藉由加熱促進前驅物的環化反應，硬化物的機械特性或耐藥品性變良好，例如作為半導體封裝中所包含之再配線層用層間絕緣膜的性能變良好。 作為鹼產生劑，可以為離子型鹼產生劑，亦可以為非離子型鹼產生劑。作為從鹼產生劑產生之鹼，例如，可以舉出二級胺、三級胺。 本發明之鹼產生劑並沒有特別限制，能夠使用公知的鹼產生劑。作為公知的鹼產生劑，例如，能夠使用胺甲醯基肟化合物、胺甲醯基羥基胺化合物、胺甲酸化合物、甲醯胺化合物、乙醯胺化合物、胺基甲酸酯化合物、苄基胺基甲酸酯化合物、硝基苄基胺基甲酸酯化合物、磺醯胺化合物、咪唑衍生物化合物、胺醯亞胺化合物、吡啶衍生物化合物、α-胺基苯乙酮衍生物化合物、四級銨鹽衍生物化合物、吡啶鎓鹽、α-內酯環衍生物化合物、胺基醯亞胺化合物、鄰苯二甲醯亞胺衍生物化合物、醯氧基亞胺化合物等。 ＜Base generator＞ The resin composition of the present invention may contain a base generator. Here, a base generator refers to a compound capable of generating a base through physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. When the resin composition contains a thermal base generator, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties or chemical resistance of the cured product can be improved, for example, it can be used as an interlayer insulation for a rewiring layer included in a semiconductor package. The performance of the membrane becomes better. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator of the present invention is not particularly limited, and known base generators can be used. As well-known base generators, for example, carbamate oxime compounds, carbamate hydroxylamine compounds, carbamate compounds, formamide compounds, acetylamine compounds, carbamate compounds, and benzylamine can be used. methyl formate compound, nitrobenzyl carbamate compound, sulfonamide compound, imidazole derivative compound, amine imine compound, pyridine derivative compound, α-aminoacetophenone derivative compound, tetracarbamate compound Grade ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amino acyl imine compounds, phthalyl imine derivative compounds, acyl oxy imine compounds, etc.

在本發明的樹脂組成物包含鹼產生劑的情況下，鹼產生劑的含量相對於本發明的樹脂組成物中的樹脂100質量份係0.1～50質量份為較佳。下限為0.3質量份以上為更佳，0.5質量份以上為進一步較佳。上限係30質量份以下為更佳，20質量份以下為進一步較佳，10質量份以下為更進一步較佳，可以為5質量份以下，亦可以為4質量份以下。 鹼產生劑能夠使用1種或2種以上。在使用2種以上的情況下，合計量在上述範圍內為較佳。 When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. It is more preferable that the lower limit is 0.3 parts by mass or more, and it is still more preferable that it is 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less. It may be 5 parts by mass or less, or it may be 4 parts by mass or less. One type or two or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.

＜金屬接著性改良劑＞ 本發明的樹脂組成物包含用於提高與在電極或配線等中所使用之金屬材料的接著性之金屬接著性改良劑為較佳。作為金屬接著性改良劑，可以舉出具有烷氧基矽基之矽烷偶合劑、鋁系接著助劑、鈦系接著助劑、具有磺醯胺結構之化合物及具有硫脲結構之化合物、磷酸衍生物化合物、β酮酸酯化合物、胺基化合物等。 該等之中，本發明的樹脂組成物進一步包含矽烷偶合劑為較佳。 ＜Metal adhesion improver＞ The resin composition of the present invention preferably contains a metal adhesion improving agent for improving the adhesion to metal materials used for electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, and phosphoric acid derivatives. compounds, beta ketoacid ester compounds, amine compounds, etc. Among these, it is preferable that the resin composition of the present invention further contains a silane coupling agent.

〔矽烷偶合劑〕 作為矽烷偶合劑，例如，可以舉出國際公開第2015/199219號0167段中所記載之化合物、日本特開2014-191002號公報0062～0073段中所記載之化合物、國際公開第2011/080992號0063～0071段中所記載之化合物、日本特開2014-191252號公報0060～0061段中所記載之化合物、日本特開2014-041264號公報0045～0052段中所記載之化合物、國際公開第2014/097594號0055段中所記載之化合物、日本特開2018-173573的0067～0078段中所記載之化合物，該等內容編入本說明書中。又，如日本特開2011-128358號公報的0050～0058段中所記載，使用不同之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，Me表示甲基，Et表示乙基。 [Silane coupling agent] Examples of the silane coupling agent include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, and the compounds described in International Publication No. 2011/080992. Compounds described in paragraphs 0063 to 0071, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, International Publication No. 2014 The compounds described in paragraph 0055 of /097594 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Laid-Open No. 2018-173573 are incorporated into this specification. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. In addition, it is also preferable to use the following compounds as a silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[化學式21] [Chemical formula 21]

〔鋁系接著助劑〕 作為鋁系接著助劑，例如，能夠舉出三（乙醯乙酸乙酯）鋁、三（乙醯丙酮）鋁、乙醯乙酸乙酯二異丙酯鋁等。 [Aluminum-based adhesion additives] Examples of aluminum-based adhesive aids include tris(acetyl ethyl acetate)aluminum, tris(acetyl acetonate)aluminum, acetyl ethyl acetate diisopropyl aluminum, and the like.

又，作為其他金屬接著性改良劑，亦能夠使用日本特開2014-186186號公報的0046～0049段中所記載之化合物、日本特開2013-072935號公報的0032～0043段中所記載之硫醚系化合物，該等內容編入本說明書中。In addition, as other metal adhesion improvers, the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186, and the sulfur compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can also be used. Ether compounds are included in this specification.

金屬接著性改良劑的含量相對於特定樹脂100質量份，較佳為0.01～30質量份，更佳為0.1～10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，圖案與金屬層的接著性變良好，藉由設為上述上限值以下，圖案的耐熱性、機械特性變良好。金屬接著性改良劑可以為僅1種，亦可以為2種以上。在使用2種以上的情況下，其合計在上述範圍內為較佳。The content of the metal adhesion improving agent is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.1 to 10 parts by mass, and further preferably in the range of 0.5 to 5 parts by mass based on 100 parts by mass of the specific resin. By setting it as above the said lower limit value, the adhesiveness of a pattern and a metal layer becomes good, and by setting it as below the said upper limit value, the heat resistance and mechanical characteristics of a pattern become good. The number of metal adhesion improving agents may be only one type, or two or more types. When two or more types are used, it is preferable that the total is within the above range.

＜遷移抑制劑＞ 本發明的樹脂組成物可以進一步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）之金屬離子轉移到膜內。 ＜Migration inhibitor＞ The resin composition of the present invention may preferably further contain a migration inhibitor. By including a migration inhibitor, it is possible to effectively suppress the transfer of metal ions from the metal layer (metal wiring) into the membrane.

作為遷移抑制劑，並沒有特別限制，可以舉出具有雜環（吡咯環、呋喃環、噻吩環、咪唑環、噁唑環、噻唑環、吡唑環、異噁唑環、異噻唑環、四唑環、吡啶環、嗒口井環、嘧啶環、吡口井環、哌啶環、哌口井環、口末啉環、2H-哌喃環及6H-哌喃環、三口井環）之化合物、具有硫脲類及氫硫基之化合物、受阻酚系化合物、水楊酸衍生物系化合物、醯肼衍生物系化合物。尤其，能夠較佳地使用1,2,4-三唑、苯并三唑、3-胺基-1,2,4-三唑、3,5-二胺基-1,2,4-三唑等三唑系化合物、1H-四唑、5-苯基四唑、5-胺基-1H-四唑等四唑系化合物。The migration inhibitor is not particularly limited, and examples thereof include heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, azole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperazine ring, endoline ring, 2H-pyran ring and 6H-pyran ring, three ring) Compounds, compounds having thiourea and hydrogen sulfide groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazine derivative compounds. In particular, 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole can be preferably used. Triazole compounds such as azole, tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole.

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

在本發明的樹脂組成物具有遷移抑制劑的情況下，遷移抑制劑的含量相對於本發明的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。When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, and more preferably 0.05 to 2.0 mass% relative to the total solid content of the resin composition of the present invention. , 0.1 to 1.0% by mass is more preferred.

遷移抑制劑可以為僅1種，亦可以為2種以上。在遷移抑制劑為2種以上的情況下，其合計在上述範圍內為較佳。There may be only one type of migration inhibitor, or two or more types of migration inhibitors. When there are two or more types of migration inhibitors, the total number is preferably within the above range.

＜聚合抑制劑＞ 本發明的樹脂組成物包含聚合抑制劑為較佳。作為聚合抑制劑，可以舉出酚系化合物、醌系化合物、胺基系化合物、N-氧自由基化合物系化合物、硝基系化合物、亞硝基系化合物、雜芳香環系化合物、金屬化合物等。 ＜Polymerization inhibitor＞ The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenol compounds, quinone compounds, amine compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds, etc. .

在本發明的樹脂組成物具有聚合抑制劑的情況下，聚合抑制劑的含量相對於本發明的樹脂組成物的總固體成分係0.01～20質量%為較佳，0.02～15質量%為更佳，0.05～10質量%為進一步較佳。When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, and more preferably 0.02 to 15 mass % relative to the total solid content of the resin composition of the present invention. , 0.05 to 10% by mass is more preferred.

聚合抑制劑可以為僅1種，亦可以為2種以上。在聚合抑制劑為2種以上的情況下，其合計在上述範圍內為較佳。The number of polymerization inhibitors may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total number is preferably within the above range.

＜酸捕捉劑＞ 為了減少從曝光至加熱為止的經時而引起之性能變化，本發明的樹脂組成物含有酸捕捉劑為較佳。其中，酸捕捉劑係指，藉由存在於系統中而能夠捕捉產生酸之化合物，酸度低且pKa高的化合物為較佳。作為酸捕捉劑，具有胺基之化合物為較佳，一級胺、二級胺、三級胺、銨鹽、三級醯胺等為較佳，一級胺、二級胺、三級胺、銨鹽為較佳，二級胺、三級胺、銨鹽為更佳。 作為酸捕捉劑，能夠較佳地舉出具有咪唑結構、二氮雜雙環結構、鎓結構、三烷基胺結構、苯胺結構或吡啶結構之化合物、具有羥基和/或醚鍵之烷基胺衍生物、具有羥基和/或醚鍵之苯胺衍生物等。在具有鎓結構之情況下，酸捕捉劑係具有選自銨、重氮、錪、鋶、鏻、吡啶鎓等之陽離子和酸度比由酸產生劑所產生之酸更低的酸的陰離子之鹽為較佳。 ＜Acid capture agent＞ In order to reduce performance changes caused by time from exposure to heating, the resin composition of the present invention preferably contains an acid scavenger. Among them, the acid capture agent refers to a compound that can capture acid by being present in the system, and a compound with low acidity and high pKa is preferred. As acid capture agents, compounds with amine groups are preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, and tertiary amide are preferred. Primary amines, secondary amines, tertiary amines, and ammonium salts are preferred. is preferred, and secondary amines, tertiary amines, and ammonium salts are even more preferred. Preferred acid capture agents include compounds having an imidazole structure, a diazabicyclic structure, an onium structure, a trialkylamine structure, an aniline structure or a pyridine structure, and alkylamine derivatives having a hydroxyl group and/or an ether bond. substances, aniline derivatives with hydroxyl and/or ether bonds, etc. In the case of having an onium structure, the acid capture agent is a salt having a cation selected from the group consisting of ammonium, diazo, iodonium, sulfonium, phosphonium, pyridinium, etc. and an anion of an acid having a lower acidity than the acid generated by the acid generator. For better.

該等酸捕捉劑可以單獨使用1種，亦可以組合使用2種以上。 本發明之組成物可以含有酸捕捉劑，亦可以不含有酸捕捉劑，但是在含有之情況下，酸捕捉劑的含量以組成物的總固體成分為基準，通常為0.001～10質量%，較佳為0.01～5質量%。 One type of these acid scavengers may be used alone, or two or more types may be used in combination. The composition of the present invention may or may not contain an acid scavenger. However, if it does, the content of the acid scavenger is based on the total solid content of the composition, which is usually 0.001 to 10% by mass, which is less than 0.001% by mass. Preferably, it is 0.01 to 5% by mass.

酸產生劑與酸捕捉劑的使用比例係酸產生劑/酸捕捉劑（莫耳比）=2.5～300為較佳。亦即，從靈敏度、解析度的觀點考慮，莫耳比為2.5以上為較佳，從抑制曝光後到加熱處理為止的經時中浮雕圖案變厚所引起之解析度降低的觀點考慮，300以下為較佳。酸產生劑/酸捕捉劑（莫耳比）更佳為5.0～200，進一步較佳為7.0～150。The ratio of acid generator to acid capture agent is preferably acid generator/acid capture agent (molar ratio) = 2.5 to 300. That is, from the viewpoint of sensitivity and resolution, a molar ratio of 2.5 or more is preferred, and from the viewpoint of suppressing a decrease in resolution caused by thickening of the relief pattern over time from exposure to heat treatment, a molar ratio of 300 or less is preferred. For better. The acid generator/acid capture agent (molar ratio) is more preferably 5.0 to 200, further preferably 7.0 to 150.

＜其他添加劑＞ 本發明的樹脂組成物在可以獲得本發明的效果之範圍內，能夠根據需要配合各種的添加物，例如界面活性劑、高級脂肪酸衍生物、熱聚合起始劑、無機粒子、紫外線吸收劑、有機鈦化合物、抗氧化劑、抗凝聚劑、酚系化合物、其他高分子化合物、可塑劑及其他助劑類（例如，消泡劑、阻燃劑等）等。藉由適當地含有該等成分，能夠調整膜物理性質等性質。關於該等成分，例如，能夠參考日本特開2012-003225號公報的0183段以後（對應之美國專利申請公開第2013/0034812號說明書的0237段）的記載、日本特開2008-250074號公報的0101～0104、0107～0109段等的記載，該等內容編入本說明書中。在配合該等添加劑的情況下，將其合計配合量設為本發明的樹脂組成物的固體成分的3質量%以下為較佳。 ＜Other additives＞ The resin composition of the present invention can be blended with various additives as needed, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic Titanium compounds, antioxidants, anti-coagulants, phenolic compounds, other polymer compounds, plasticizers and other additives (for example, defoaming agents, flame retardants, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. Regarding these components, for example, reference can be made to the descriptions of paragraphs 0183 and onwards of Japanese Patent Application Laid-Open No. 2012-003225 (corresponding to paragraph 0237 of the specification of U.S. Patent Application Publication No. 2013/0034812), and the descriptions of Japanese Patent Application Laid-Open No. 2008-250074. The descriptions in paragraphs 0101 to 0104, 0107 to 0109, etc. are incorporated into this manual. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

〔界面活性劑〕 作為界面活性劑，能夠使用氟系界面活性劑、聚矽氧系界面活性劑、烴系界面活性劑等各種界面活性劑。界面活性劑可以為非離子型界面活性劑，可以為陽離子型界面活性劑，亦可以為陰離子型界面活性劑。 〔Surface active agent〕 As the surfactant, various surfactants such as fluorine-based surfactants, polysiloxane-based surfactants, and hydrocarbon-based surfactants can be used. The surfactant can be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

藉由在本發明的感光性樹脂組成物中含有界面活性劑，能夠進一步提高製成塗佈液時的液體特性（尤其流動性），並進一步改善塗佈厚度的均勻性或省液性。亦即，在利用適用了含有界面活性劑之組成物之塗佈液形成膜的情況下，被塗佈面與塗佈液之間的界面張力下降，藉此改善對被塗佈面的潤濕性，並提高對被塗佈面的塗佈性。因此，能夠進一步較佳地形成厚度不均少的均勻厚度的膜。By containing a surfactant in the photosensitive resin composition of the present invention, the liquid characteristics (especially fluidity) when the coating liquid is prepared can be further improved, and the uniformity of the coating thickness or the liquid saving property can be further improved. That is, when a film is formed using a coating liquid using a composition containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, thereby improving the wetting of the surface to be coated. properties and improve coating properties on the coated surface. Therefore, a film with a uniform thickness and less uneven thickness can be formed more preferably.

界面活性劑可以僅使用1種，亦可以組合使用2種類以上。 界面活性劑的含量相對於組成物的總固體成分係0.001～2.0質量%為較佳，0.005～1.0質量%為更佳。 Only one type of surfactant may be used, or two or more types may be used in combination. The content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass relative to the total solid content of the composition.

〔高級脂肪酸衍生物〕 為了防止由氧導致的聚合阻礙，本發明的樹脂組成物中可以添加二十二酸或二十二酸醯胺之類的高級脂肪酸衍生物而使其在塗佈後的乾燥過程中偏在於本發明的樹脂組成物的表面。 [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 resin composition of the present invention to bias the resin composition during the drying process after coating. The surface of the resin composition of the invention.

又，高級脂肪酸衍生物亦能夠使用國際公開第2015/199219號的0155段中所記載之化合物，該內容編入本說明書中。In addition, compounds described in paragraph 0155 of International Publication No. 2015/199219 can also be used as the higher fatty acid derivatives, and this content is incorporated into this specification.

在本發明的樹脂組成物含有高級脂肪酸衍生物的情況下，高級脂肪酸衍生物的含量相對於本發明的樹脂組成物的總固體成分，0.1～10質量%為較佳。高級脂肪酸衍生物可以僅為1種，亦可以為2種以上。在高級脂肪酸衍生物為2種以上的情況下，其合計在上述範圍內為較佳。When the 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 resin composition of the present invention. The number of higher fatty acid derivatives may be only one type, or two or more types. When there are two or more types of higher fatty acid derivatives, the total number is preferably within the above range.

〔熱聚合起始劑〕 本發明的樹脂組成物可以包含熱聚合起始劑，尤其可以包含熱自由基聚合起始劑。熱自由基聚合起始劑係藉由熱能而產生自由基，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，亦能夠使樹脂及聚合性化合物進行聚合反應，因此能夠進一步提高耐溶劑性。又，有時上述光聚合起始劑亦具有藉由熱而開始聚合之作用，有時能夠作為熱聚合起始劑添加。 [Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, especially a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates free radicals through thermal energy and starts or promotes the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the resin and the polymerizable compound can also be polymerized, so the solvent resistance can be further improved. In addition, the above-mentioned photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

作為熱自由基聚合起始劑，具體而言，可以舉出日本特開2008-063554號公報的0074～0118段中所記載之化合物，該內容編入本說明書中。Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554, the contents of which are incorporated in this specification.

在包含熱聚合起始劑的情況下，其含量相對於本發明的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%。熱聚合起始劑可以僅含有1種，亦可以含有2種以上。在含有2種以上熱聚合起始劑的情況下，合計量在上述範圍內為較佳。When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.5 to 30% by mass relative to the total solid content of the resin composition of the present invention. 15% by mass. The thermal polymerization initiator may contain only one type or two or more types. When two or more types of thermal polymerization initiators are contained, the total amount is preferably within the above range.

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

作為上述無機粒子的平均粒徑，0.01～2.0μm為較佳，0.02～1.5μm為更佳，0.03～1.0μm為進一步較佳，0.04～0.5μm為特佳。 微粒子的上述平均粒徑為一次粒徑，又，為體積平均粒徑。體積平均粒徑能夠藉由基於Nanotrac WAVE II EX-150（NIKKISO CO.,LTD.製）之動態光散射法測定。 在難以進行上述測定的情況下，亦能夠藉由離心沉降透光法、X射線透射法、雷射衍射/散射法測定。 The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above-mentioned average particle diameter of fine particles is a primary particle diameter, and is a volume average particle diameter. The volume average particle size can be measured by a dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO., LTD.). When it is difficult to perform the above measurement, it can also be measured by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method.

〔紫外線吸收劑〕 本發明的組成物可以包含紫外線吸收劑。作為紫外線吸收劑，能夠使用水楊酸酯系、二苯甲酮系、苯并三唑系、取代丙烯腈系、三口井系等紫外線吸收劑。 [UV absorber] The compositions of the present invention may contain ultraviolet absorbers. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and Sankui-based ultraviolet absorbers can be used.

在本發明中，上述各種紫外線吸收劑可以單獨使用1種，亦可以組合使用2種以上。 本發明的組成物可以包含紫外線吸收劑，亦可以不包含紫外線吸收劑，但包含的情況下，紫外線吸收劑的含量相對於本發明的組成物的總固體成分質量，0.001質量%以上且1質量%以下為較佳，0.01質量%以上且0.1質量%以下為更佳。 In the present invention, one of the various ultraviolet absorbers mentioned above may be used alone, or two or more types may be used in combination. The composition of the present invention may or may not contain an ultraviolet absorber. However, when it is included, the content of the ultraviolet absorber shall be 0.001% by mass or more and 1 mass% relative to the total solid mass of the composition of the present invention. % or less is preferred, and 0.01 mass % or more and 0.1 mass % or less is even more preferred.

〔有機鈦化合物〕 本實施形態的樹脂組成物可以含有有機鈦化合物。藉由樹脂組成物含有有機鈦化合物，在低溫下硬化的情況下亦能夠形成耐藥品性優異之樹脂層。 [Organotitanium compound] The resin composition of this embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer with excellent chemical resistance can be formed even when cured at low temperature.

作為能夠使用的有機鈦化合物，可以舉出有機基團經由共價鍵或離子鍵與鈦原子鍵結者。 在以下I）～VII）中示出有機鈦化合物的具體例： I）螯合鈦化合物：其中，從樹脂組成物的保存穩定性良好且可以獲得良好的硬化圖案的方面考慮，具有2個以上烷氧基之螯合鈦化合物為更佳。 Examples of organic titanium compounds that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown in the following I) to VII): I) Chelated titanium compound: Among them, a chelated titanium compound having two or more alkoxy groups is more preferable in terms of good storage stability of the resin composition and good hardened pattern.

在配合有機鈦化合物的情況下，其配合量相對於100質量份的特定樹脂，0.05～10質量份為較佳，更佳為0.1～2質量份。在配合量為0.05質量份以上的情況下，所獲得之硬化圖案更有效地顯示出良好的耐熱性及耐藥品性，另一方面，10質量份以下的情況下，組成物的保存穩定性更優異。When an organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass relative to 100 parts by mass of the specific resin. When the blending amount is 0.05 parts by mass or more, the obtained hardened pattern exhibits good heat resistance and chemical resistance more effectively. On the other hand, when the blending amount is 10 parts by mass or less, the composition has better storage stability. Excellent.

〔抗氧化劑〕 本發明的組成物可以包含抗氧化劑。藉由含有抗氧化劑作為添加劑，能夠提高硬化後的膜的拉伸特性、與金屬材料的密接性。作為抗氧化劑，可以舉出酚化合物、亞磷酸酯化合物、硫醚化合物等。 〔Antioxidants〕 The compositions of the present invention may contain antioxidants. By containing antioxidants as additives, the tensile properties of the cured film and the adhesion to metal materials can be improved. Examples of antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like.

抗氧化劑的添加量相對於特定樹脂100質量份，0.1～10質量份為較佳，0.5～5質量份為更佳。藉由將添加量設為0.1質量份以上，即使在高溫高濕環境下，亦容易獲得拉伸特性、提高對金屬材料的密接性的效果，又，藉由設為10質量份以下，例如利用與感光劑的相互作用，樹脂組成物的靈敏度提高。抗氧化劑可以僅使用1種，亦可以使用2種以上。使用2種以上的情況下，該等的合計量在上述範圍內為較佳。The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass based on 100 parts by mass of the specific resin. By setting the addition amount to 0.1 parts by mass or more, tensile properties and the effect of improving adhesion to metal materials can be easily obtained even in high-temperature and high-humidity environments, and by setting the addition amount to 10 parts by mass or less, for example, using The interaction with the photosensitizer improves the sensitivity of the resin composition. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

〔抗凝聚劑〕 本實施形態的樹脂組成物可根據需要含有抗凝聚劑。作為抗凝聚劑，可以舉出聚丙烯酸鈉等。 [Anti-agglomeration agent] The resin composition of this embodiment may contain an anti-aggregation agent if necessary. Examples of anti-aggregation agents include sodium polyacrylate and the like.

本發明中，可以單獨使用1種抗凝聚劑，亦可以組合使用2種以上。 本發明的組成物可以包含抗凝聚劑，亦可以不包含抗凝聚劑，但在包含的情況下，抗凝聚劑的含量相對於本發明的組成物的總固體成分質量，0.01質量%以上且10質量%以下為較佳，0.02質量%以上且5質量%以下為更佳。 In the present invention, one type of anti-aggregation agent may be used alone, or two or more types may be used in combination. The composition of the present invention may or may not contain an anti-coagulant. However, in the case where it is included, the content of the anti-coagulant shall be 0.01% by mass or more and 10% or more relative to the total solid mass of the composition of the present invention. It is more preferable that it is 0.02 mass % or less and 5 mass % or less.

〔酚系化合物〕 本實施形態的樹脂組成物可以根據需要含有酚系化合物。作為酚系化合物，可以舉出Bis-Z、BisP-EZ、TekP-4HBPA、TrisP-HAP、TrisP-PA、BisOCHP-Z、BisP-MZ、BisP-PZ、BisP-IPZ、BisOCP-IPZ、BisP-CP、BisRS-2P、BisRS-3P、BisP-OCHP、Methylene Tris-FR-CR、BisRS-26X（以上為商品名，Honshu Chemical Industry Co.,Ltd.製）、BIP-PC、BIR-PC、BIR-PTBP、BIR-BIPC-F（以上為商品名，ASAHI YUKIZAI CORPORATION製）等。 [Phenolic compounds] The resin composition of this embodiment may contain a phenolic compound as needed. Examples of the phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP- CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X (the above are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR -PTBP, BIR-BIPC-F (the above are trade names, manufactured by ASAHI YUKIZAI CORPORATION), etc.

在本發明中，酚系化合物可以單獨使用1種，亦可以組合使用2種以上。 本發明的組成物可以包含酚系化合物，亦可以不包含酚系化合物，但在包含的情況下，酚系化合物的含量相對於本發明的組成物的總固體成分質量，0.01質量%以上且30質量%以下為較佳，0.02質量%以上且20質量%以下為更佳。 In the present invention, one type of phenolic compound may be used alone, or two or more types may be used in combination. The composition of the present invention may or may not contain a phenolic compound. However, when it is included, the content of the phenolic compound shall be 0.01% by mass or more and 30% or more relative to the total solid mass of the composition of the present invention. It is more preferable that it is 0.02 mass % or less and 20 mass % or less.

〔其他高分子化合物〕 作為其他高分子化合物，可以舉出矽氧烷樹脂、與（甲基）丙烯酸共聚的（甲基）丙烯酸聚合物、酚醛清漆樹脂、甲階酚醛樹脂、多羥基苯乙烯樹脂及該等的共聚物等。其他高分子化合物可以為導入了羥甲基、烷氧基甲基、環氧基等交聯基之改質體。 [Other polymer compounds] Examples of other polymer compounds include siloxane resin, (meth)acrylic acid polymer copolymerized with (meth)acrylic acid, novolac resin, resol phenolic resin, polyhydroxystyrene resin, and copolymers thereof. wait. Other polymer compounds may be modified products in which cross-linking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups are introduced.

本發明中，其他高分子化合物可以單獨使用1種，亦可以組合使用2種以上。 本發明的組成物可以包含其他高分子化合物，亦可以不包含其他高分子化合物，但在包含的情況下，其他高分子化合物的含量相對於本發明的組成物的總固體成分質量，0.01質量%以上且30質量%以下為較佳，0.02質量%以上且20質量%以下為更佳。 In the present invention, one type of other polymer compounds may be used alone, or two or more types may be used in combination. The composition of the present invention may or may not contain other polymer compounds. However, in the case of inclusion, the content of other polymer compounds shall be 0.01% by mass relative to the total solid mass of the composition of the present invention. More than 30 mass % is preferred, and 0.02 mass % or more and 20 mass % or less is more preferred.

＜樹脂組成物的特性＞ 本發明的樹脂組成物的黏度能夠根據樹脂組成物的固體成分濃度調整。從塗佈膜厚的觀點考慮，1,000mm 2/s～12,000mm 2/s為較佳，2,000mm 2/s～10,000mm 2/s為更佳，2,500mm 2/s～8,000mm 2/s為進一步較佳。只要在上述範圍內，則容易獲得均勻性高的塗佈膜。例如，若為1,000mm 2/s以上，則容易以作為再配線用絕緣膜所需的膜厚塗佈，若為12,000mm 2/s以下，則可以獲得塗佈面狀優異之塗膜。 <Characteristics of the resin composition> The viscosity of the resin composition of the present invention can be adjusted according to the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000mm 2 /s to 12,000mm 2 /s is preferred, 2,000mm 2 /s to 10,000mm 2 /s is more preferred, and 2,500mm 2 /s to 8,000mm 2 /s For further improvement. As long as it is within the above range, it is easy to obtain a highly uniform coating film. For example, if it is 1,000 mm 2 /s or more, it is easy to coat with a film thickness required as an insulating film for rewiring, and if it is 12,000 mm 2 /s or less, a coating film with excellent coating surface shape can be obtained.

＜對樹脂組成物含有物質的限制＞ 本發明的樹脂組成物的含水率小於2.0質量%為較佳，小於1.5質量%為更佳，小於1.0質量%為進一步較佳。若小於2.0%，則樹脂組成物的保存穩定性提高。 作為維持含水量的方法，可以舉出保管條件下的濕度調整、保管時的收容容器的孔隙率降低等。 <Restrictions on substances contained in resin compositions> The moisture content of the resin composition of the present invention is preferably less than 2.0 mass%, more preferably less than 1.5 mass%, and still more preferably less than 1.0 mass%. If it is less than 2.0%, the storage stability of the resin composition will be improved. Examples of methods for maintaining the moisture content include humidity adjustment under storage conditions, reduction of the porosity of the storage container during storage, and the like.

從絕緣性的觀點考慮，本發明的樹脂組成物的金屬含量小於5質量ppm（parts per million（百萬分率））為較佳，小於1質量ppm為更佳，小於0.5質量ppm為進一步較佳。作為金屬，可以舉出鈉、鉀、鎂、鈣、鐵、銅、鉻、鎳等，但作為有機化合物與金屬的錯合物來包含之金屬除外。包含複數種金屬的情況下，該等金屬的合計在上述範圍內為較佳。From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. good. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., except for metals contained as complexes of organic compounds and metals. When a plurality of metals are included, the total amount of these metals is preferably within the above range.

又，作為減少意外包含在本發明的樹脂組成物中的金屬雜質之方法，能夠舉出如下方法：選擇金屬含量少的原料作為構成本發明的樹脂組成物之原料，對構成本發明的樹脂組成物之原料進行過濾器過濾，用聚四氟乙烯等對裝置內進行內襯而在盡可能抑制污染的條件下進行蒸餾等。In addition, as a method of reducing metal impurities accidentally contained in the resin composition of the present invention, the following method can be cited: selecting a raw material with a small metal content as a raw material constituting the resin composition of the present invention, and adjusting the composition of the resin composition of the present invention. The raw materials are filtered, the inside of the device is lined with polytetrafluoroethylene, etc., and distillation is performed under conditions that suppress contamination as much as possible.

關於本發明的樹脂組成物，若考慮作為半導體材料的用途，則從配線腐蝕性的觀點考慮，鹵素原子的含量小於500質量ppm為較佳，小於300質量ppm為更佳，小於200質量ppm為進一步較佳。其中，以鹵素離子的狀態存在者小於5質量ppm為較佳，小於1質量ppm為更佳，小於0.5質量ppm為進一步較佳。作為鹵素原子，可以舉出氯原子及溴原子。氯原子及溴原子或氯離子及溴離子的合計分別在上述範圍內為較佳。 作為調整鹵素原子的含量的方法，可較佳地舉出離子交換處理等。 Regarding the resin composition of the present invention, if the use as a semiconductor material is considered, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm. Better still. Among them, the amount of halogen ions present in the state is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and still more preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total number of chlorine atoms and bromine atoms or chlorine ions and bromide ions is within the above range. Preferable methods for adjusting the content of halogen atoms include ion exchange treatment and the like.

作為本發明的樹脂組成物的收容容器，能夠使用以往公知的收容容器。又，作為收容容器，以抑制雜質混入原材料或本發明的樹脂組成物中為目的，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。作為該種容器，例如，可以舉出日本特開2015-123351號公報中所記載之容器。As a container for storing the resin composition of the present invention, a conventionally known container can be used. In addition, as a storage container, for the purpose of suppressing the mixing of impurities into the raw materials or the resin composition of the present invention, a multi-layer bottle with an inner wall composed of six types of six resins or a bottle with a seven-layer structure using six types of resins is used. Better. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

＜樹脂組成物的硬化物＞ 藉由硬化本發明的樹脂組成物，能夠獲得該樹脂組成物的硬化物， 本發明的硬化物為硬化本發明的樹脂組成物而成之硬化物。 樹脂組成物的硬化藉由加熱進行為較佳，加熱溫度在120℃～400℃的範圍內為更佳，在140℃～380℃的範圍內為進一步較佳，在160℃～350℃的範圍內為特佳。樹脂組成物的硬化物的形態並沒有特別限定，能夠根據用途選擇膜狀、棒狀、球狀、顆粒狀等。本發明中，該硬化物為膜狀為較佳。又，藉由樹脂組成物的圖案加工，亦能夠根據在壁面形成保護膜、形成導通用通孔、調整阻抗、靜電電容或內部應力、賦予散熱功能等用途選擇該硬化物的形狀。該硬化物（由硬化物構成之膜）的膜厚為0.5μm以上且150μm以下為較佳。 本發明的樹脂組成物硬化時的收縮率為50%以下為較佳，45%以下為更佳，40%以下為進一步較佳。在此，收縮率係指樹脂組成物的硬化前後的體積變化的百分率，能夠根據下述式算出。 收縮率[%]=100-（硬化後的體積÷硬化前的體積）×100 ＜Cure product of resin composition＞ By curing the resin composition of the present invention, a cured product of the resin composition can be obtained, The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. Hardening of the resin composition is preferably carried out by heating. The heating temperature is more preferably in the range of 120°C to 400°C, further preferably in the range of 140°C to 380°C, and in the range of 160°C to 350°C. The inside is excellent. The form of the cured product of the resin composition is not particularly limited, and film, rod, spherical, granular, etc. can be selected according to the use. In the present invention, it is preferable that the cured material is in the form of a film. In addition, by patterning the resin composition, the shape of the cured product can be selected according to purposes such as forming a protective film on the wall surface, forming via holes for conduction, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function. The film thickness of the cured material (film composed of the cured material) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and still more preferably 40% or less. Here, the shrinkage rate refers to the percentage of volume change of the resin composition before and after curing, and can be calculated based on the following formula. Shrinkage rate [%] = 100 - (volume after hardening ÷ volume before hardening) × 100

＜樹脂組成物的硬化物的特性＞ 本發明的樹脂組成物的硬化物的醯亞胺化反應率為70%以上為較佳，80%以上為更佳，90%以上為進一步較佳。若為70%以上，則有時會成為機械特性優異之硬化物。 本發明的樹脂組成物的硬化物的斷裂伸長率為30%以上為較佳，40%以上為更佳，50%以上為進一步較佳。 本發明的樹脂組成物的硬化物的玻璃轉移溫度（Tg）為180℃以上為較佳，210℃以上為更佳，230℃以上為進一步較佳。 <Characteristics of hardened product of resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If it is 70% or more, a hardened material with excellent mechanical properties may be obtained. The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and further preferably 50% or more. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and further preferably 230°C or higher.

＜樹脂組成物的製備＞ 本發明的樹脂組成物能夠藉由混合上述各成分來製備。混合方法並沒有特別限定，能夠藉由以往公知的方法來進行。 混合能夠採用基於攪拌葉片之混合、基於球磨機之混合、使罐本身旋轉的混合等。 混合中的溫度為10～30℃為較佳，15～25℃為更佳。 <Preparation of resin composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be performed by conventionally known methods. Mixing can be done by mixing with a stirring blade, mixing by a ball mill, mixing by rotating the tank itself, etc. The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

又，以去除本發明的樹脂組成物中的灰塵或微粒等異物為目的，進行使用過濾器之過濾為較佳。關於過濾器孔徑，例如可以舉出5μm以下之態樣，1μm以下為較佳，0.5μm以下為更佳，0.1μm以下為進一步較佳。過濾器的材質為聚四氟乙烯、聚乙烯或尼龍為較佳。過濾器的材質為聚乙烯的情況下，HDPE（高密度聚乙烯）為更佳。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，複數種過濾器可以串聯或並聯連接使用。使用複數種過濾器的情況下，可以組合使用孔徑或材質不同之過濾器。作為連接態樣，例如，可以舉出如下態樣：將孔徑1μm的HDPE過濾器作為第一段，將孔徑0.2μm的HDPE過濾器作為第二段，將兩者串聯連接。又，可以將各種材料過濾複數次。過濾複數次的情況下，可以為循環過濾。又，可以進行加壓過濾。進行加壓過濾的情況下，例如可以舉出所施加的壓力為0.01MPa以上且1.0MPa以下之態樣，0.03MPa以上且0.9MPa以下為較佳，0.05MPa以上且0.7MPa以下為更佳，0.05MPa以上且0.5MPa以下為進一步較佳。 除了使用過濾器之過濾以外，亦可以進行使用吸附材料之雜質去除處理。亦可以組合過濾器過濾和使用吸附材料之雜質去除處理。作為吸附材料，能夠使用公知的吸附材料。例如，可以舉出矽膠、沸石等無機系吸附材料、活性碳等有機系吸附材料。 可以在用過濾器進行過濾之後，進一步實施將填充於瓶中的樹脂組成物放置於減壓下進行脫氣之步驟。 In addition, for the purpose of removing foreign matter such as dust or particles in the resin composition of the present invention, it is preferable to perform filtration using a filter. The filter pore size is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is better. Filters can be pre-cleaned with organic solvents. In the filtration step of the filter, multiple types of filters can be connected in series or in parallel. When using multiple types of filters, filters with different pore sizes or materials can be used in combination. As a connection aspect, for example, an aspect can be cited in which an HDPE filter with a pore size of 1 μm is used as the first stage, an HDPE filter with a pore size of 0.2 μm is used as the second stage, and the two are connected in series. In addition, various materials can be filtered multiple times. When filtering multiple times, circular filtering can be used. In addition, pressure filtration can be performed. When performing pressure filtration, for example, the applied pressure is 0.01 MPa or more and 1.0 MPa or less. Preferably, it is 0.03 MPa or more and 0.9 MPa or less. More preferably, it is 0.05 MPa or more and 0.7 MPa or less. It is further more preferable that it is 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using filters, impurity removal using adsorbent materials can also be performed. It is also possible to combine filter filtration and impurity removal using adsorbent materials. As the adsorbent material, known adsorbent materials can be used. Examples include inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon. After filtration with a filter, the resin composition filled in the bottle may be placed under reduced pressure to degas.

（硬化物的製造方法） 本發明的硬化物的製造方法包括在基材上適用樹脂組成物來形成膜之膜形成步驟為較佳。 又，本發明的硬化物的製造方法包括上述膜形成步驟、對藉由膜形成步驟形成之膜進行選擇性曝光之曝光步驟及使用顯影液對藉由曝光步驟被曝光的膜進行顯影來形成圖案之顯影步驟為更佳。 本發明的硬化物的製造方法包括上述膜形成步驟、上述曝光步驟、上述顯影步驟、以及對藉由顯影步驟獲得之圖案進行加熱之加熱步驟及對藉由顯影步驟獲得之圖案進行曝光之顯影後曝光步驟中的至少1個為特佳。 又，本發明的製造方法包括上述膜形成步驟及加熱上述膜之步驟亦為較佳。 以下，對各步驟的詳細內容進行說明。 (How to make hardened materials) The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition to a base material to form a film. Furthermore, the method for manufacturing a cured product of the present invention includes the above-mentioned film forming step, an exposure step of selectively exposing the film formed by the film forming step, and developing the film exposed by the exposure step using a developer to form a pattern. The development step is better. The manufacturing method of the cured product of the present invention includes the above-mentioned film formation step, the above-mentioned exposure step, the above-mentioned development step, a heating step of heating the pattern obtained by the development step, and a post-development step of exposing the pattern obtained by the development step. At least one of the exposure steps is particularly preferred. Furthermore, it is also preferable that the manufacturing method of the present invention includes the above-mentioned film forming step and the step of heating the above-mentioned film. The details of each step are explained below.

＜膜形成步驟＞ 本發明的樹脂組成物能夠在適用於基材上來形成膜之膜形成步驟中使用。 本發明的硬化物的製造方法包括在基材上適用樹脂組成物來形成膜之膜形成步驟為較佳。 <Film formation step> The resin composition of the present invention can be used in a film forming step suitable for forming a film on a base material. The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition to a base material to form a film.

〔基材〕 基材的種類能夠根據用途適當確定，可以舉出矽、氮化矽、聚矽、氧化矽、非晶矽等半導體製作用基材、石英、玻璃、光學膜、陶瓷材料、沉積膜、磁性膜、反射膜、Ni、Cu、Cr、Fe等金屬基材（例如，由金屬形成之基材及金屬層例如可以為藉由鍍覆、沉積等形成之基材中的任一種）、紙、SOG（Spin On Glass：旋塗式玻璃）、TFT（薄膜電晶體）陣列基材、鑄模基材、電漿顯示面板（PDP）的電極板等，並沒有特別限制。本發明中，尤其，半導體製作用基材為較佳，矽基材、Cu基材、鑄模基材為更佳。 又，可以在該等基材的表面設置有由六甲基二矽氮烷（HMDS）等形成之密接層、氧化層等層。 又，基材的形狀並沒有特別限定，可以為圓形形狀，亦可以為矩形形狀。 作為基材的尺寸，若為圓形形狀，則例如直徑為100～450mm，較佳為200～450mm。若為矩形形狀，則例如短邊的長度為100～1000mm，較佳為200～700mm。 又，作為基材，例如可以使用板狀，較佳為使用面板狀基材（基板）。 [Substrate] The type of base material can be appropriately determined according to the application, and examples thereof include base materials for semiconductor production such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical films, ceramic materials, deposited films, and magnetic films. , reflective film, metal substrates such as Ni, Cu, Cr, Fe (for example, the substrate and the metal layer formed of metal can be any of the substrates formed by plating, deposition, etc.), paper, SOG (Spin On Glass: spin-on glass), TFT (thin film transistor) array substrate, mold substrate, electrode plate of plasma display panel (PDP), etc., are not particularly limited. In the present invention, a base material for semiconductor production is particularly preferred, and a silicon base material, a Cu base material, and a mold base material are more preferred. In addition, layers such as an adhesion layer and an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided on the surfaces of the base materials. In addition, the shape of the base material is not particularly limited, and may be a circular shape or a rectangular shape. As for the size of the base material, if it has a circular shape, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. In the case of a rectangular shape, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm. In addition, as the base material, for example, a plate-like base material (substrate) can be used, and a panel-like base material (substrate) is preferably used.

又，在樹脂層（例如，由硬化物構成之層）的表面、金屬層的表面適用樹脂組成物來形成膜的情況下，樹脂層、金屬層成為基材。Furthermore, when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured material) or a metal layer to form a film, the resin layer or the metal layer becomes the base material.

作為將本發明的樹脂組成物適用於基材上之方法，塗佈為較佳。As a method for applying the resin composition of the present invention to a base material, coating is preferred.

作為適用方法，具體而言，可以例示出浸塗法、氣刀塗佈法、簾塗法、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。從膜的厚度均勻性的觀點考慮，更佳為旋塗法、狹縫塗佈法、噴塗法或噴墨法，從膜的厚度均勻性的觀點及生產性的觀點考慮，旋塗法及狹縫塗佈法為較佳。根據方法調整樹脂組成物的固體成分濃度、塗佈條件，藉此能夠獲得所期望厚度的膜。又，能夠根據基材的形狀適當選擇塗佈方法，若為晶圓等圓形基材，則旋塗法或噴塗法、噴墨法等為較佳，若為矩形基材，則狹縫塗佈法或噴塗法、噴墨法等為較佳。在旋塗法的情況下，例如能夠以500～3,500rpm的轉速適用10秒鐘～3分鐘左右。 又，亦能夠適用將藉由上述賦予方法預先在偽支撐體上賦予而形成之塗膜轉印在基材上之方法。 關於轉印方法，在本發明中，亦能夠較佳地利用日本特開2006-023696號公報的0023、0036～0051段或日本特開2006-047592號公報的0096～0108段中所記載之製作方法。 又，亦可以進行在基材的端部去除多餘膜之步驟。關於該種步驟的例子，可以舉出邊珠沖洗（edge bead rinse：EBR）、背面沖洗等。 又，亦可以採用如下預濕步驟：將樹脂組成物塗佈於基材之前，對基材塗佈各種溶劑以提高基材的潤濕性之後，塗佈樹脂組成物。 Specific examples of applicable methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, and narrow coating. Slit coating method and inkjet method, etc. From the viewpoint of film thickness uniformity, spin coating, slit coating, spray coating or inkjet are more preferred. From the viewpoint of film thickness uniformity and productivity, spin coating and slit coating are preferred. Slit coating method is better. By adjusting the solid content concentration and coating conditions of the resin composition according to the method, a film with a desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. If it is a round substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred. If it is a rectangular substrate, slit coating is suitable. Distribution method, spray coating method, inkjet method, etc. are preferred. In the case of the spin coating method, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes, for example. Furthermore, a method of transferring a coating film formed by applying it on a dummy support in advance by the above-mentioned application method to a base material can also be applied. Regarding the transfer method, in the present invention, the method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used. method. In addition, a step of removing excess film from the end portion of the base material may also be performed. Examples of such steps include edge bead rinse (EBR), backside rinse, and the like. Alternatively, a pre-wet step may be adopted: before applying the resin composition to the base material, various solvents are applied to the base material to improve the wettability of the base material, and then the resin composition is applied.

＜乾燥步驟＞ 上述膜可以在膜形成步驟（層形成步驟）之後，對所形成之膜（層）進行乾燥之步驟（乾燥步驟）以去除溶劑。 亦即，本發明的硬化物的製造方法可以包括對藉由膜形成步驟形成之膜進行乾燥之乾燥步驟。 又，上述乾燥步驟在膜形成步驟之後且曝光步驟之前進行為較佳。 乾燥步驟中的膜的乾燥溫度為50～150℃為較佳，70℃～130℃為更佳，90℃～110℃為進一步較佳。又，可以藉由減壓進行乾燥。作為乾燥時間，可以例示出30秒鐘～20分鐘，1分鐘～10分鐘為較佳，2分鐘～7分鐘為更佳。 ＜Drying step＞ For the above film, after the film forming step (layer forming step), the formed film (layer) may be subjected to a drying step (drying step) to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step. Moreover, it is preferable to perform the said drying process after the film formation process, and before the exposure process. The drying temperature of the film in the drying step is preferably 50°C to 150°C, more preferably 70°C to 130°C, and still more preferably 90°C to 110°C. In addition, drying can be performed by reducing pressure. Examples of the drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

＜曝光步驟＞ 上述膜可以用於對膜進行選擇性曝光之曝光步驟。 亦即，本發明的硬化物的製造方法可以包括對藉由膜形成步驟形成之膜進行選擇性曝光之曝光步驟。 選擇性曝光係指對膜的一部分進行曝光。又，藉由選擇性曝光，在膜上形成經曝光之區域（曝光部）及未曝光之區域（非曝光部）。 曝光量只要能夠硬化本發明的樹脂組成物，則並沒有特別限定，例如，以波長365nm處的曝光能量換算計，50～10,000mJ/cm 2為較佳，200～8,000mJ/cm 2為更佳。 <Exposure step> The above film can be used in an exposure step of selectively exposing the film. That is, the manufacturing method of the hardened|cured material of this invention may include the exposure process of selectively exposing the film formed by the film formation process. Selective exposure means exposing a portion of the film. Furthermore, by selective exposure, an exposed area (exposed part) and an unexposed area (non-exposed part) are formed on the film. The amount of exposure is not particularly limited as long as it can harden the resin composition of the present invention. For example, in terms of exposure energy conversion at a wavelength of 365 nm, 50 to 10,000 mJ/cm 2 is preferred, and 200 to 8,000 mJ/cm 2 is more preferred. good.

曝光波長能夠在190～1,000nm的範圍內適當確定，240～550nm為較佳。The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and 240 to 550 nm is preferred.

關於曝光波長，若以與光源的關係來說，則可以舉出（1）半導體雷射（波長830nm、532nm、488nm、405nm、375nm、355nm等）、（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種波長）、（4）準分子雷射、KrF準分子雷射（波長248nm）、ArF準分子雷射（波長193nm）、F 2準分子雷射（波長157nm）、（5）極紫外線；EUV（波長13.6nm）、（6）電子束、（7）YAG雷射的二次諧波532nm、三次諧波355nm等。關於本發明的樹脂組成物，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，尤其可獲得高曝光靈敏度。 又，曝光的方式並沒有特別限定，只要為由本發明的樹脂組成物構成之膜的至少一部分被曝光之方式即可，可以舉出使用了光罩之曝光、基於雷射直接成像法之曝光等。 Regarding the exposure wavelength, in relation to the light source, (1) semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamp, (3) High-pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (three wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F 2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG The second harmonic of laser is 532nm, the third harmonic is 355nm, etc. Regarding the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-rays is particularly preferred. By this, particularly high exposure sensitivity can be achieved. In addition, the method of exposure is not particularly limited as long as at least a part of the film composed of the resin composition of the present invention is exposed. Examples include exposure using a photomask, exposure based on laser direct imaging, etc. .

＜曝光後加熱步驟＞ 上述膜可以在曝光後用於加熱步驟（曝光後加熱步驟）。 亦即，本發明的硬化物的製造方法可以包括對藉由曝光步驟被曝光的膜進行加熱之曝光後加熱步驟。 曝光後加熱步驟能夠在曝光步驟後、顯影步驟前進行。 曝光後加熱步驟中的加熱溫度為50℃～140℃為較佳，60℃～120℃為更佳。 曝光後加熱步驟中的加熱時間為30秒鐘～300分鐘為較佳，1分鐘～10分鐘為更佳。 關於曝光後加熱步驟中的升溫速度，從加熱開始時的溫度至最高加熱溫度為止為1～12℃/分鐘為較佳，2～10℃/分鐘為更佳，3～10℃/分鐘為進一步較佳。 又，升溫速度可以在加熱過程中適當變更。 作為曝光後加熱步驟中的加熱方法，並沒有特別限定，能夠使用公知的加熱板、烘箱、紅外線加熱器等。 又，加熱時，藉由流通氮、氦、氬等惰性氣體，在低氧濃度的環境下進行亦為較佳。 ＜Post-exposure heating step＞ The above film can be used in a heating step after exposure (post-exposure heating step). That is, the manufacturing method of the hardened|cured material of this invention may include the post-exposure heating process of heating the film exposed by the exposure process. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature rise rate in the post-exposure heating step is preferably 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and furthermore 3 to 10°C/min. Better. In addition, the temperature rise rate can be appropriately changed during the heating process. The heating method in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, etc. can be used. Furthermore, it is also preferable to perform heating in an environment with a low oxygen concentration by flowing inert gases such as nitrogen, helium, and argon.

＜顯影步驟＞ 曝光後的上述膜可以在用顯影液進行顯影來形成圖案之顯影步驟中使用。 亦即，本發明的硬化物的製造方法可以包括使用顯影液對藉由曝光步驟被曝光的膜進行顯影來形成圖案之顯影步驟。 藉由進行顯影，膜的曝光部及非曝光部中的一個被去除，形成圖案。 在此，將藉由顯影步驟去除膜的非曝光部之顯影稱為負型顯影，將藉由顯影步驟影去除膜的曝光部之顯影稱為正型顯影。 ＜Development step＞ The exposed film can be used in a development step of developing a pattern using a developer. That is, the manufacturing method of the hardened|cured material of this invention may include the development step of developing the film exposed by the exposure step using a developer to form a pattern. By performing development, one of the exposed part and the non-exposed part of the film is removed, and a pattern is formed. Here, the development in which the non-exposed part of the film is removed in the development step is called negative development, and the development in which the exposed part of the film is removed in the development step is called positive development.

〔顯影液〕 作為在顯影步驟中所使用之顯影液，可以舉出鹼水溶液或包含有機溶劑之顯影液。 [Developer] Examples of the developer used in the development step include an alkali aqueous solution or a developer containing an organic solvent.

在顯影液為鹼性水溶液的情況下，作為鹼性水溶液可以包含之鹼性化合物，可以舉出無機鹼類、一級胺類、二級胺類、三級胺類、四級銨鹽。例如使用TMAH的情況下，顯影液中鹼性化合物的含量在顯影液總質量中為0.01～10質量%為較佳，0.1～5質量%為更佳，0.3～3質量%為進一步較佳。When the developer is an alkaline aqueous solution, examples of alkaline compounds that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. For example, when using TMAH, the content of the alkaline compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.3 to 3% by mass based on the total mass of the developer.

在顯影液包含有機溶劑的情況下，關於有機溶劑，作為酯類，例如可較佳地舉出乙酸乙酯、乙酸正丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯、ε-己內酯、δ-戊內酯、烷氧基乙酸烷基酯（例如：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，以及作為醚類，例如可較佳地舉出二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基賽路蘇乙酸酯、乙基賽路蘇乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚（PGME）、丙二醇單甲醚乙酸酯（PGMEA）、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯等，以及作為酮類，例如可較佳地舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、N-甲基-2-吡咯啶酮等，以及作為環狀烴類，例如可較佳地舉出甲苯、二甲苯、大茴香醚等芳香族烴類、檸檬烯等環式萜烯類，以及作為亞碸類，可較佳地舉出二甲基亞碸，以及作為醇類，可較佳地舉出甲醇、乙醇、丙醇、異丙醇、丁醇、戊醇、辛醇、二乙二醇、丙二醇、甲基異丁基甲醇、三乙二醇等，以及作為醯胺類，可較佳地舉出N-甲基吡咯啶酮、N-乙基吡咯啶酮、二甲基甲醯胺等。When the developer contains an organic solvent, preferred examples of the organic solvent as esters include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, and propionic acid. Butyl ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxyacetate esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl alkoxyacetate) Oxyacetic acid methyl ester, ethoxyethyl acetate, etc.)), 3-alkoxypropionic acid alkyl esters (such as: 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-Alkoxy Alkyl propionates (for example: methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, 2-methoxypropionate Methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy -Methyl 2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2- Ethyl methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetyl acetate, ethyl acetyl acetate, methyl 2-oxobutyrate, 2-oxobutanate Acid ethyl ether, etc., and as ethers, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methylcelusu acetate, ethyl glycol Kisselusu acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Ketones, N-methyl-2-pyrrolidinone, etc., and preferred examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene. Preferable examples of sersions include dimethylsterine, and examples of alcohols include methanol, ethanol, propanol, isopropyl alcohol, butanol, pentanol, octanol, and dimethyl alcohol. Ethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and preferred examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylpyrrolidone. Formamide, etc.

又，在顯影液包含有機溶劑的情況下，有機溶劑能夠使用1種或混合使用2種以上。本發明中，尤其包含選自包括環戊酮、γ-丁內酯、二甲基亞碸、N-甲基-2-吡咯啶酮及環己酮之群組中之至少1種之顯影液為較佳，包含選自包括環戊酮、γ-丁內酯及二甲基亞碸之群組中之至少1種之顯影液為更佳，包括環戊酮之顯影液為最佳。In addition, when the developer contains an organic solvent, one type of organic solvent can be used or two or more types of organic solvents can be mixed and used. In the present invention, in particular, at least one developer selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylstyrene, N-methyl-2-pyrrolidone and cyclohexanone is included. More preferably, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl teroxide is more preferred, and a developer containing cyclopentanone is most preferred.

在顯影液包含有機溶劑的情況下，相對於顯影液的總質量之有機溶劑的含量為50質量%以上為較佳，70質量%以上為更佳，80質量%以上為進一步較佳，90質量%以上為特佳。又，上述含量亦可以為100質量%。When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and 90% by mass. % or above is considered excellent. Moreover, the said content may be 100 mass %.

顯影液可以進一步包含其他成分。 作為其他成分，例如，可以舉出公知的界面活性劑和公知的消泡劑等。 The developer may further contain other ingredients. Examples of other components include known surfactants, known defoaming agents, and the like.

〔顯影液的供給方法〕 只要能夠形成所期望圖案，則顯影液的供給方法並沒有特別限制，有如下方法：將形成有膜之基材浸漬於顯影液中之方法、用噴嘴對形成於基材上之膜供給顯影液之旋覆浸沒顯影或連續供給顯影液之方法。噴嘴的種類並沒有特別限制，可以舉出直流噴嘴、噴淋噴嘴、噴霧噴嘴等。 [How to supply developer] The method of supplying the developer is not particularly limited as long as the desired pattern can be formed. The method includes the following methods: immersing the base material on which the film is formed in the developer; and using a nozzle to supply the developer to the film formed on the base material. The method of spin immersion development or continuous supply of developer solution. The type of nozzle is not particularly limited, and examples include direct flow nozzles, shower nozzles, spray nozzles, and the like.

作為顯影時間，10秒鐘～10分鐘為較佳，20秒鐘～5分鐘為更佳。顯影時的顯影液的溫度並沒有特別限定，較佳為能夠在10～45℃下進行，更佳為能夠在18℃～30℃下進行。The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but it is preferably 10 to 45°C, and more preferably 18 to 30°C.

〔沖洗液〕 在顯影液為鹼水溶液的情況下，作為沖洗液，例如能夠使用水。在顯影液為包含有機溶劑之顯影液的情況下，作為沖洗液，例如，能夠使用與顯影液中所包含之溶劑不同之溶劑（例如，水、與顯影液中所包含之有機溶劑不同之有機溶劑）。 [rinsing fluid] When the developer is an alkali aqueous solution, water can be used as the rinse liquid, for example. When the developer contains an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid. solvent).

作為沖洗時間，10秒鐘～10分鐘為較佳，20秒鐘～5分鐘為更佳。沖洗時的沖洗液的溫度並沒有特別限定，較佳為能夠在10～45℃下進行，更佳為能夠在18℃～30℃下進行。The flushing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinse liquid during rinse is not particularly limited, but it is preferably 10°C to 45°C, and more preferably 18°C to 30°C.

＜加熱步驟＞ 藉由顯影步驟獲得之圖案（進行沖洗步驟的情況下為沖洗後的圖案）可以用於對藉由上述顯影獲得之圖案進行加熱之加熱步驟。 亦即，本發明的硬化物的製造方法可以包括對藉由顯影步驟獲得之圖案進行加熱之加熱步驟。 又，本發明的硬化物的製造方法亦可以包括對未進行顯影步驟而藉由其另一方法來獲得之圖案或藉由膜形成步驟獲得之膜進行加熱之加熱步驟。 加熱步驟中，聚醯亞胺前驅物等樹脂環化成為聚醯亞胺等樹脂。 又，亦進行特定樹脂或除特定樹脂以外的交聯劑中的未反應的交聯性基的交聯等。 作為加熱步驟中的加熱溫度（最高加熱溫度），50～450℃為較佳，150～350℃為更佳，150～250℃為進一步較佳，160～250℃為更進一步較佳，160～230℃為特佳。 ＜Heating step＞ The pattern obtained by the development step (the pattern after washing when the rinse step is performed) can be used in the heating step of heating the pattern obtained by the development. That is, the method of manufacturing a hardened product of the present invention may include a heating step of heating the pattern obtained by the development step. Moreover, the manufacturing method of the hardened|cured material of this invention may also include the heating process of heating the pattern obtained by another method without performing a development process, or the film obtained by the film formation process. In the heating step, resins such as polyimide precursors are cyclized into resins such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in a specific resin or a crosslinking agent other than the specific resin is also performed. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, still more preferably 150 to 250°C, still more preferably 160 to 250°C, and 160 to 160°C. 230℃ is particularly good.

加熱步驟為如下步驟為較佳：利用藉由加熱從上述鹼產生劑產生之鹼等的作用，在上述圖案內促進上述聚醯亞胺前驅物的環化反應。The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted in the pattern by utilizing the action of a base or the like generated from the base generator by heating.

＜顯影後曝光步驟＞ 藉由顯影步驟獲得之圖案（進行沖洗步驟的情況下為沖洗後的圖案）代替上述加熱步驟或者除了上述加熱步驟以外，亦可以用於對顯影步驟後的圖案進行曝光之顯影後曝光步驟。 亦即，本發明的硬化物的製造方法可以包括對藉由顯影步驟獲得之圖案進行曝光之顯影後曝光步驟。 ＜Exposure step after development＞ The pattern obtained by the development step (the pattern after the development step in the case of performing the development step) may be used in a post-development exposure step in which the pattern after the development step is exposed instead of or in addition to the above-mentioned heating step. That is, the manufacturing method of the hardened|cured material of this invention may include the exposure process after development which exposes the pattern obtained by the development process.

＜金屬層形成步驟＞ 藉由顯影步驟獲得之圖案（在加熱步驟及顯影後曝光步驟中的至少1個中使用者為較佳）可以用於在圖案上形成金屬層之金屬層形成步驟。 亦即，本發明的硬化物的製造方法包括在藉由顯影步驟獲得之圖案（在加熱步驟及顯影後曝光步驟中的至少1種步驟中使用者為較佳）上形成金屬層之金屬層形成步驟為較佳。 <Metal layer formation step> The pattern obtained by the development step (it is preferable to use at least one of the heating step and the post-development exposure step) can be used in the metal layer forming step of forming the metal layer on the pattern. That is, the method of manufacturing a hardened product of the present invention includes forming a metal layer on a pattern obtained by a development step (it is preferred to use at least one of a heating step and a post-development exposure step). The steps are better.

＜用途＞ 作為能夠適用本發明的硬化物的製造方法或本發明的硬化物的領域，可以舉出電子元件的絕緣膜、再配線層用層間絕緣膜、應力緩衝膜等。除此以外，可以舉出密封膜、基板材料（柔性印刷電路板的基底膜或覆蓋膜、層間絕緣膜）或藉由蝕刻在上述之類的實際安裝用途的絕緣膜上形成圖案之情況等。關於該等用途，例如，能夠參考Science & Technology Co.,Ltd.“聚醯亞胺的高功能化和應用技術”2008年4月、柿本雅明/監修、CMC技術圖書館“聚醯亞胺材料的基礎和開發”2011年11月發行，日本聚醯亞胺•芳香族系高分子研究會/編“最新聚醯亞胺 基礎和應用”NTS，2010年8月等。 ＜Use＞ Examples of fields to which the method for producing a cured product of the present invention or the cured product of the present invention can be applied include insulating films for electronic components, interlayer insulating films for rewiring layers, stress buffering films, and the like. In addition, examples include sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or the case where a pattern is formed on an insulating film for actual mounting purposes such as the above by etching. Regarding such uses, for example, you can refer to Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaaki Kakimoto/Supervisor, CMC Technical Library "Polyimide Materials" "Basics and Development of Polyimides" published in November 2011, Japan Polyimide and Aromatic Polymer Research Society/edited "Latest Basics and Applications of Polyimides" NTS, August 2010, etc.

又，本發明的硬化物的製造方法或本發明的硬化物亦能夠用於膠印版面或網版版面等版面的製造、成形部件在蝕刻中的使用、電子、尤其微電子中的保護漆及介電層的製造等。Furthermore, the method for producing a cured product of the present invention or the cured product of the present invention can also be used in the production of offset printing plates, screen plates, etc., use of molded parts in etching, and protective paints and media in electronics, especially microelectronics. Manufacturing of electrical layers, etc.

（積層體及積層體的製造方法） 本發明的積層體係指具有複數層由本發明的硬化物構成之層之結構體。 本發明的積層體係包含2層以上由硬化物構成之層之積層體，亦可以為積層3層以上而成之積層體。 上述積層體中所包含之2層以上的上述由硬化物構成之層中，至少1層為由本發明的硬化物構成之層，從抑制硬化物的收縮或伴隨上述收縮產生之硬化物的變形等觀點考慮，上述積層體中所包含之由硬化物構成之層全部為由本發明的硬化物構成之層亦為較佳。 (Laminated body and method of manufacturing the laminated body) The laminated system of the present invention refers to a structure having a plurality of layers composed of the hardened material of the present invention. The laminate system of the present invention includes a laminate composed of two or more layers of hardened materials, and may be a laminate in which three or more layers are laminated. Among the two or more layers composed of the cured material contained in the above-mentioned laminate, at least one layer is a layer composed of the cured material of the present invention, thereby suppressing shrinkage of the cured material or deformation of the cured material accompanying the above-mentioned shrinkage, etc. From this viewpoint, it is also preferable that all the layers composed of the cured material included in the above-mentioned laminate are layers composed of the cured material of the present invention.

亦即，本發明的積層體的製造方法包括本發明的硬化物的製造方法為較佳，包括重複複數次本發明的硬化物的製造方法之步驟為更佳。That is, it is preferable that the manufacturing method of the laminated body of this invention includes the manufacturing method of the hardened material of this invention, and it is more preferable that it includes repeating the steps of the manufacturing method of the hardened material of this invention several times.

本發明的積層體包含2層以上由硬化物構成之層，由上述硬化物構成之任意層彼此之間包含金屬層之態樣為較佳。上述金屬層藉由上述金屬層形成步驟形成為較佳。 亦即，本發明的積層體的製造方法在進行複數次硬化物的製造方法之間進一步包括在由硬化物構成之層上形成金屬層之金屬層形成步驟為較佳。金屬層形成步驟的較佳態樣為如上所述。 作為上述積層體，例如，可以舉出至少包含依序積層有由第一硬化物構成之層、金屬層、由第二硬化物構成之層的3個層之層結構之積層體作為較佳者。 上述由第一硬化物構成之層及上述由第二硬化物構成之層均為由本發明的硬化物構成之層為較佳。用於形成由上述第一硬化物構成之層之本發明的樹脂組成物和用於形成由上述第二硬化物構成之層之本發明的樹脂組成物可以為組成相同的組成物，亦可以為組成不同之組成物。本發明的積層體中的金屬層可較佳地用作再配線層等金屬配線。 The laminated body of the present invention includes two or more layers made of a hardened material, and it is preferable that any of the layers made of the hardened material include a metal layer between them. The above-mentioned metal layer is preferably formed by the above-mentioned metal layer forming step. That is, it is preferable that the manufacturing method of the laminated body of this invention further includes the metal layer formation step of forming a metal layer on the layer consisting of a hardened material between a plurality of manufacturing methods of a hardened material. A preferred aspect of the metal layer forming step is as described above. As the above-mentioned laminated body, for example, a laminated body having a layer structure including at least three layers in which a layer made of a first hardened material, a metal layer, and a layer made of a second hardened material are laminated in this order can be cited as a preferred example. . It is preferred that the layer composed of the first cured material and the layer composed of the second cured material are both layers composed of the cured material of the present invention. The resin composition of the present invention used to form the layer composed of the first cured material and the resin composition of the present invention used to form the layer composed of the second cured material may have the same composition, or they may be Compositions of different compositions. The metal layer in the laminated body of the present invention can be preferably used as a metal wiring such as a rewiring layer.

＜積層步驟＞ 本發明的積層體的製造方法包括積層步驟為較佳。 積層步驟為包括在圖案（樹脂層）或金屬層的表面，再次依序進行（a）膜形成步驟（層形成步驟）、（b）曝光步驟、（c）顯影步驟、（d）加熱步驟及顯影後曝光步驟中的至少1個之一系列步驟。其中，可以為重複（a）的膜形成步驟、（d）加熱步驟及顯影後曝光步驟中的至少1個之態樣。又，可以在（d）加熱步驟及顯影後曝光步驟的中的至少1個之後包括（e）金屬層形成步驟。積層步驟中顯然可以適當地進一步包括上述乾燥步驟等。 ＜Layering Steps＞ The method for manufacturing a laminated body of the present invention preferably includes a lamination step. The lamination step includes sequentially performing (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step and A series of steps of at least one of the post-development exposure steps. However, at least one of the film forming step (a), the heating step (d) and the post-development exposure step may be repeated. Furthermore, (e) the metal layer forming step may be included after at least one of (d) the heating step and the post-development exposure step. It goes without saying that the above-mentioned drying step and the like may be further appropriately included in the layering step.

在積層步驟之後進一步進行積層步驟的情況下，可以在上述曝光步驟後，上述加熱步驟後或上述金屬層形成步驟後進一步進行表面活性化處理步驟。作為表面活性化處理，例示電漿處理。關於表面活性化處理的詳細內容，在後面進行說明。When the lamination step is further performed after the lamination step, the surface activation treatment step may be further performed after the above-mentioned exposure step, after the above-mentioned heating step, or after the above-mentioned metal layer forming step. As surface activation treatment, plasma treatment is exemplified. Details of the surface activation treatment will be described later.

（表面活性化處理步驟） 本發明的積層體的製造方法包括對上述金屬層及樹脂組成物層的至少一部分進行表面活性化處理之表面活性化處理步驟為較佳。 表面活性化處理步驟通常在金屬層形成步驟之後進行，但亦可以在上述顯影步驟之後（較佳為加熱步驟及顯影後曝光步驟中的至少1個之後）、對樹脂組成物層進行表面活性化處理步驟之後進行金屬層形成步驟。 (Surface activation treatment step) The method for manufacturing a laminated body of the present invention preferably includes a surface activation treatment step of subjecting at least part of the metal layer and the resin composition layer to a surface activation treatment. The surface activation treatment step is usually performed after the metal layer forming step, but the surface activation of the resin composition layer may also be performed after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step). The processing step is followed by a metal layer forming step.

（半導體元件的製造方法） 本發明亦公開一種包含本發明的硬化物或本發明的積層體之半導體元件。 本發明亦公開包括本發明的硬化物的製造方法或本發明的積層體的製造方法之半導體元件的製造方法。作為將本發明的樹脂組成物用於形成再配線層用層間絕緣膜之半導體元件的具體例，能夠參考日本特開2016-027357號公報的0213～0218段的記載及圖1的記載，該等內容編入本說明書中。 [實施例] (Method for manufacturing semiconductor components) The present invention also discloses a semiconductor element including the cured product of the present invention or the laminated body of the present invention. The present invention also discloses a method for manufacturing a semiconductor element including the method for manufacturing a hardened product of the invention or the method for manufacturing a laminated body of the invention. As a specific example of a semiconductor element in which the resin composition of the present invention is used to form an interlayer insulating film for a rewiring layer, reference can be made to the description in paragraphs 0213 to 0218 of Japanese Patent Application Laid-Open No. 2016-027357 and the description in FIG. 1 . The contents are incorporated 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。以下實施例所示之材料、使用量、比例、處理內容、處理順序等，只要不脫離本發明的主旨，則能夠適當變更。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，則“份”、“%”為質量基準。Hereinafter, the present invention will be described in further detail with reference to examples. The materials, usage amounts, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate 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 based on mass.

＜合成例1：樹脂A-1-1的合成＞ 在具備攪拌機、冷凝器及安裝有內部溫度計之平底接頭之乾燥反應器中，使氧基二鄰苯二甲酸二酐20.0g（0.0645mol）懸浮於二甘二甲醚140mL中。繼續添加甲基丙烯酸2-羥基乙酯16.8g（0.129mol）、氫醌0.05g及吡啶10.7g（0.135mol），並在60℃的溫度下攪拌了18小時。接著，將混合物冷卻至-20℃之後，經90分鐘滴加了亞硫醯氯16.1g（0.136mol）。獲得了吡啶鎓鹽酸鹽的白色沉澱。接著，將混合物溫熱至室溫，攪拌2小時之後，添加吡啶9.7g（0.123mol）及N-甲基吡咯啶酮（NMP）25ml而獲得了透明溶液。接著，將使4,4’-二胺基二苯醚11.8g（0.0587mol）溶解於NMP100ml中的溶劑，經1小時藉由滴加而添加到透明溶液中。在添加4,4’-二胺基二苯醚期間，黏度增加。接著，在混合物中添加乙醇10.0g之後攪拌了2小時。接著，在4升的水中使聚醯亞胺前驅物樹脂沉澱，並將水-聚醯亞胺前驅物樹脂混合物以5000rpm的速度攪拌了15分鐘。過濾並獲取聚醯亞胺前驅物樹脂，在4升的水中再次攪拌30分鐘，並再次進行了濾過。接著，藉由對所獲得之聚醯亞胺前驅物樹脂進行真空乾燥，獲得了粉末狀聚醯亞胺前驅物樹脂A-1-1。 <Synthesis Example 1: Synthesis of Resin A-1-1> In a dry reactor equipped with a stirrer, a condenser, and a flat-bottomed joint equipped with an internal thermometer, 20.0 g (0.0645 mol) of oxydiphthalic dianhydride was suspended in 140 mL of diglylene dimethyl ether. 16.8g (0.129mol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone and 10.7g of pyridine (0.135mol) were added, and the mixture was stirred at a temperature of 60°C for 18 hours. Next, the mixture was cooled to -20°C, and then 16.1 g (0.136 mol) of thionite chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Next, the mixture was warmed to room temperature and stirred for 2 hours, and then 9.7 g (0.123 mol) of pyridine and 25 ml of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Next, a solvent in which 11.8 g (0.0587 mol) of 4,4'-diaminodiphenyl ether was dissolved in 100 ml of NMP was added dropwise to the transparent solution over 1 hour. During the addition of 4,4’-diaminodiphenyl ether, the viscosity increased. Next, 10.0 g of ethanol was added to the mixture, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 5000 rpm for 15 minutes. Filter to obtain the polyimide precursor resin, stir it again in 4 liters of water for 30 minutes, and filter it again. Next, the obtained polyimide precursor resin was vacuum-dried to obtain a powdery polyimide precursor resin A-1-1.

＜合成例2：樹脂A-1-2的合成＞ 將氧基二鄰苯二甲酸二酐155.1g（500毫莫耳）加入到2升容量的分離式燒瓶中。接著，添加甲基丙烯酸2-羥乙酯（HEMA）131.2g（1000毫莫耳）及γ-丁內酯400ml，在室溫下一邊攪拌一邊添加吡啶81.5g（1030毫莫耳），從而獲得了反應混合物。對於該反應混合物，在基於反應之發熱結束之後，自然冷卻至室溫，進一步靜置了16小時。接著，在冰冷下，一邊攪拌將二環己基碳化二醯亞胺（DCC）206.3g（1000毫莫耳）溶解於γ-丁內酯180ml之溶液進行一邊將其經40分鐘加入到上述反應混合物中，接著，一邊攪拌使4,4’-二胺基二苯基醚93.0g（464毫莫耳）懸浮於γ-丁內酯350ml之者一邊將其經60分鐘加入。進一步繼續在室溫下攪拌2小時，加入乙醇30ml，並攪拌1小時，然後，加入了γ-丁內酯400ml。藉由過濾去除該反應混合物中所生成之沉澱物，藉此獲得了反應液。將所獲得之反應液投入到3升的乙醇中，生成了由粗聚合物組成之沉澱物。濾取所生成之粗聚合物，將其溶解於四氫呋喃1.5升中而獲得了粗聚合物溶液。將所獲得之粗聚合物溶液滴加於28升的水中並使聚醯亞胺前驅物樹脂沉澱，濾取所獲得之沉澱物，並進行真空乾燥，藉此獲得了粉末狀聚醯亞胺前驅物樹脂A-1-2。 <Synthesis Example 2: Synthesis of Resin A-1-2> 155.1 g (500 mmol) of oxydiphthalic dianhydride was added to a separate flask with a capacity of 2 liters. Next, 131.2 g (1000 mmol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and 81.5 g of pyridine (1030 mmol) was added while stirring at room temperature to obtain reaction mixture. After the heat generated by the reaction was completed, the reaction mixture was naturally cooled to room temperature and left to stand for 16 hours. Next, a solution of 206.3 g (1000 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the above reaction mixture over 40 minutes while stirring under ice-cooling. Then, 93.0 g (464 mmol) of 4,4'-diaminodiphenyl ether was suspended in 350 ml of γ-butyrolactone while stirring for 60 minutes. Stirring was continued at room temperature for 2 hours, 30 ml of ethanol was added, and the mixture was stirred for 1 hour. Then, 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration, thereby obtaining a reaction liquid. The obtained reaction liquid was added to 3 liters of ethanol, and a precipitate consisting of a crude polymer was formed. The produced crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polyimide precursor resin. The obtained precipitate was filtered and vacuum dried to obtain a powdery polyimide precursor. Physical resin A-1-2.

＜合成例3：樹脂A-2的合成＞ 將3,3’,4,4’-聯苯四羧酸二酐147.1g（500毫莫耳）加入到2升容量的分離式燒瓶中。接著，添加甲基丙烯酸2-羥乙酯（HEMA）131.2g（1000毫莫耳）及γ-丁內酯400ml，在室溫下一邊攪拌一邊添加吡啶81.5g（1030毫莫耳），從而獲得了反應混合物。對於該反應混合物，在基於反應之發熱結束之後，自然冷卻至室溫，進一步靜置了16小時。接著，在冰冷下，一邊攪拌將二環己基碳化二醯亞胺（DCC）206.3g（1000毫莫耳）溶解於γ-丁內酯180ml之溶液進行一邊將其經40分鐘加入到上述反應混合物中，接著，一邊攪拌使4,4’-二胺基二苯基醚93.0g（464毫莫耳）懸浮於γ-丁內酯350ml之者一邊將其經60分鐘加入。進一步繼續在室溫下攪拌2小時，加入乙醇30ml，並攪拌1小時，然後，加入了γ-丁內酯400ml。藉由過濾去除該反應混合物中所生成之沉澱物，藉此獲得了反應液。將所獲得之反應液投入到3升的乙醇中，生成了由粗聚合物組成之沉澱物。濾取所生成之粗聚合物，將其溶解於四氫呋喃1.5升中而獲得了粗聚合物溶液。將所獲得之粗聚合物溶液滴加於28升的水中並使聚醯亞胺前驅物樹脂沉澱，濾取所獲得之沉澱物，並進行真空乾燥，藉此獲得了粉末狀聚醯亞胺前驅物樹脂A-2。 <Synthesis Example 3: Synthesis of Resin A-2> 147.1 g (500 mmol) of 3,3’,4,4’-biphenyltetracarboxylic dianhydride was added to a separate flask with a capacity of 2 liters. Next, 131.2 g (1000 mmol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and 81.5 g of pyridine (1030 mmol) was added while stirring at room temperature to obtain reaction mixture. After the heat generated by the reaction was completed, the reaction mixture was naturally cooled to room temperature and left to stand for 16 hours. Next, a solution of 206.3 g (1000 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the above reaction mixture over 40 minutes while stirring under ice-cooling. Then, 93.0 g (464 mmol) of 4,4'-diaminodiphenyl ether was suspended in 350 ml of γ-butyrolactone while stirring for 60 minutes. Stirring was continued at room temperature for 2 hours, 30 ml of ethanol was added, and the mixture was stirred for 1 hour. Then, 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration, thereby obtaining a reaction liquid. The obtained reaction liquid was added to 3 liters of ethanol, and a precipitate consisting of a crude polymer was generated. The produced crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polyimide precursor resin. The obtained precipitate was filtered and vacuum dried to obtain a powdery polyimide precursor. Physical resin A-2.

＜合成例4：樹脂A-3的合成＞ 將氧基二鄰苯二甲酸二酐77.5g（250毫莫耳）和3,3’,4,4’-聯苯四羧酸二酐147.1g（250毫莫耳）加入到2升容量的分離式燒瓶中。接著，添加甲基丙烯酸2-羥乙酯（HEMA）131.2g（1000毫莫耳）及γ-丁內酯400ml，在室溫下一邊攪拌一邊添加吡啶81.5g（1030毫莫耳），從而獲得了反應混合物。對於該反應混合物，在基於反應之發熱結束之後，自然冷卻至室溫，進一步靜置了16小時。接著，在冰冷下，一邊攪拌將二環己基碳化二醯亞胺（DCC）206.3g（1000毫莫耳）溶解於γ-丁內酯180ml之溶液進行一邊將其經40分鐘加入到上述反應混合物中，接著，一邊攪拌使4,4’-二胺基二苯基醚93.0g（464毫莫耳）懸浮於γ-丁內酯350ml之者一邊將其經60分鐘加入。進一步繼續在室溫下攪拌2小時，加入乙醇30ml，並攪拌1小時，然後，加入了γ-丁內酯400ml。 藉由過濾去除該反應混合物中所生成之沉澱物，藉此獲得了反應液。將所獲得之反應液投入到3升的乙醇中，生成了由粗聚合物組成之沉澱物。濾取所生成之粗聚合物，將其溶解於四氫呋喃1.5升中而獲得了粗聚合物溶液。將所獲得之粗聚合物溶液滴加於28升的水中並使聚醯亞胺前驅物樹脂沉澱，濾取所獲得之沉澱物，並進行真空乾燥，藉此獲得了粉末狀聚醯亞胺前驅物樹脂A-3。 <Synthesis Example 4: Synthesis of Resin A-3> Add 77.5g (250 mmol) of oxydiphthalic dianhydride and 147.1g (250 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride into a 2-liter container. in a separate flask. Next, 131.2 g (1000 mmol) of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added, and 81.5 g of pyridine (1030 mmol) was added while stirring at room temperature to obtain reaction mixture. After the heat generated by the reaction was completed, the reaction mixture was naturally cooled to room temperature and left to stand for 16 hours. Next, a solution of 206.3 g (1000 mmol) of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the above reaction mixture over 40 minutes while stirring under ice-cooling. Then, 93.0 g (464 mmol) of 4,4'-diaminodiphenyl ether was suspended in 350 ml of γ-butyrolactone while stirring for 60 minutes. Stirring was continued at room temperature for 2 hours, 30 ml of ethanol was added, and the mixture was stirred for 1 hour. Then, 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration, thereby obtaining a reaction liquid. The obtained reaction liquid was added to 3 liters of ethanol, and a precipitate consisting of a crude polymer was generated. The produced crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polyimide precursor resin. The obtained precipitate was filtered and vacuum dried to obtain a powdery polyimide precursor. Physical resin A-3.

＜合成例5：樹脂A-4的合成＞ 將3,3’,4,4’-二苯醚四羧酸二酐7.07g和2,2’-二甲基聯苯-4,4’-二胺4.12g溶解於N-甲基-2-吡咯啶酮（NMP）30g中，在30℃下攪拌4小時，然後在室溫下攪拌一晚，獲得了聚醯胺酸。然後，在水冷下添加9.45g三氟乙酸酐，在45℃下攪拌3小時，並添加了甲基丙烯酸2-羥基乙酯（HEMA）7.08g。將該反應液滴加於蒸留水中，藉由過濾析出沉澱物，並進行減壓乾燥，獲得了聚醯亞胺前驅物樹脂A-4。 <Synthesis Example 5: Synthesis of Resin A-4> Dissolve 7.07g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and 4.12g of 2,2'-dimethylbiphenyl-4,4'-diamine in N-methyl-2 - 30 g of pyrrolidinone (NMP) was stirred at 30°C for 4 hours and then at room temperature overnight to obtain polyamide. Then, 9.45 g of trifluoroacetic anhydride was added under water cooling, the mixture was stirred at 45° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added. The reaction liquid was added dropwise to the distilled water, and the precipitate was precipitated by filtration and dried under reduced pressure to obtain polyimide precursor resin A-4.

＜合成例6：樹脂A-5的合成＞ 在乾燥氮氣流下，使氧基二鄰苯二甲酸二酐62.04g（0.2莫耳）溶解於1000g的NMP中。在此，與NMP100g一起添加下述式（HA）所表示之結構的二胺（HA）96.72g（0.16莫耳）和1,3-雙（3-胺基丙基）四甲基二矽氧烷（SiDA）4.97g（0.02莫耳），並使其在20℃下反應1小時，接著在50℃下反應2小時。接著，作為封端劑，與NMP30g一起添加3-胺基苯酚（MAP）4.37g（0.04莫耳），並使其在50℃下反映了2小時。然後，經10分鐘滴加用NMP50g稀釋了N,N-二甲基甲醯胺二甲基縮醛47.66g（0.4莫耳）之溶液。滴下後，在50℃下攪拌了3小時。攪拌結束後，將溶液冷卻至室溫之後，將溶液投入到水1L中從而獲得了沉澱。過濾析出該沉澱，並用水清洗3次之後，用80℃的真空乾燥機乾燥20小時，獲得了粉末狀聚醯亞胺前驅物樹脂A-5。 [化學式22] <Synthesis Example 6: Synthesis of Resin A-5> Under a dry nitrogen flow, 62.04 g (0.2 mol) of oxydiphthalic dianhydride was dissolved in 1000 g of NMP. Here, 96.72 g (0.16 mol) of diamine (HA) having a structure represented by the following formula (HA) and 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added together with 100 g of NMP. Alkane (SiDA) 4.97g (0.02 mol) was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, as a terminal blocking agent, 4.37 g (0.04 mol) of 3-aminophenol (MAP) was added together with 30 g of NMP, and the mixture was reacted at 50° C. for 2 hours. Then, a solution of 47.66 g (0.4 mol) of N,N-dimethylformamide dimethyl acetal diluted with 50 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50° C. for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was added to 1 L of water to obtain a precipitate. The precipitate was precipitated by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 20 hours to obtain a powdery polyimide precursor resin A-5. [Chemical formula 22]

＜合成例7：樹脂A-6的合成＞ 在乾燥氮氣流下，使2,2-雙（3-胺基-4-羥基苯基）六氟丙烷（32.78g（0.0895莫耳））和1,3-雙（3-胺基丙基）四甲基二矽氧烷（1.24g（0.005莫耳））溶解於N-甲基-2-吡咯啶酮（100g）。將雙（3,4-二羧基苯基）醚二酐（31.02g（0.10莫耳））與NMP（30g）一其加入到該溶液中，並在20℃下攪拌1小時，接著，在50℃下攪拌了4小時。向該攪拌後的溶液中加入3-胺基苯酚（1.09g（0.01莫耳）），並在50℃下攪拌2小時之後，在180℃下攪拌5小時而獲得了樹脂溶液。接著，將該樹脂溶液投入到水（3L）中而生成了白色沉澱。過濾析出該白色沉澱，並用水清洗3次之後，用80℃的真空乾燥機乾燥5小時，從而獲得了粉末狀聚醯亞胺樹脂A-6。所獲得之聚醯亞胺樹脂A-6的醯亞胺化率為94%。 <Synthesis Example 7: Synthesis of Resin A-6> Under a stream of dry nitrogen, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (32.78g (0.0895 mol)) and 1,3-bis(3-aminopropyl)tetrakis Methyl disiloxane (1.24 g (0.005 mol)) was dissolved in N-methyl-2-pyrrolidone (100 g). Bis(3,4-dicarboxyphenyl)ether dianhydride (31.02g (0.10 mol)) and NMP (30g) were added to the solution, and stirred at 20°C for 1 hour, then, at 50 °C for 4 hours. 3-aminophenol (1.09 g (0.01 mol)) was added to the stirred solution, and the mixture was stirred at 50° C. for 2 hours and then at 180° C. for 5 hours to obtain a resin solution. Next, this resin solution was put into water (3 L), and a white precipitate was formed. The white precipitate was precipitated by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 5 hours to obtain powdery polyimide resin A-6. The obtained polyimide resin A-6 had an imidization rate of 94%.

＜合成例8：樹脂A-7的合成＞ 在具備攪拌機、溫度計之0.2升的燒瓶中加入N-甲基吡咯啶酮60g，並添加2,2-雙（3-胺基-4-羥基苯基）六氟丙烷13.92g（38mmol），進行攪拌溶解。接著，一邊將溫度保持在0～5℃，一邊經10分鐘滴加十二烷二酸二氯10.69g（40mmol）之後，將燒瓶中的溶液攪拌了60分鐘。將上述溶液投入到3升的水中，回收析出物，並將其用純水清洗3次之後，進行減壓從而獲得了多羥基醯胺基（聚苯并噁唑前驅物）樹脂A-7。 <Synthesis Example 8: Synthesis of Resin A-7> Add 60 g of N-methylpyrrolidone to a 0.2-liter flask equipped with a mixer and a thermometer, and add 13.92 g (38 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. Stir to dissolve. Next, while maintaining the temperature at 0 to 5° C., 10.69 g (40 mmol) of dodecanedioic acid dichloride was added dropwise over 10 minutes, and then the solution in the flask was stirred for 60 minutes. The above solution was put into 3 liters of water, and the precipitate was recovered, washed three times with pure water, and then the pressure was reduced to obtain polyhydroxyamide-based (polybenzoxazole precursor) resin A-7.

＜合成例9：樹脂A-8的合成＞ 向具備溫度計、攪拌機、原料投入口及乾燥氮氣導入管之四口的玻璃製分離式燒瓶內加入使二苯醚-4,4’-二羧酸206.58g（0.800mol）與1-羥基-1,2，3-苯並三唑•一水和物216.19g（1.600mol）反應而獲得之二羧酸衍生物的混合物170.20g（0.346mol）、5-胺基四唑4.01g（0.047mol）、4,4’-亞甲基雙（2-胺基苯酚）45.22g（0.196mol）、4,4’-亞甲基雙（2-胺基-3,6二甲苯酚）56.24g（0.196mol）。然後，向上述分離式燒瓶內加入578.3g的NMP，並使各原料成分溶解。接著，使用油浴，在90℃下反映了5小時。接著，向上述分離式燒瓶內加入24.34g（0.141mol）的4-鄰苯二甲酸酐、121.7g的NMP，一邊在90℃下攪拌2小時一邊使其反應之後，冷卻至23℃而結束了反應。將過濾分離式燒瓶內之反應混合物而獲得之濾過物投入到水/異丙醇=7/4（容積比）的溶液中。然後，過濾出沉澱物，用水充分清洗之後，在真空下進行乾燥，藉此獲得了多羥基醯胺基（聚苯并噁唑前驅物）樹脂A-8。 <Synthesis Example 9: Synthesis of Resin A-8> Add 206.58g (0.800mol) of diphenyl ether-4,4'-dicarboxylic acid and 1-hydroxy-1 into a glass separate flask equipped with a thermometer, a stirrer, a raw material input port, and a dry nitrogen gas inlet. , 170.20g (0.346mol) of a mixture of dicarboxylic acid derivatives obtained by reacting 216.19g (1.600mol) of 2,3-benzotriazole monohydrate, 4.01g (0.047mol) of 5-aminotetrazole , 4,4'-methylenebis(2-aminophenol) 45.22g (0.196mol), 4,4'-methylenebis(2-amino-3,6xylenol) 56.24g (0.196 mol). Then, 578.3 g of NMP was added to the above-mentioned separate flask, and each raw material component was dissolved. Next, using an oil bath, it was reacted at 90°C for 5 hours. Next, 24.34 g (0.141 mol) of 4-phthalic anhydride and 121.7 g of NMP were added to the above-mentioned separate flask, and the reaction was carried out while stirring at 90° C. for 2 hours, and then cooled to 23° C. to complete the process. reaction. The filtrate obtained by filtering the reaction mixture in the separate flask was put into a solution of water/isopropyl alcohol = 7/4 (volume ratio). Then, the precipitate was filtered out, thoroughly washed with water, and dried under vacuum to obtain polyhydroxyamide-based (polybenzoxazole precursor) resin A-8.

＜實施例及比較例＞ 在各實施例中，分別將下述表中所記載的成分進行混合，獲得了各感光性樹脂組成物。又，在各比較例中，分別混合下述表中所記載之成分，藉此獲得了各比較用組成物。 具體而言，將表中所記載之各成分的含量（配合量）設為表的各欄的“添加量”的欄中所記載之量（質量份）。 但是，溶劑C的含量設為使溶劑C的含有質量份相對於組成物的總質量成為“相對於組成物整體之含量〔ppm〕”的欄中所記載之值（ppm）。 利用細孔寬度為0.8μm的聚四氟乙烯製過濾器，對所獲得之感光性樹脂組成物及比較用組成物進行了加壓過濾。 例如，表中的“NMP/乳酸乙酯”“160/40”的記載表示使用NMP160質量份、使用乳酸乙酯40質量份。 又，在表中，“-”的記載表示組成物不含有相應成分。 <Examples and Comparative Examples> In each Example, the components described in the following table were mixed, and each photosensitive resin composition was obtained. In addition, in each comparative example, each comparative composition was obtained by mixing the components described in the following table. Specifically, the content (compounding amount) of each component described in the table is the amount (parts by mass) described in the "added amount" column of each column of the table. However, the content of the solvent C is set to the value (ppm) described in the column of "content relative to the entire composition [ppm]" so that the content by mass of the solvent C relative to the total mass of the composition becomes the value (ppm). The obtained photosensitive resin composition and the comparative composition were pressure-filtered using a polytetrafluoroethylene filter with a pore width of 0.8 μm. For example, the description of "NMP/ethyl lactate" and "160/40" in the table indicates that 160 parts by mass of NMP and 40 parts by mass of ethyl lactate are used. In addition, in the table, the description of "-" indicates that the composition does not contain the corresponding component.

[表1]    樹脂 溶劑B 溶劑C 感光劑 增感劑 交聯劑 聚合抑制劑 密接性改良劑 遷移抑制劑 抗氧化劑 熱鹼產生劑 其他 乾燥後的 膜厚均勻性 曝光部的顯影 前後的膜厚變化率 斷裂伸長率 種類 添加量 種類 添加量 種類 SP值 [（J/cm 3） 0.5] 沸點 [℃] 相對於組成物整體之含量 [ppm] 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 實施例 1 A-1-1 100 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 2 A-1-2 100 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 3 A-2 100 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 4 A-3 100 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 5 A-4 100 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 6 A-5 100 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A B 7 A-6 100 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A B 8 A-7 100 GBL 200 1,4-二噁烷 18.5 110 50 D-5 10 - - F-4 20 - - H-2 1.5 I-1 0.02 J-1 1.5 - - - - A - C 9 A-8 100 GBL 200 1,4-二噁烷 18.5 110 50 D-5 10 - - F-4 20 - - H-2 1.5 I-1 0.02 J-1 1.5 - - - - A - C 10 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 11 A-1-2/A3 50/50 NMP/EL 100/25 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 12 A-1-2/A3 50/50 NMP/EL 125/31 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 13 A-1-2/A3 50/50 NMP/EL 200/50 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 14 A-1-2/A3 50/50 NMP/EL 244/56 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 15 A-1-2/A3 50/50 NMP/PGME 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C A A 16 A-1-2/A3 50/50 NMP 200 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B A 17 A-1-2/A3 50/50 GBL/DMSO 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 18 A-1-2/A3 50/50 DMSO 200 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C C A 19 A-1-2/A3 50/50 GBL 200 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 20 A-1-2/A3 50/50 GBL/NMP 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 21 A-1-2/A3 50/50 GBL/DMI 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B A 22 A-1-2/A3 50/50 S-1/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A [Table 1] Resin Solvent B Solvent C Sensitizer Sensitizer Cross-linking agent polymerization inhibitor Adhesion improver migration inhibitor Antioxidants Thermal base generator other Film thickness uniformity after drying Film thickness change rate of exposed portion before and after development Elongation at break Kind Adding amount Kind Adding amount Kind SP value [(J/cm 3 ) 0.5 ] Boiling point [℃] Content relative to the entire composition [ppm] Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example 1 A-1-1 100 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 2 A-1-2 100 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 3 A-2 100 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 4 A-3 100 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 5 A-4 100 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 6 A-5 100 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A B 7 A-6 100 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A B 8 A-7 100 GBL 200 1,4-dioxane 18.5 110 50 D-5 10 - - F-4 20 - - H-2 1.5 I-1 0.02 J-1 1.5 - - - - A - C 9 A-8 100 GBL 200 1,4-dioxane 18.5 110 50 D-5 10 - - F-4 20 - - H-2 1.5 I-1 0.02 J-1 1.5 - - - - A - C 10 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 11 A-1-2/A3 50/50 NMP/EL 100/25 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 12 A-1-2/A3 50/50 NMP/EL 125/31 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 13 A-1-2/A3 50/50 NMP/EL 200/50 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 14 A-1-2/A3 50/50 NMP/EL 244/56 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 15 A-1-2/A3 50/50 NMP/PGME 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C A A 16 A-1-2/A3 50/50 NMP 200 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B A 17 A-1-2/A3 50/50 GBL/DMSO 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 18 A-1-2/A3 50/50 DMSO 200 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C C A 19 A-1-2/A3 50/50 GBL 200 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 20 A-1-2/A3 50/50 GBL/NMP 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A twenty one A-1-2/A3 50/50 GBL/DMI 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B A twenty two A-1-2/A3 50/50 S-1/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A

[表2]    樹脂 溶劑B 溶劑C 感光劑 增感劑 交聯劑 聚合抑制劑 密接性改良劑 遷移抑制劑 抗氧化劑 熱鹼產生劑 其他 乾燥後的 膜厚均勻性 曝光部的顯影 前後的膜厚變化率 斷裂伸長率 種類 添加量 種類 添加量 種類 SP值 [（J/cm 3） 0.5] 沸點 [℃] 相對於組成物整體之含量 [ppm] 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 實施例 23 A-1-2/A3 50/50 S-1/PGME 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 24 A-1-2/A3 50/50 S-1 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 25 A-1-2/A3 50/50 DMI/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B A 26 A-1-2/A3 50/50 DMI/PGME 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C B A 27 A-1-2/A3 50/50 DMI 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C B A 28 A-1-2/A3 50/50 NMP/EL 160/40 乙酸乙酯 18.5 77 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B B 29 A-1-2/A3 50/50 NMP/EL 160/40 乙酸異丙酯 17.5 89 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 30 A-1-2/A3 50/50 NMP/EL 160/40 乙酸正丙酯 17.9 102 50 D-5 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 31 A-1-2/A3 50/50 NMP/EL 160/40 乙酸丁酯 17.7 126 50 D-5 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B A 32 A-1-2/A3 50/50 NMP/EL 160/40 己烷 14.9 68 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C C C 33 A-1-2/A3 50/50 NMP/EL 160/40 庚烷 15.2 98 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C B B 34 A-1-2/A3 50/50 NMP/EL 160/40 苯 19.7 80 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B B 35 A-1-2/A3 50/50 NMP/EL 160/40 甲醇 29.9 64 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B B 36 A-1-2/A3 50/50 NMP/EL 160/40 乙醇 25.0 78 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A B A 37 A-1-2/A3 50/50 NMP/EL 160/40 乙烯 碳酸酯 30.2 244 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B B 38 A-1-2/A3 50/50 NMP/EL 160/40 丙烯 碳酸酯 26.5 242 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B A 39 A-1-2/A3 50/50 NMP/EL 160/40 THF 18.3 65 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 40 A-1-2/A3 50/50 NMP/EL 160/40 1,4-二噁烷 20.5 101 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 41 A-1-2/A3 50/50 NMP/EL 160/40 二乙二醇 二甲醚 18.3 162 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 42 A-1-2/A3 50/50 NMP/EL 160/40 二乙二醇 二乙醚 17.5 188 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A B A 43 A-1-2/A3 50/50 NMP/EL 160/40 PGMEA 18.3 146 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A B A [Table 2] Resin Solvent B Solvent C Sensitizer Sensitizer Cross-linking agent polymerization inhibitor Adhesion improver migration inhibitor Antioxidants Thermal base generator other Film thickness uniformity after drying Film thickness change rate of exposed portion before and after development Elongation at break Kind Adding amount Kind Adding amount Kind SP value [(J/cm 3 ) 0.5 ] Boiling point [℃] Content relative to the entire composition [ppm] Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example twenty three A-1-2/A3 50/50 S-1/PGME 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A twenty four A-1-2/A3 50/50 S-1 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 25 A-1-2/A3 50/50 DMI/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B A 26 A-1-2/A3 50/50 DMI/PGME 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C B A 27 A-1-2/A3 50/50 DMI 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C B A 28 A-1-2/A3 50/50 NMP/EL 160/40 Ethyl acetate 18.5 77 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B B 29 A-1-2/A3 50/50 NMP/EL 160/40 Isopropyl acetate 17.5 89 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 30 A-1-2/A3 50/50 NMP/EL 160/40 n-propyl acetate 17.9 102 50 D-5 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 31 A-1-2/A3 50/50 NMP/EL 160/40 Butyl acetate 17.7 126 50 D-5 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B A 32 A-1-2/A3 50/50 NMP/EL 160/40 Hexane 14.9 68 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C C C 33 A-1-2/A3 50/50 NMP/EL 160/40 Heptane 15.2 98 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C B B 34 A-1-2/A3 50/50 NMP/EL 160/40 benzene 19.7 80 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B B 35 A-1-2/A3 50/50 NMP/EL 160/40 Methanol 29.9 64 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B B 36 A-1-2/A3 50/50 NMP/EL 160/40 ethanol 25.0 78 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A B A 37 A-1-2/A3 50/50 NMP/EL 160/40 Ethylene carbonate 30.2 244 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B B 38 A-1-2/A3 50/50 NMP/EL 160/40 Acrylic carbonate 26.5 242 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B B A 39 A-1-2/A3 50/50 NMP/EL 160/40 THF 18.3 65 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 40 A-1-2/A3 50/50 NMP/EL 160/40 1,4-dioxane 20.5 101 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 41 A-1-2/A3 50/50 NMP/EL 160/40 Diethylene glycol dimethyl ether 18.3 162 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 42 A-1-2/A3 50/50 NMP/EL 160/40 Diethylene glycol diethyl ether 17.5 188 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A B A 43 A-1-2/A3 50/50 NMP/EL 160/40 PGMEA 18.3 146 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A B A

[表3]    樹脂 溶劑B 溶劑C 感光劑 增感劑 交聯劑 聚合抑制劑 密接性改良劑 遷移抑制劑 抗氧化劑 熱鹼產生劑 其他 乾燥後的 膜厚均勻性 曝光部的顯影前後的膜厚變化率 斷裂伸長率 種類 添加量 種類 添加量 種類 SP值 [（J/cm 3） 0.5] 沸點 [℃] 相對於組成物整體之含量 [ppm] 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 種類 添加量 實施例 44 A-1-2/A3 50/50 NMP/EL 160/40 環戊酮 20.6 130 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A B A 45 A-1-2/A3 50/50 NMP/EL 160/40 環戊酮 20.3 155 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A B A 46 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 /乙醇 18.5/ 25.0 110/ 78 25/ 25 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 47 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 /THF 18.5/ 18.3 110/ 65 25/ 25 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 48 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 /THF /乙醇 18.5/ 18.3/ 25 110/ 65/ 78 20/ 20/ 20 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 49 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 1 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A C C 50 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 10 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A B B 51 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 100 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 52 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 1000 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 53 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 10000 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C B B 54 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 50 D-1 2 E-1 /E-2 2/1 F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 55 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 50 D-2 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 56 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 50 D-4 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 57 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 58 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 59 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-2 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 60 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-3 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 61 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-1 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 62 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-2 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 63 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-1 1.5 I-1 0.02 J-1 1.5 - - - - A A A 64 A-1-2/A3 50/50 NMP/EL 160/40 甲苯 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-2 0.02 J-1 1.5 - - - - A A A [table 3] Resin Solvent B Solvent C Sensitizer Sensitizer Cross-linking agent polymerization inhibitor Adhesion improver migration inhibitor Antioxidants Thermal base generator other Film thickness uniformity after drying Film thickness change rate of exposed portion before and after development Elongation at break Kind Adding amount Kind Adding amount Kind SP value [(J/cm 3 ) 0.5 ] Boiling point [℃] Content relative to the entire composition [ppm] Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example 44 A-1-2/A3 50/50 NMP/EL 160/40 cyclopentanone 20.6 130 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A B A 45 A-1-2/A3 50/50 NMP/EL 160/40 cyclopentanone 20.3 155 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A B A 46 A-1-2/A3 50/50 NMP/EL 160/40 Toluene/ethanol 18.5/ 25.0 110/78 25/25 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 47 A-1-2/A3 50/50 NMP/EL 160/40 Toluene/THF 18.5/ 18.3 110/65 25/25 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 48 A-1-2/A3 50/50 NMP/EL 160/40 Toluene/THF/Ethanol 18.5/ 18.3/ 25 110/ 65/ 78 20/ 20/ 20 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 49 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 1 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A C C 50 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 10 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A B B 51 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 100 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 52 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 1000 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - B A A 53 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 10000 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - C B B 54 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 50 D-1 2 E-1 /E-2 2/1 F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 55 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 50 D-2 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 56 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 50 D-4 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 57 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 58 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 59 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-2 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 60 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-3 8 G-3 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 61 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-1 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 62 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-2 0.05 H-2 1.5 I-1 0.02 J-1 1.5 - - - - A A A 63 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-1 1.5 I-1 0.02 J-1 1.5 - - - - A A A 64 A-1-2/A3 50/50 NMP/EL 160/40 Toluene 18.5 110 50 D-3 2 - - F-1 8 G-3 0.05 H-2 1.5 I-2 0.02 J-1 1.5 - - - - A A A

Figure 111109965-A0305-02-0095-2
Figure 111109965-A0305-02-0095-2

表中所記載之縮寫的詳細內容如下。The details of the abbreviations listed in the table are as follows.

〔樹脂〕 •樹脂A-1-1～A-1-2、A-2～A-8：藉由上述合成例獲得之樹脂A-1-1～A-1-2、A-2～A-8 〔Resin〕 •Resins A-1-1 to A-1-2, A-2 to A-8: Resins A-1-1 to A-1-2, A-2 to A-8 obtained by the above synthesis example

〔溶劑B〕 •NMP：N-甲基-2-吡咯啶酮 •DMSO：二甲基亞碸 •GBL：γ-丁內酯 •PGME：丙二醇單甲醚 •DMI：1,3-二甲基-2-咪唑啶酮 •S-1：3-甲氧基-N,N-二甲基丙醯胺 •EL：乳酸乙酯 [Solvent B] •NMP: N-methyl-2-pyrrolidone •DMSO: dimethylsulfoxide •GBL: gamma-butyrolactone •PGME: propylene glycol monomethyl ether •DMI: 1,3-dimethyl-2-imidazolidinone •S-1: 3-methoxy-N,N-dimethylpropylamine •EL: Ethyl lactate

〔溶劑C〕 •THF：四氫呋喃 PGMEA：丙二醇單甲醚乙酸酯 [Solvent C] •THF: Tetrahydrofuran PGMEA: propylene glycol monomethyl ether acetate

〔感光劑〕 •D-1～D-7：下述結構的化合物 [化學式23] [Photosensitizer] •D-1～D-7: Compounds with the following structure [Chemical Formula 23]

〔增感劑〕 •E-1～E-3：下述結構的化合物 [化學式24] [Sensitizer] •E-1 to E-3: Compounds with the following structures [Chemical Formula 24]

〔交聯劑（聚合性化合物）〕 •F-1～F-6：下述結構的化合物、Me表示甲基。 [化學式25] [Crosslinking agent (polymerizable compound)] •F-1 to F-6: Compounds with the following structures, Me represents a methyl group. [Chemical formula 25]

〔聚合抑制劑〕 •G-1～G-4：下述結構的化合物 [化學式26] [Polymerization inhibitor] •G-1 to G-4: Compounds with the following structures [Chemical Formula 26]

〔密接性改良劑（金屬接著性改良劑）〕 •H-1～H-3：下述結構的化合物、Et表示乙基。 [化學式27] [Adhesion improver (metal adhesion improver)] •H-1 to H-3: Compounds with the following structures, Et represents an ethyl group. [Chemical formula 27]

〔遷移抑制劑〕 •I-1～I-3：下述結構的化合物 [化學式28] [Migration Inhibitor] •I-1 to I-3: Compounds with the following structures [Chemical Formula 28]

〔抗氧化劑〕 •J-1：下述結構的化合物 [化學式29] [Antioxidant] •J-1: Compound with the following structure [Chemical Formula 29]

〔熱鹼產生劑〕 •K-1～K-3：下述結構的化合物 [化學式30] [Thermal base generator] •K-1 to K-3: Compounds with the following structures [Chemical Formula 30]

〔其他〕 •L-1：下述結構的化合物 [化學式31] [Others] •L-1: Compound with the following structure [Chemical Formula 31]

＜評價＞ 〔基於剛製備後的組成物之膜厚均勻性的評價〕 在各實施例或比較例中，分別將剛製備後的各感光性樹脂組成物或比較用組成物藉由旋塗法並以層狀適用（塗佈）於直徑8英吋的圓形狀的矽晶圓上。 將上述塗佈後的矽晶圓在加熱板上，在100℃下乾燥4分鐘，從而在矽晶圓上形成了膜厚19μm的樹脂膜。膜厚設為面內10處的膜厚的算術平均值。 在矽晶圓的直徑上的上述樹脂膜中，在包含上述樹脂膜的兩端之等間隔的計10處測定上述樹脂膜的膜厚，並將上述10處的測定值的最大值與最小值之差設為面內最大膜厚差（μm）。 根據下述評價基準，對由剛製備後的組成物形成之膜的膜厚均勻性進行了評價。評價結果記載於表中的“乾燥後的膜厚均勻性”的欄中。上述面內最大膜厚差（μm）愈小，代表塗佈性愈優異。-評價基準- A：上述面內最大膜厚差（μm）為0.5μm以下。 B：上述面內最大膜厚差（μm）大於0.5μm且為0.8μm以下。 C：上述面內最大膜厚差（μm）大於0.8μm且為1.0μm以下。 D：上述面內最大膜厚差（μm）大於1.0μm。 ＜Evaluation＞ [Evaluation based on film thickness uniformity of the composition immediately after preparation] In each of the Examples or Comparative Examples, each photosensitive resin composition or comparative composition immediately after preparation was applied (coated) in a layered form to a circular silicone sheet with a diameter of 8 inches by spin coating. on the wafer. The coated silicon wafer was dried on a hot plate at 100° C. for 4 minutes, thereby forming a resin film with a thickness of 19 μm on the silicon wafer. The film thickness is the arithmetic mean of the film thicknesses at 10 locations in the plane. In the above-mentioned resin film on the diameter of the silicon wafer, the film thickness of the above-mentioned resin film is measured at 10 points at equal intervals including both ends of the above-mentioned resin film, and the maximum value and the minimum value of the measured values at the above 10 points are The difference is set as the maximum film thickness difference in the plane (μm). The film thickness uniformity of the film formed from the composition immediately after preparation was evaluated based on the following evaluation criteria. The evaluation results are described in the column of "Film thickness uniformity after drying" in the table. The smaller the above-mentioned maximum film thickness difference (μm) in the plane, the better the coating properties. -Evaluation criteria- A: The maximum film thickness difference (μm) in the above plane is 0.5μm or less. B: The maximum film thickness difference (μm) in the above plane is greater than 0.5 μm and less than 0.8 μm. C: The maximum film thickness difference (μm) in the above plane is greater than 0.8 μm and less than 1.0 μm. D: The maximum film thickness difference (μm) in the above plane is greater than 1.0μm.

〔曝光部的顯影前後的膜厚變化率〕 在各實施例或比較例中，分別將剛製備後的各感光性樹脂組成物或比較用組成物藉由旋塗法並以層狀塗佈於直徑8英吋的圓形狀的矽晶圓上。將上述塗佈後的矽晶圓在加熱板上，在100℃下乾燥4分鐘，從而在矽晶圓上形成了膜厚19μm的樹脂膜。將該樹脂膜的面內10處的膜厚的算術平均值設為顯影前的膜厚。 使用步進機（Nikon NSR 2005 i9C）對上述矽晶圓上的樹脂膜的整面進行了曝光。在曝光中使用i射線，在波長365nm下，以200mJ/cm 2進行了曝光。將上述曝光後的樹脂膜用環戊酮顯影60秒鐘之後，用PGMEA沖洗了60秒鐘。將上述顯影後的樹脂膜的面內10處的膜厚的算術平均值設為顯影後的膜厚，並根據下述式求出曝光部的顯影前後的膜厚變化率（%）。按照下述評價基準進行評價，將評價結果記載於表的“曝光部的顯影前後的膜厚變化率”的欄中。又，在評價結果的欄中記載為“-”之例中，未進行本評價。曝光部的顯影前後的膜厚變化率愈小，表示曝光前後的膜厚均勻性愈優異。 曝光部的顯影前後的膜厚變化率（%）=（1-顯影後的膜厚/顯影前的膜厚）×100 -評價基準- A：曝光部的顯影前後的膜厚變化率（%）小於5%。 B：曝光部的顯影前後的膜厚變化率（%）為5%以上且小於7%。 C：曝光部的顯影前後的膜厚變化率（%）為7%以上且小於10%。 D：曝光部的顯影前後的膜厚變化率（%）為10%以上。 [Film thickness change rate before and after development of the exposed part] In each of the Examples or Comparative Examples, each photosensitive resin composition or the comparative composition immediately after preparation was applied in a layer by spin coating. On a round silicon wafer with a diameter of 8 inches. The coated silicon wafer was dried on a hot plate at 100° C. for 4 minutes, thereby forming a resin film with a thickness of 19 μm on the silicon wafer. The arithmetic mean value of the film thickness at 10 locations in the surface of the resin film was defined as the film thickness before development. The entire surface of the resin film on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). I-rays were used for exposure, and exposure was performed at 200 mJ/cm 2 at a wavelength of 365 nm. The exposed resin film was developed with cyclopentanone for 60 seconds and then rinsed with PGMEA for 60 seconds. The arithmetic mean value of the film thickness at 10 locations in the surface of the resin film after development was taken as the film thickness after development, and the film thickness change rate (%) of the exposed portion before and after development was calculated based on the following formula. Evaluation was performed in accordance with the following evaluation criteria, and the evaluation results were recorded in the column of the "film thickness change rate of the exposed portion before and after development" of the table. In addition, in the case where "-" is written in the column of the evaluation result, this evaluation was not performed. The smaller the film thickness change rate before and after development of the exposed portion, the better the film thickness uniformity before and after exposure. Film thickness change rate of the exposed part before and after development (%) = (1 - Film thickness after development / Film thickness before development) × 100 - Evaluation criteria - A: Film thickness change rate of the exposed part before and after development (%) Less than 5%. B: The film thickness change rate (%) of the exposed part before and after development is 5% or more and less than 7%. C: The film thickness change rate (%) of the exposed part before and after development is 7% or more and less than 10%. D: The film thickness change rate (%) of the exposed part before and after development is 10% or more.

〔膜強度（斷裂伸長率）〕 在各實施例或比較例中，分別將表中所記載之各感光性樹脂組成物或比較用組成物藉由旋塗法適用於矽晶圓上從而形成了樹脂組成物層。將適用了所獲得之樹脂組成物層之矽晶圓在加熱板上，在100℃下乾燥5分鐘，從而在矽晶圓上獲得了約15μm厚度的均勻的樹脂組成物層。將所獲得之樹脂組成物層（樹脂層）在氮氣氣氛下，以10℃/分鐘的升溫速度進行升溫，達到230℃之後，加熱了3小時。將硬化後的樹脂層（硬化膜）浸漬於4.9%氫氟酸溶液中，並從矽晶圓剝離了硬化膜。用衝孔機將所剝離之硬化膜製作成寬度3mm、試樣長度30mm的試驗片。利用拉伸試驗機（TENSILON），以十字頭速度300mm/分鐘、在試驗片的長度方向上、25℃、65%RH（相對濕度）的環境下，遵照JIS-K6251，測定了所獲得之試驗片。評價各實施5次，對試驗片斷裂時的伸長率（斷裂伸長率）使用了其平均值。 按照下述評價基準進行評價，將評價結果記載於表中的“斷裂伸長率”的欄中。斷裂伸長率愈大，表示膜強度愈高。 -評價基準- A：上述斷裂伸長率為65%以上。 B：上述斷裂伸長率為60%以上且小於65%。 C：上述斷裂伸長率為55%以上且60%。 D：上述斷裂伸長率小於55%。 [Film strength (elongation at break)] In each of the examples or comparative examples, each photosensitive resin composition or comparative composition described in the table was applied on a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes, thereby obtaining a uniform resin composition layer with a thickness of about 15 μm on the silicon wafer. The obtained resin composition layer (resin layer) was heated at a heating rate of 10°C/min in a nitrogen atmosphere. After reaching 230°C, it was heated for 3 hours. The hardened resin layer (cured film) was immersed in a 4.9% hydrofluoric acid solution, and the cured film was peeled off from the silicon wafer. Use a punching machine to prepare a test piece with a width of 3 mm and a sample length of 30 mm from the peeled cured film. The obtained test was measured using a tensile testing machine (TENSILON) at a crosshead speed of 300 mm/min, in the length direction of the test piece, in an environment of 25°C and 65%RH (relative humidity) in accordance with JIS-K6251. piece. Each evaluation was performed five times, and the average value was used for the elongation at break of the test piece (elongation at break). Evaluation was performed according to the following evaluation criteria, and the evaluation results were recorded in the column of "elongation at break" in the table. The greater the elongation at break, the higher the film strength. -Evaluation criteria- A: The above-mentioned elongation at break is 65% or more. B: The above-mentioned elongation at break is 60% or more and less than 65%. C: The above-mentioned elongation at break is 55% or more and 60%. D: The above elongation at break is less than 55%.

根據以上的結果可知，藉由使用本發明的感光性樹脂組成物，所獲得之硬化物的斷裂伸長率（膜強度）提高。 比較例1中的比較用組成物不包含溶劑C。又，比較例2～3之比較用組成物中，溶劑C的含量不包含在1ppm以上且10,000ppm以下的範圍內。比較例4中的比較用組成物中，溶劑的沸點不是60℃以上。 在該等比較例之態樣中，可知所獲得之硬化物的斷裂伸長率（膜強度）差。 From the above results, it is understood that by using the photosensitive resin composition of the present invention, the elongation at break (film strength) of the obtained cured product is improved. The comparative composition in Comparative Example 1 does not contain solvent C. In addition, in the comparative compositions of Comparative Examples 2 to 3, the content of the solvent C is not included in the range of 1 ppm or more and 10,000 ppm or less. In the comparative composition in Comparative Example 4, the boiling point of the solvent is not 60° C. or higher. In the aspects of these comparative examples, it was found that the obtained cured products had poor elongation at break (film strength).

＜實施例101＞ 藉由旋塗法將實施例1中所使用之樹脂組成物以層狀適用於表面形成有銅薄層之樹脂基材的銅薄層表面，在100℃下乾燥5分鐘，藉此形成了膜厚20μm的感光膜之後，用步進機（Nikon Corporation製，NSR1505 i6）進行了曝光。隔著遮罩（圖案為1:1線與空間，線寬為10μm的二元遮罩），在波長365nm處進行了曝光。上述曝光之後，用環己酮顯影2分鐘，用PGMEA沖洗30秒，藉此獲得了層的圖案。 接著，在氮氣環境下，以10℃/分鐘的升溫速度進行升溫，達到230℃之後，在230℃維持180分鐘，藉此形成了再配線層用層間絕緣膜。該再配線層用層間絕緣膜的絕緣性優異。 又，使用該等再配線層用層間絕緣膜製造半導體元件之結果，確認到正常工作。 <Example 101> The resin composition used in Example 1 was applied in a layered manner to the surface of the copper thin layer of the resin base material on which the copper thin layer was formed by the spin coating method, and dried at 100° C. for 5 minutes to form a film. After the photosensitive film with a thickness of 20 μm was exposed, it was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10 μm). After the above exposure, the layer pattern was obtained by developing with cyclohexanone for 2 minutes and rinsing with PGMEA for 30 seconds. Next, the temperature was raised at a heating rate of 10° C./min in a nitrogen atmosphere. After reaching 230° C., the temperature was maintained at 230° C. for 180 minutes, thereby forming an interlayer insulating film for a rewiring layer. This interlayer insulating film for rewiring layers has excellent insulation properties. Furthermore, the results of manufacturing semiconductor elements using these interlayer insulating films for rewiring layers confirmed normal operation.

無。without.

Claims (19)

一種感光性樹脂組成物，其係包含：環化樹脂或其前驅物；溶劑B，SP值為21.0(J/cm3)0.5以上且小於25.0(J/cm3)0.5；溶劑C，SP值小於21.0(J/cm3)0.5或為25.0(J/cm3)0.5以上且沸點為60℃以上；感光劑；及交聯劑，前述溶劑C的含量相對於感光性樹脂組成物的總質量為1ppm以上且10,000ppm以下。 A photosensitive resin composition, which contains: cyclized resin or its precursor; solvent B, SP value is 21.0 (J/cm 3 ) 0.5 or more and less than 25.0 (J/cm 3 ) 0.5 ; solvent C, SP value Less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or more and the boiling point is above 60°C; photosensitive agent; and cross-linking agent, the content of the aforementioned solvent C relative to the total mass of the photosensitive resin composition 1ppm or more and 10,000ppm or less. 如請求項1所述之感光性樹脂組成物，其中前述溶劑C為選自包括乙酸乙酯、乙酸異丙酯、乙酸正丙酯、乙酸丁酯、己烷、庚烷、苯、甲苯、甲醇、乙醇、四氫呋喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二乙醚、丙二醇單甲醚乙酸酯、環戊酮及環己酮之群組中之至少1種。 The photosensitive resin composition according to claim 1, wherein the solvent C is selected from the group consisting of ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, hexane, heptane, benzene, toluene, and methanol. At least 1 of the group consisting of , ethanol, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone and cyclohexanone species. 一種感光性樹脂組成物，其係包含：環化樹脂或其前驅物；溶劑B，SP值為21.0(J/cm3)0.5以上且小於25.0(J/cm3)0.5；溶劑C，其為乙酸乙酯、乙酸異丙酯、乙酸正丙酯、乙酸丁酯、己烷、 庚烷、苯、甲苯、甲醇、乙醇、四氫呋喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二乙醚、丙二醇單甲醚乙酸酯、環戊酮或環己酮；感光劑；及交聯劑，前述溶劑C的含量相對於感光性樹脂組成物的總質量為1ppm以上且10,000ppm以下。 A photosensitive resin composition, which contains: cyclized resin or its precursor; solvent B, with an SP value of 21.0 (J/cm 3 ) 0.5 or more and less than 25.0 (J/cm 3 ) 0.5 ; solvent C, which is Ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, hexane, heptane, benzene, toluene, methanol, ethanol, tetrahydrofuran, 1,4-dioxane, diglyme, Diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone or cyclohexanone; photosensitive agent; and cross-linking agent, the content of the aforementioned solvent C is more than 1 ppm relative to the total mass of the photosensitive resin composition and Below 10,000ppm. 如請求項1至請求項3之任一項所述之感光性樹脂組成物，其中前述溶劑B包含選自包括γ-丁內酯、二甲基亞碸、N-甲基-2-吡咯啶酮、丙二醇單甲醚及乳酸乙酯之群組中之至少1種。 The photosensitive resin composition according to any one of claims 1 to 3, wherein the aforementioned solvent B contains γ-butyrolactone, dimethylsulfoxide, and N-methyl-2-pyrrolidine. At least one of the group consisting of ketone, propylene glycol monomethyl ether and ethyl lactate. 如請求項1至請求項3之任一項所述之感光性樹脂組成物，其中前述溶劑B的含量相對於感光性樹脂組成物的總質量為40質量%以上且小於90質量%。 The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of the solvent B is 40 mass % or more and less than 90 mass % with respect to the total mass of the photosensitive resin composition. 如請求項1至請求項3之任一項所述之感光性樹脂組成物，其中前述溶劑B包含γ-丁內酯或N-甲基-2-吡咯啶酮。 The photosensitive resin composition according to any one of claims 1 to 3, wherein the solvent B contains γ-butyrolactone or N-methyl-2-pyrrolidone. 如請求項1至請求項3之任一項所述之感光性樹脂組成物，其中前述溶劑C為甲苯、四氫呋喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二乙醚或環戊酮。 The photosensitive resin composition according to any one of claims 1 to 3, wherein the solvent C is toluene, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, or diethylene glycol. Diethyl ether or cyclopentanone. 如請求項1至請求項3之任一項所述之感光性樹脂組成物，其中前述溶劑C為甲苯、四氫呋喃、1,4-二噁烷或二乙二醇二甲醚。 The photosensitive resin composition according to any one of claims 1 to 3, wherein the solvent C is toluene, tetrahydrofuran, 1,4-dioxane or diethylene glycol dimethyl ether. 如請求項1至請求項3之任一項所述之感光性樹脂組成物，其中前述感光劑為光自由基聚合起始劑。 The photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive agent is a photoradical polymerization initiator. 如請求項1至請求項3之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。 The photosensitive resin composition according to any one of claims 1 to 3, further comprising a radically polymerizable compound. 如請求項1至請求項3之任一項所述之感光性樹脂組成物，其還包含矽烷偶合劑。 The photosensitive resin composition according to any one of claims 1 to 3, further comprising a silane coupling agent. 如請求項1至請求項3之任一項所述之感光性樹脂組成物，其用於形成供負型顯影之感光膜。 The photosensitive resin composition according to any one of claims 1 to 3, which is used to form a photosensitive film for negative development. 如請求項1至請求項3之任一項所述之感光性樹脂組成物，其用於形成再配線層用層間絕緣膜。 The photosensitive resin composition according to any one of claims 1 to 3, which is used to form an interlayer insulating film for a rewiring layer. 一種硬化物，其係硬化請求項1至請求項13之任一項所述之感光性樹脂組成物而成。 A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 13. 一種積層體，其係包含2層以上由請求項14所述之硬化物構成之層， 在由前述硬化物構成之任意層之間包含金屬層。 A laminated body including two or more layers composed of the hardened material described in claim 14, A metal layer is included between arbitrary layers composed of the aforementioned hardened material. 一種硬化物的製造方法，其係包括在基板上適用請求項1至請求項13之任一項所述之感光性樹脂組成物來形成膜之膜形成步驟。 A method for manufacturing a cured product, which includes a film forming step of forming a film on a substrate by applying the photosensitive resin composition according to any one of claims 1 to 13. 如請求項16所述之硬化物的製造方法，其包括：曝光步驟，對前述膜進行曝光；及顯影步驟，對前述膜進行顯影。 The method for manufacturing a hardened product according to claim 16, which includes: an exposure step of exposing the film; and a development step of developing the film. 如請求項16所述之硬化物的製造方法，其包括在50~450℃下加熱前述膜之加熱步驟。 The method for manufacturing a hardened product according to claim 16, which includes a heating step of heating the film at 50 to 450°C. 一種半導體元件，其係包含請求項14所述之硬化物。A semiconductor element including the hardened material according to claim 14.
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