TW202234156A - Resin composition, cured product, laminate, production method for cured product, semiconductor device, and compound - Google Patents

Resin composition, cured product, laminate, production method for cured product, semiconductor device, and compound Download PDF

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Publication number
TW202234156A
TW202234156A TW110147272A TW110147272A TW202234156A TW 202234156 A TW202234156 A TW 202234156A TW 110147272 A TW110147272 A TW 110147272A TW 110147272 A TW110147272 A TW 110147272A TW 202234156 A TW202234156 A TW 202234156A
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group
preferable
formula
acid
compound
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TW110147272A
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Chinese (zh)
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浅川大輔
青島俊栄
小泉孝徳
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日商富士軟片股份有限公司
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Publication of TW202234156A publication Critical patent/TW202234156A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/14—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C235/34—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C235/36—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/84—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/30—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by doubly bound oxygen or sulfur atoms or by two oxygen or sulfur atoms singly bound to the same carbon atom
    • C07D211/32—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by doubly bound oxygen or sulfur atoms or by two oxygen or sulfur atoms singly bound to the same carbon atom by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • C07D303/06—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms in which the oxirane rings are condensed with a carbocyclic ring system having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • G—PHYSICS
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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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
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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
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    • 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
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    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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    • G03F7/40—Treatment after imagewise removal, e.g. baking

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)

Abstract

Provided are: a resin composition that includes at least one type of resin selected from the group consisting of cyclic resins and precursors thereof and also includes a polymerizable compound having an amide bond with polymerizable groups bonded to one another with a linking group therebetween, wherein the amide bond is bonded to the linking group at a carbonyl group side thereof, and, if the polymerizable compound is used to synthesize a homopolymer, the property in which the homopolymer generates a base released from the main chain by means of heating to 250 DEG C is exhibited; a cured product obtained by curing said resin composition; a laminate including the cured product; a production method for the cured product; a semiconductor device including the cured product or the laminate; and a novel compound.

Description

樹脂組成物、硬化物、積層體、硬化物之製造方法及半導體元件以及化合物Resin composition, cured product, laminated body, manufacturing method of cured product, semiconductor element, and compound

本發明係有關一種樹脂組成物、硬化物、積層體、硬化物之製造方法及半導體元件以及化合物。The present invention relates to a resin composition, a cured product, a laminate, and a method for producing the cured product, a semiconductor element, and a compound.

聚醯亞胺等環化樹脂的耐熱性及絕緣性等優異，因此適用於各種用途。作為上述用途並無特別限定，但是若舉出實際安裝用半導體元件為例，則可以舉出作為絕緣膜或密封材料的材料或保護膜的利用。又，亦可以用作撓性基板的基底膜或覆蓋膜等。Cyclized resins such as polyimide have excellent heat resistance and insulating properties, and are therefore suitable for various applications. Although it does not specifically limit as said use, If the semiconductor element for actual mounting is mentioned as an example, the use as a material of an insulating film or a sealing material, or a protective film can be mentioned. Moreover, 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一者之樹脂組成物的形態使用。 將該種樹脂組成物例如藉由塗佈等適用於基材上而形成感光膜，之後依據需要進行曝光、顯影、加熱等，從而能夠將硬化物形成於基材上。 聚醯亞胺前驅物等上述環化樹脂的前驅物例如藉由加熱而環化，並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而適用，因此可以說製造上的適應性優異，例如所適用之樹脂組成物在適用時的形狀、大小、適用位置等設計的自由度高等。除了聚醯亞胺等環化樹脂所具有之高性能以外，從該種製造上的適應性優異之觀點考慮，越來越期待上述樹脂組成物在產業上的應用開發。 For example, in the above application, a cyclized resin such as polyimide is used in the form of a resin composition containing at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin. Such a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and thereafter, as necessary, exposure, development, heating, and the like are performed to form a cured product on the substrate. The precursor of the above-mentioned cyclized resin, such as a polyimide precursor, is cyclized by, for example, heating, and becomes a cyclized resin such as polyimide in a cured product. Since the resin composition can be applied by a known coating method or the like, it can be said that it is excellent in suitability for manufacturing, for example, the applied resin composition has a high degree of freedom in designing the shape, size, and application position at the time of application. In addition to the high performance possessed by cyclized resins such as polyimide, the industrial application development of the above-mentioned resin composition is increasingly expected from the viewpoint of excellent suitability for such production.

例如，在專利文獻1中，記載有一種感光性樹脂組成物，其含有藉由鹼性物質或藉由在鹼性物質的存在下進行加熱而促進對最終產物的反應之高分子前驅物及具有特定的結構且藉由電磁波的照射和加熱而產生鹼之鹼產生劑。For example, Patent Document 1 describes a photosensitive resin composition containing a polymer precursor that promotes a reaction to a final product by an alkaline substance or by heating in the presence of an alkaline substance, and has An alkali generator which has a specific structure and generates alkali by irradiation and heating of electromagnetic waves.

[專利文獻1]日本特開2013-194205號公報[Patent Document 1] Japanese Patent Laid-Open No. 2013-194205

在包含環化樹脂及環化樹脂的前驅物中的至少一者之樹脂組成物中，要求所獲得之硬化物的膜收縮降低。 膜收縮是指，與硬化前的組成物（例如，加熱前的組成物膜）相比，硬化後所獲得之硬化物（例如，硬化膜）的體積減少（收縮）。從容易獲得目標尺寸的硬化物的觀點和硬化物與基材的密接性的觀點等考慮，要求硬化物的體積的減少小亦即膜收縮降低。 In the resin composition containing at least one of the cyclized resin and the precursor of the cyclized resin, the film shrinkage of the obtained cured product is required to be reduced. Film shrinkage means that the volume of the cured product (eg, cured film) obtained after curing is reduced (shrinked) compared to the composition before curing (eg, the composition film before heating). From the viewpoint of easily obtaining a cured product of a target size, the adhesiveness between the cured product and the base material, and the like, it is required that the reduction in volume of the cured product is small, that is, the reduction in film shrinkage.

本發明的目的為，提供一種所獲得之硬化物的膜收縮降低之樹脂組成物、將上述樹脂組成物硬化而成之硬化物、包含上述硬化物之積層體、上述硬化物之製造方法及包含上述硬化物或上述積層體之半導體元件。 又，本發明的目的為，提供一種新的化合物。 An object of the present invention is to provide a resin composition in which film shrinkage of the obtained cured product is reduced, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, and a method for producing the cured product. The above cured product or the semiconductor element of the above laminated body. Another object of the present invention is to provide a novel compound.

將本發明的代表性實施態樣的例子示於以下。 ＜1＞一種樹脂組成物，其係包含： 選自包括環化樹脂及其前驅物之群組中的至少1種樹脂；以及 具有經由連接基相互鍵結之聚合性基和醯胺鍵之聚合性化合物， 上述醯胺鍵與上述連接基在羰基側鍵結， 在使用上述聚合性化合物合成了單聚物的情況下，上述單聚物顯示藉由在250℃下進行加熱而產生從主鏈游離之鹼之性質。 ＜2＞如＜1＞所述之樹脂組成物，其中，上述聚合性化合物中之上述聚合性基為自由基聚合性基。 ＜3＞如＜1＞或＜2＞所述之樹脂組成物，其中，上述聚合性化合物為下述式（1-1）所表示之化合物。 [化學式1]

Figure 02_image001
式（1-1）中，R 1分別獨立地為氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，R 2分別獨立地為氫原子、鹵素原子或1價的有機基，至少2個R 2可以鍵結而形成環結構，L 1表示3價的有機基。 ＜4＞如＜1＞至＜3＞之任一項所述之樹脂組成物，其中，上述聚合性化合物為下述式（1-2）所表示之化合物。 [化學式2]
Figure 02_image003
式（1-2）中，R 1分別獨立地表示氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，L 2表示單鍵或2價的連接基，Cy表示環結構，L 3表示單鍵或2價的連接基，R 2分別獨立地表示氫原子、鹵素原子或1價的有機基，至少2個R 2可以鍵結而形成環結構。 ＜5＞如＜1＞至＜4＞之任一項所述之樹脂組成物，其中，上述樹脂具有聚合性基。 ＜6＞如＜1＞至＜5＞之任一項所述之樹脂組成物，其係進一步包含光聚合起始劑。 ＜7＞如＜1＞至＜6＞之任一項所述之樹脂組成物，其係進一步包含與上述聚合性化合物不同之聚合性化合物。 ＜8＞如＜1＞至＜7＞之任一項所述之樹脂組成物，其係用於形成再配線層用層間絕緣膜。 ＜9＞一種硬化物，其係將＜1＞至＜8＞之任一項所述之樹脂組成物硬化而成。 ＜10＞一種積層體，其係包括2層以上的由＜9＞所述之硬化物形成之層，並且在由上述硬化物形成之層之間的任一個之間包括金屬層。 ＜11＞一種硬化物之製造方法，其係包括將＜1＞至＜8＞之任一項所述之樹脂組成物適用於基材上而形成膜之膜形成步驟。 ＜12＞如＜11＞所述之硬化物之製造方法，其係包括選擇性地曝光上述膜之曝光步驟及使用顯影液對上述膜進行顯影而形成圖案之顯影步驟。 ＜13＞如＜11＞或＜12＞所述之硬化物之製造方法，其係包括在50～450℃下對上述膜進行加熱之加熱步驟。 ＜14＞一種半導體元件，其係包含＜9＞所述之硬化物或＜10＞所述之積層體。 ＜15＞一種化合物，其係由下述式（1-1）表示。 [化學式3]
Figure 02_image001
式（1-1）中，R 1分別獨立地為氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，R 2分別獨立地為氫原子、鹵素原子或1價的有機基，至少2個R 2可以鍵結而形成環結構，L 1表示3價的有機基。 ＜16＞一種化合物，其係由下述式（1-2）表示。 [化學式4]
Figure 02_image006
式（1-2）中，R 1分別獨立地表示氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，L 2表示單鍵或2價的連接基，Cy表示環結構，L 3表示單鍵或2價的連接基，R 2分別獨立地表示氫原子、鹵素原子或1價的有機基，至少2個R 2可以鍵結而形成環結構。 [發明效果] Examples of typical embodiments of the present invention are shown below. <1> A resin composition comprising: at least one resin selected from the group consisting of a cyclized resin and a precursor thereof; and a polymer having a polymerizable group mutually bonded via a linking group and an amide bond The above-mentioned amide bond and the above-mentioned linking group are bonded at the carbonyl side, and when a monomer is synthesized using the above-mentioned polymerizable compound, the above-mentioned monomer shows that by heating at 250° C., a polymer from the main chain is generated. Properties of free bases. <2> The resin composition according to <1>, wherein the polymerizable group in the polymerizable compound is a radical polymerizable group. <3> The resin composition according to <1> or <2>, wherein the polymerizable compound is a compound represented by the following formula (1-1). [Chemical formula 1]
Figure 02_image001
In formula (1-1), R 1 is independently a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, and R 2 is independently a hydrogen atom, a halogen atom or a monovalent organic group. In the organic group, at least two R 2 can be bonded to form a ring structure, and L 1 represents a trivalent organic group. <4> The resin composition according to any one of <1> to <3>, wherein the polymerizable compound is a compound represented by the following formula (1-2). [Chemical formula 2]
Figure 02_image003
In formula (1-2), R 1 independently represents a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, L 2 represents a single bond or a divalent linking group, and Cy represents a ring Structure, L 3 represents a single bond or a divalent linking group, R 2 independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and at least two R 2 can be bonded to form a ring structure. <5> The resin composition according to any one of <1> to <4>, wherein the resin has a polymerizable group. <6> The resin composition according to any one of <1> to <5>, which further contains a photopolymerization initiator. <7> The resin composition according to any one of <1> to <6>, which further contains a polymerizable compound different from the above-mentioned polymerizable compound. <8> The resin composition according to any one of <1> to <7>, which is used for forming an interlayer insulating film for a rewiring layer. <9> A cured product obtained by curing the resin composition according to any one of <1> to <8>. <10> A layered body comprising two or more layers formed of the cured product described in <9>, and including a metal layer between any of the layers formed of the cured product. <11> A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of <1> to <8> on a substrate to form a film. <12> The manufacturing method of the hardened|cured material as described in <11> which comprises the exposure process of selectively exposing the said film, and the development process of developing the said film using a developing solution, and forming a pattern. <13> The manufacturing method of the hardened|cured material as described in <11> or <12> which comprises the heating process of heating the said film at 50-450 degreeC. <14> A semiconductor element comprising the cured product described in <9> or the laminated body described in <10>. <15> A compound represented by the following formula (1-1). [Chemical formula 3]
Figure 02_image001
In formula (1-1), R 1 is independently a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, and R 2 is independently a hydrogen atom, a halogen atom or a monovalent organic group. In the organic group, at least two R 2 can be bonded to form a ring structure, and L 1 represents a trivalent organic group. <16> A compound represented by the following formula (1-2). [Chemical formula 4]
Figure 02_image006
In formula (1-2), R 1 independently represents a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, L 2 represents a single bond or a divalent linking group, and Cy represents a ring Structure, L 3 represents a single bond or a divalent linking group, R 2 independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and at least two R 2 can be bonded to form a ring structure. [Inventive effect]

依據本發明，提供一種所獲得之硬化物的膜收縮降低之樹脂組成物、將上述樹脂組成物硬化而成之硬化物、包含上述硬化物之積層體、上述硬化物之製造方法及包含上述硬化物或上述積層體之半導體元件。 又，依據本發明，提供一種新的化合物。 According to the present invention, there are provided a resin composition in which the film shrinkage of the obtained cured product is reduced, a cured product obtained by curing the above resin composition, a laminate comprising the above cured product, a method for producing the above cured product, and the above described cured product. or the semiconductor element of the above-mentioned laminate. Furthermore, according to the present invention, a novel compound is provided.

以下，對本發明的主要實施形態進行說明。然而，本發明並不限於所明示之實施形態。 在本說明書中，用“～”記號表示之數值範圍表示將記載於“～”的前後之數值分別作為下限值及上限值包括之範圍。 在本說明書中，“步驟”這一用語不僅表示獨立之步驟，只要能夠實現該步驟所預期之作用，則亦表示包括無法與其他步驟明確區分之步驟。 關於本說明書中之基團（原子團）的標記，未標註經取代及未經取代的標記同時包括不具有取代基的基團（原子團）和具有取代基之基團（原子團）。例如，“烷基”不僅包括不具有取代基的烷基（未經取代的烷基），而且還包括具有取代基之烷基（取代烷基）。 在本說明書中，除非另有說明，則“曝光”不僅包括利用光之曝光，而且還包括利用電子束、離子束等粒子束之曝光。又，作為用於曝光之光，可以舉出水銀燈的明線光譜、以準分子雷射為代表之遠紫外線、極紫外線（EUV光）、X射線、電子束等光化射線或放射線。 在本說明書中，“（甲基）丙烯酸酯”表示“丙烯酸酯”及“甲基丙烯酸酯”這兩者或其中任一者，“（甲基）丙烯酸”表示“丙烯酸”及“甲基丙烯酸”這兩者或其中任一者，“（甲基）丙烯醯基”表示“丙烯醯基”及“甲基丙烯醯基”這兩者或其中任一者。 在本說明書中，結構式中的Me表示甲基，Et表示乙基，Bu表示丁基，Ph表示苯基。 在本說明書中，總固體成分是指組成物的所有成分中除了溶劑以外之成分的總質量。又，在本說明書中，固體成分濃度為除了溶劑以外之其他成分相對於組成物的總質量之質量百分率。 在本說明書中，除非另有說明，則重量平均分子量（Mw）及數量平均分子量（Mn）為使用凝膠滲透層析（GPC）法進行測定之值，並且被定義為聚苯乙烯換算值。在本說明書中，關於重量平均分子量（Mw）及數量平均分子量（Mn），例如能夠藉由使用HLC-8220GPC（TOSOH CORPORATION製），並將保護管柱HZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000及TSKgel Super HZ2000（以上為TOSOH CORPORATION製）串聯連接而用作管柱來求出。除非另有說明，則該等分子量為使用THF（四氫呋喃）作為洗提液進行測定者。其中，在溶解性低的情況等THF不適合作為洗提液的情況下，亦能夠使用NMP（N-甲基-2-吡咯啶酮）。又，除非另有說明，則GPC測定中之檢測為使用UV線（紫外線）的波長254nm檢測器者。 在本說明書中，關於構成積層體之各層的位置關係，記載為“上”或“下”時，只要在所關注之複數層中成為基準之層的上側或下側存在其他層即可。亦即，亦可以在成為基準之層與上述其他層之間進一步夾有第3層或要素，並且成為基準之層與上述其他層無需接觸。又，除非另有說明，則將對於基材逐漸堆疊層之方向稱為“上”，或者，在具有樹脂組成物層之情況下，將從基材朝向樹脂組成物層之方向稱為“上”，將其相反方向稱為“下”。再者，該種上下方向的設定係為了便於說明本說明書，在實際態樣中，本說明書中之“上”方向亦可以與鉛直朝上不同。 在本說明書中，除非另有說明，則作為組成物中所包含之各成分，組成物亦可以包含與該成分對應之2種以上的化合物。又，除非另有說明，則組成物中之各成分的含量表示與該成分對應之所有化合物的合計含量。 在本說明書中，除非另有說明，則溫度為23℃，氣壓為101,325Pa（1氣壓），相對濕度為50%RH。 在本說明書中，較佳態樣的組合為更佳態樣。 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 shown by "-" symbol shows the range which includes the numerical value described before and after "-" as a lower limit value and an upper limit value, respectively. In this specification, the term "step" not only refers to an independent step, but also refers to a step that cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved. With regard to the labels of groups (atomic groups) in this specification, the labels of unsubstituted and unsubstituted groups include both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure with light but also exposure with particle beams such as electron beams, ion beams, and the like. Moreover, as light used for exposure, the bright-line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams and other actinic rays and radiation can be mentioned. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", and "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid" "Both or either, "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". 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 the present specification, the total solid content refers to the total mass of the components other than the solvent among all the components of the composition. In addition, in this specification, the solid content concentration is the mass percentage with respect to the total mass of a composition of other components except a solvent. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, and are defined as polystyrene conversion values. In this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION), and combining guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (the above are manufactured by TOSOH CORPORATION) were connected in series and used as a column to obtain the determination. Unless otherwise stated, the molecular weights are determined using THF (tetrahydrofuran) as the eluent. Among them, NMP (N-methyl-2-pyrrolidone) can also be used when THF is not suitable as an eluent such as when the solubility is low. In addition, unless otherwise specified, the detection in the GPC measurement was performed using a detector with a wavelength of 254 nm of UV rays (ultraviolet rays). In this specification, when the positional relationship of each layer constituting the layered product is described as "upper" or "lower", other layers may be present on the upper side or lower side of the reference layer among the plurality of layers concerned. That is, a third layer or element may be further interposed between the layer serving as the reference and the other layers described above, and the layer serving as the reference and the other layers described above do not need to be in contact. Also, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the base material is referred to as "up", or, in the case of a resin composition layer, the direction from the base material toward the resin composition layer is referred to as "up" , and the opposite direction is called "down". Furthermore, the setting of the up-down direction is for the convenience of explaining this specification, and in an actual aspect, the "up" direction in this specification can also be different from the vertical upward direction. In this specification, unless otherwise stated, as each component contained in a composition, a composition may contain 2 or more types of compounds corresponding to this component. In addition, unless otherwise specified, the content of each component in the composition represents the total content of all the compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 air pressure), and the relative humidity is 50% RH. In this specification, the combination of the preferred aspects is the more preferred aspect.

（樹脂組成物） 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的至少1種樹脂（以下，亦稱為“特定樹脂”。）以及具有經由連接基相互鍵結之聚合性基和醯胺鍵之聚合性化合物（以下，亦稱為“特定聚合性化合物”。），上述醯胺鍵與上述連接基在羰基側鍵結，在使用上述聚合性化合物合成了單聚物的情況下，上述單聚物顯示藉由在250℃下進行加熱而產生從主鏈游離之鹼之性質。又，上述單聚物顯示藉由在220℃下進行加熱而產生從主鏈游離之鹼之性質為較佳，顯示藉由在200℃下進行加熱而產生從主鏈游離之鹼之性質為更佳，顯示藉由在190℃下進行加熱而產生從主鏈游離之鹼之性質為進一步較佳，顯示藉由在180℃下進行加熱而產生從主鏈游離之鹼之性質為特佳。 (resin composition) The resin composition of the present invention includes at least one resin (hereinafter, also referred to as "specific resin") selected from the group consisting of a cyclized resin and a precursor thereof, and a polymerizable group having mutually bonded via a linking group A polymerizable compound with an amide bond (hereinafter, also referred to as a "specific polymerizable compound".), the amide bond and the linking group are bonded on the carbonyl side, and when a monomer is synthesized using the polymerizable compound Below, the above-mentioned monomer shows the property of generating base free from the main chain by heating at 250°C. In addition, the above-mentioned monomers show that the property of generating base free from the main chain by heating at 220°C is better, and it shows that the property of generating base free from the main chain by heating at 200°C is better. Preferably, the property showing the generation of base free from the main chain by heating at 190°C is further preferred, and the property showing the generation of base free from the main chain by heating at 180°C is particularly good.

本發明的樹脂組成物用於形成供於曝光及顯影之感光膜為較佳，用於形成供於曝光及使用了包含有機溶劑之顯影液之顯影之膜為較佳。 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於正型顯影之感光膜，亦可以用於形成供於負型顯影之感光膜。 在本發明中，負型顯影是指在曝光及顯影中，藉由顯影而去除非曝光部之顯影，正型顯影是指藉由顯影而去除曝光部之顯影。 作為上述曝光的方法、上述顯影液及上述顯影的方法，例如使用在後述硬化物之製造方法的說明中之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 for forming a photosensitive film for exposure and development, and is 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 for a semiconductor element, an interlayer insulating film for rewiring layers, a stress buffer film, and the like, and is preferably used for forming an interlayer insulating film for rewiring layers. In addition, the resin composition of the present invention can be used to form a photosensitive film for positive-tone development, and can also be used to form a photosensitive film for negative-tone development. In the present invention, negative-type development refers to development in which a non-exposed portion is removed by development during exposure and development, and positive-type development refers to development in which an exposed portion is removed by development. As the above-mentioned exposure method, the above-mentioned developer solution, and the above-mentioned development method, the exposure method described in the exposure step in the description of the manufacturing method of the cured product described later, the developer solution and the development method described in the development step are used, for example.

在本發明的樹脂組成物中，所獲得之硬化物的膜收縮降低。 可以獲得上述效果之機制雖尚不明確，但是推測為如下。 In the resin composition of the present invention, the film shrinkage of the obtained cured product is reduced. Although the mechanism by which the above-mentioned effects can be obtained is not clear, it is presumed as follows.

特定聚合性化合物具有經由連接基相互鍵結之聚合性基和醯胺鍵，並且上述醯胺鍵與上述連接基在羰基側鍵結。 特定聚合性化合物為藉由加熱使醯胺鍵斷裂而產生鹼之化合物。 亦即，本發明的樹脂組成物包含作為在與所產生之鹼不同之一側（羰基側）具有聚合性基之化合物之特定聚合性化合物。其中，在對由本發明的樹脂組成物組成之硬化前的組成物進行加熱之情況下，藉由加熱而產生鹼之後的特定聚合性化合物的分解物成為聚合之狀態。 藉此，認為由於在加熱時膜中的低分子成分減少，並且由於特定聚合性化合物具有聚合性基而藉由聚合來提高膜的交聯密度，膜的玻璃轉移溫度（Tg）上升，因此加熱時的膜收縮降低。 又，認為殘存於所獲得之硬化物中之低分子成分減少，因此耐藥品性亦提高。 進而，推測為如下：在加熱前進行曝光時使特定聚合性化合物聚合之情況下，能夠抑制由顯影引起之特定聚合性化合物的溶出，因此在加熱時所產生之鹼的量增加，硬化物的斷裂伸長率提高。再者，認為從特定聚合性化合物產生之鹼本身沒有聚合，因此容易在膜內擴散。因此，認為例如在使用特定樹脂的前驅物作為特定樹脂之情況下，基於鹼之特定樹脂的前驅物的環化促進效果大。 另外，認為特定聚合性化合物的鹼產生前的結構接近中性，包含此之樹脂組成物的樹脂組成物本身的保存穩定性亦優異。 The specific polymerizable compound has a polymerizable group and an amide bond mutually bonded via a linking group, and the aforementioned amide bond and the aforementioned linking group are bonded on the carbonyl side. The specific polymerizable compound is a compound that generates a base by cleaving an amide bond by heating. That is, the resin composition of the present invention contains a specific polymerizable compound as a compound having a polymerizable group on the side (carbonyl side) different from the generated base. Here, when the composition before hardening consisting of the resin composition of the present invention is heated, the decomposed product of the specific polymerizable compound after generating an alkali by heating is in a state of polymerization. From this, it is considered that the glass transition temperature (Tg) of the film rises because the low molecular weight component in the film decreases during heating, and the specific polymerizable compound has a polymerizable group to increase the crosslinking density of the film by polymerization. film shrinkage is reduced. Moreover, it is thought that the low molecular components remaining in the obtained hardened|cured material decreased, and chemical resistance also improved. Furthermore, it is presumed that when the specific polymerizable compound is polymerized during exposure before heating, the elution of the specific polymerizable compound due to development can be suppressed, so that the amount of alkali generated during heating increases and the cured product becomes Elongation at break increased. In addition, it is considered that the base generated from the specific polymerizable compound itself is not polymerized, and therefore easily diffuses in the membrane. Therefore, for example, when a precursor of a specific resin is used as the specific resin, the cyclization promoting effect of the precursor of the specific resin based on an alkali is considered to be large. In addition, it is considered that the structure before generation of the alkali of the specific polymerizable compound is close to neutrality, and the resin composition itself including the resin composition is considered to have excellent storage stability.

其中，在專利文獻1中，對特定聚合性化合物沒有記載。Among them, Patent Document 1 does not describe a specific polymerizable compound.

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的至少1種樹脂（特定樹脂）。 環化樹脂為在主鏈結構中包含醯亞胺環結構或㗁唑環結構之樹脂為較佳。 在本發明中，主鏈表示在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、聚苯并㗁唑、聚醯胺醯亞胺等。 環化樹脂的前驅物是指因外部刺激產生化學結構的變化而成為環化樹脂之樹脂，藉由熱產生化學結構的變化而成為環化樹脂之樹脂為較佳，藉由熱產生閉環反應而形成環結構以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、聚苯并㗁唑前驅物、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、聚苯并㗁唑、聚苯并㗁唑前驅物、聚醯胺醯亞胺及聚醯胺醯亞胺前驅物之群組中的至少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，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之情況下，本發明的樹脂組成物包含後述自由基聚合起始劑為較佳，包含後述自由基聚合起始劑且包含後述自由基交聯劑為更佳。進而，依據需要，能夠包含後述敏化劑。由該種本發明的樹脂組成物例如形成負型感光膜。 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之情況下，本發明的樹脂組成物包含後述光酸產生劑為較佳。由該種本發明的樹脂組成物例如形成作為化學增幅型之正型感光膜或負型感光膜。 又，在特定樹脂具有聚合性基之情況下，特定樹脂具有能夠與特定聚合性化合物聚合的聚合性基為較佳。推測為如下：依據該種態樣，即使在特定樹脂與特定聚合性化合物之間亦進行聚合，並在藉由聚合而形成之聚合物中特定聚合性化合物隔開間隔而分布。其結果，推測為如下：膜中之鹼的產生位置不易產生偏移，例如容易促進環化樹脂的前驅物的閉環或容易促進藉由鹼而聚合之聚合性化合物的聚合。 例如，特定樹脂具有自由基聚合性基，並且特定聚合性化合物具有自由基聚合性基之態樣亦為本發明的較佳態樣之一。 ＜Specific resin＞ The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of a cyclized resin and a precursor thereof. The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain represents the relatively longest bonding chain in the resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, polyimide, and the like. The precursor of the cyclized resin refers to the resin that changes its chemical structure due to external stimuli and becomes the cyclized resin. More preferably, a resin that forms a ring structure to become a cyclized resin. As a precursor of a cyclized resin, a polyimide precursor, a polybenzoxazole precursor, a polyimide imide precursor, etc. are mentioned. That is, the resin composition of the present invention comprises a compound selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyimide imide and polyimide imide. At least one resin (specific resin) in the group of imine precursors is preferably used as the specific resin. The resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin. Moreover, it is preferable that a specific resin has a polymerizable group, and it is more preferable that it contains a radical polymerizable group. When the specific resin has a radically polymerizable group, it is preferable that the resin composition of the present invention contains a radical polymerization initiator described later, and it is more preferable that it includes a radical polymerization initiator described later and a radical crosslinking agent described later. . Furthermore, the sensitizer mentioned later can be contained as needed. For example, a negative photosensitive film is formed from the resin composition of the present invention. In addition, the specific resin may have a polarity conversion group such as an acid-decomposable group. When a specific resin has an acid-decomposable group, it is preferable that the resin composition of this invention contains the photoacid generator mentioned later. From the resin composition of the present invention, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film is formed. Moreover, when a specific resin has a polymerizable group, it is preferable that a specific resin has a polymerizable group which can polymerize with a specific polymerizable compound. It is presumed that, according to this aspect, the polymerization proceeds between the specific resin and the specific polymerizable compound, and the specific polymerizable compound is distributed at intervals in the polymer formed by the polymerization. As a result, it is presumed that the generation position of the alkali in the film is not easily shifted, for example, the ring closure of the precursor of the cyclized resin or the polymerization of the polymerizable compound polymerized by the alkali is easily accelerated. For example, the specific resin has a radically polymerizable group, and the aspect in which the specific polymerizable compound has a radically polymerizable group is also one of the preferred aspects of the present invention.

〔聚醯亞胺前驅物〕 本發明中所使用之聚醯亞胺前驅物的種類等並無特別規定，但是包含下述式（2）所表示之重複單元為較佳。 [化學式5]

Figure 02_image008
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價的有機基，R 115表示4價的有機基，R 113及R 114分別獨立地表示氫原子或1價的有機基。 [Polyimide Precursor] The type and the like of the polyimide precursor used in the present invention are not particularly limited, but it is preferable to include a repeating unit represented by the following formula (2). [Chemical formula 5]
Figure 02_image008
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 a monovalent organic group.

式（2）中之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）中之R 111表示2價的有機基。作為2價的有機基，可以例示包含直鏈或支鏈的脂肪族基、環狀脂肪族基及芳香族基之基團，包括碳數2～20的直鏈或支鏈的脂肪族基、碳數3～20的環狀脂肪族基、碳數3～20的芳香族基或該等組合之基團為較佳，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可以經鏈中的烴基包含雜原子之基團取代，並且上述環狀的脂肪族基及芳香族基可以經環員的烴基包含雜原子之基團取代。作為本發明的較佳的實施形態，可以例示-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為包括單鍵或可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO 2-或-NHCO-或上述中的2個以上的組合之基團。該等較佳範圍如上所述。 A 1 and A 2 in the formula (2) each independently represent an oxygen atom or -NH-, preferably an oxygen atom. R 111 in formula (2) represents a divalent organic group. As the divalent organic group, there can be exemplified groups including linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including 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 combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. The straight-chain or branched aliphatic group may be substituted with a hydrocarbon group in the chain containing a heteroatom, and the cyclic aliphatic and aromatic groups may be substituted with a ring-membered hydrocarbon group containing a heteroatom. As a preferable embodiment of this invention, the group represented by -Ar- and -Ar-L-Ar- can be illustrated, and the group represented by -Ar-L-Ar- is especially preferable. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms including a single bond or substituted by a fluorine atom, -O-, -CO-, -S-, -SO 2 - or -NHCO- or a combination of two or more of the above. These preferred ranges are as described above.

R 111衍生自二胺為較佳。作為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的脂肪族、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，包含包括碳數2～20的直鏈或支鏈的脂肪族基、碳數3～20的環狀脂肪族基、碳數3～20的芳香族基或該等組合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可以經鏈中的烴基包含雜原子之基團取代，並且上述環狀的脂肪族基及芳香族基可以經環員的烴基包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。 Preferably R 111 is derived from a diamine. As a diamine used for manufacture of a polyimide precursor, a linear or branched aliphatic, cyclic aliphatic, or aromatic diamine etc. are mentioned. Only one type of diamine may be used, or two or more types may be used. Specifically, the group 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. The diamine is preferable, and the diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The straight-chain or branched aliphatic group may be substituted with a hydrocarbon group in the chain containing a heteroatom, and the cyclic aliphatic and aromatic groups may be substituted with a ring-membered hydrocarbon group containing a heteroatom. As an example of the group containing an aromatic group, the following are mentioned.

[化學式6]

Figure 02_image010
式中，A表示單鍵或2價的連接基，選自單鍵或可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-C（=O）-、-S-、-SO 2-、-NHCO-或該等組合中之基團為較佳，選自單鍵、可以經氟原子取代的碳數1～3的伸烷基、-O-、-C（=O）-、-S-或-SO 2-中之基團為更佳，-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 6]
Figure 02_image010
In the formula, A represents a single bond or a divalent linking group, and is selected from a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -C(=O)-, and -S- which may be substituted by a fluorine atom. , -SO 2 -, -NHCO- or groups in these combinations are preferably selected from single bonds, alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C (= The group in O)-, -S- or -SO 2 - is more preferred, -CH 2 -, -O-, -S-, -SO 2 -, -C(CF 3 ) 2 - or -C ( CH 3 ) 2 - is further preferred. In the formula, * represents a bonding site with other structures.

作為二胺，具體而言，可以舉出選自1,2-二胺基乙烷、1,2-二胺基丙烷、1,3-二胺基丙烷、1,4-二胺基丁烷或1,6-二胺基己烷；1,2-二胺基環戊烷或1,3-二胺基環戊烷、1,2-二胺基環己烷、1,3-二胺基環己烷或1,4-二胺基環己烷、1,2-雙（胺基甲基）環己烷、1,3-雙（胺基甲基）環己烷或1,4-雙（胺基甲基）環己烷、雙-（4-胺基環己基）甲烷、雙-（3-胺基環己基）甲烷、4,4’-二胺基-3,3’-二甲基環己基甲烷及異佛爾酮二胺；間苯二胺或對苯二胺、二胺基甲苯、4,4’-二胺基聯苯或3,3’-二胺基聯苯、4,4’-二胺基二苯醚、3,3’-二胺基二苯醚、4,4’-二胺基二苯基甲烷或3,3’-二胺基二苯基甲烷、4,4’-二胺基二苯基碸或3,3-二胺基二苯基碸、4,4’-二胺基二苯醚或3,3’-二胺基二苯醚、4,4’-二胺基二苯甲酮或3,3’-二胺基二苯甲酮、3,3’-二甲基-4,4’-二胺基聯苯、2,2’-二甲基-4,4’-二胺基聯苯、3,3’-二甲氧基-4,4’-二胺基聯苯、2,2-雙（4-胺基苯基）丙烷、2,2-雙（4-胺基苯基）六氟丙烷、2,2-雙（3-羥基-4-胺基苯基）丙烷、2,2-雙（3-羥基-4-胺基苯基）六氟丙烷、2,2-雙（3-胺基-4-羥基苯基）丙烷、2,2-雙（3-胺基-4-羥基苯基）六氟丙烷、雙（3-胺基-4-羥基苯基）碸、雙（4-胺基-3-羥基苯基）碸、4,4’-二胺基對聯三苯、4,4’-雙（4-胺基苯氧基）聯苯、雙[4-（4-胺基苯氧基）苯基]碸、雙[4-（3-胺基苯氧基）苯基]碸、雙[4-（2-胺基苯氧基）苯基]碸、1,4-雙（4-胺基苯氧基）苯、9,10-雙（4-胺基苯基）蒽、3,3’-二甲基-4,4’-二胺基二苯基碸、1,3-雙（4-胺基苯氧基）苯、1,3-雙（3-胺基苯氧基）苯、1,3-雙（4-胺基苯基）苯、3,3’-二乙基-4,4’-二胺基二苯基甲烷、3,3’-二甲基-4,4’-二胺基二苯基甲烷、4,4’-二胺基八氟聯苯、2,2-雙[4-（4-胺基苯氧基）苯基]丙烷、2,2-雙[4-（4-胺基苯氧基）苯基]六氟丙烷、9,9-雙（4-胺基苯基）-10-氫蒽、3,3’,4,4’-四胺基聯苯、3,3’,4,4’-四胺基二苯醚、1,4-二胺基蒽醌、1,5-二胺基蒽醌、3,3-二羥基-4,4’-二胺基聯苯、9,9’-雙（4-胺基苯基）茀、4,4’-二甲基-3,3’-二胺基二苯基碸、3,3’,5,5’-四甲基-4,4’-二胺基二苯基甲烷、2,4-二胺基枯烯及2,5-二胺基枯烯、2,5-二甲基-對苯二胺、乙醯胍胺、2,3,5,6-四甲基-對苯二胺、2,4,6-三甲基-間苯二胺、雙（3-胺基丙基）四甲基二矽氧烷、雙（對胺基苯基）八甲基五矽氧烷、2,7-二胺基茀、2,5-二胺基吡啶、1,2-雙（4-胺基苯基）乙烷、二胺基苯甲醯苯胺、二胺苯甲酸的酯、1,5-二胺基萘、二胺基三氟甲苯、1,3-雙（4-胺基苯基）六氟丙烷、1,4-雙（4-胺基苯基）八氟丁烷、1,5-雙（4-胺基苯基）十氟戊烷、1,7-雙（4-胺基苯基）十四氟庚烷、2,2-雙[4-（3-胺基苯氧基）苯基]六氟丙烷、2,2-雙[4-（2-胺基苯氧基）苯基]六氟丙烷、2,2-雙[4-（4-胺基苯氧基）-3,5-二甲基苯基]六氟丙烷、2,2-雙[4-（4-胺基苯氧基）-3,5-雙（三氟甲基）苯基]六氟丙烷、對雙（4-胺基-2-三氟甲基苯氧基）苯、4,4’-雙（4-胺基-2-三氟甲基苯氧基）聯苯、4,4’-雙（4-胺基-3-三氟甲基苯氧基）聯苯、4,4’-雙（4-胺基-2-三氟甲基苯氧基）二苯基碸、4,4’-雙（3-胺基-5-三氟甲基苯氧基）二苯基碸、2,2-雙[4-（4-胺基-3-三氟甲基苯氧基）苯基]六氟丙烷、3,3’,5,5’-四甲基-4,4’-二胺基聯苯、4,4’-二胺基-2,2’-雙（三氟甲基）聯苯、2,2’,5,5’,6,6’-六氟聯甲苯胺及4,4’-二胺基四聯苯中的至少1種二胺。Specific examples of the diamine include those selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, and 1,4-diaminobutane or 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diamine cyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4- Bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-di Methylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4'-Diaminodiphenyl ether or 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether or 3,3'-diaminodiphenyl ether, 4 ,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane , 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-amine) phenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)hexafluoropropane 3-amino-4-hydroxyphenyl) bismuth, bis(4-amino-3-hydroxyphenyl) bismuth, 4,4'-diamino-terphenyl, 4,4'-bis(4-amine bis[4-(4-aminophenoxy)phenyl]bis[4-(3-aminophenoxy)phenyl]bis[4-(3-aminophenoxy)phenyl]bis[4-(2 -Aminophenoxy)phenyl] bismuth, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene -Bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diamine diphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-( 4-Aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diamine Amino biphenyl, 9,9'-bis(4-amino) Phenyl) phenyl, 4,4'-dimethyl-3,3'-diaminodiphenyl, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenyl Phenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6- Tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octa Methylpentasiloxane, 2,7-diaminopyridine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzylaniline, bis Ester of aminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminobenzene) base) octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[ 4-(3-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4- (4-Aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoropropane) Methyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) base) biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) base) diphenyl bismuth, 4,4'-bis(3-amino-5-trifluoromethylphenoxy) diphenyl bismuth, 2,2-bis[4-(4-amino-3- Trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2 At least 1 of ,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorobenzidine and 4,4'-diaminotetraphenyl a diamine.

又，國際公開第2017/038598號的0030～0031段中所記載的二胺（DA-1）～（DA-18）亦較佳。Moreover, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. WO 2017/038598 are also preferred.

又，亦可以較佳地使用在主鏈上具有國際公開第2017/038598號的0032～0034段中所記載的2個以上的伸烷基二醇單元之二胺。Moreover, the diamine which has two or more alkylene glycol units described in the paragraphs 0032 to 0034 of International Publication No. 2017/038598 in the main chain can also be preferably used.

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為包括可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO 2-或-NHCO-或上述中的2個以上的組合之基團。Ar為伸苯基為較佳，L為可以經氟原子取代的碳數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 the flexibility of the obtained organic film, R 111 is preferably represented by -Ar-L-Ar-. Wherein, Ar is each independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO 2 - or -NHCO- which may be substituted by a fluorine atom. or a combination of two or more of the above. Preferably, Ar is a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms, -O-, -CO-, -S- or -SO 2 - which may be substituted by a fluorine atom. 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為下述式（51）或式（61）所表示之2價的有機基為較佳。尤其，從i射線透射率、易獲得性的觀點考慮，式（61）所表示之2價的有機基為更佳。 式（51） [化學式7]

Figure 02_image012
式（51）中，R 50～R 57分別獨立地為氫原子、氟原子或1價的有機基，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價的有機基，可以舉出碳數1～10（較佳為碳數1～6）的未經取代的烷基、碳數1～10（較佳為碳數1～6）的氟化烷基等。 [化學式8]
Figure 02_image014
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。 作為提供式（51）或式（61）的結構之二胺，可以舉出2,2’-二甲基聯苯胺、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。 In addition, from the viewpoint of i-ray transmittance, it is preferable that R 111 is a divalent organic group represented by the following formula (51) or formula (61). In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. Formula (51) [Chemical Formula 7]
Figure 02_image012
In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoromethyl group, * Each independently represents the bonding site to the nitrogen atom in the 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 carbon atoms of 1 to 6), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably carbon atoms of 1 to 10). 1-6) fluorinated alkyl groups, etc. [Chemical formula 8]
Figure 02_image014
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 to the nitrogen atom in the formula (2). As the diamine which provides the structure of formula (51) or formula (61), 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diamine can be mentioned Aminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These can be used alone or in combination of two or more.

式（2）中之R 115表示4價的有機基。作為4價的有機基，包含芳香環之4價的有機基為較佳，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9]

Figure 02_image016
式（5）中，R 112為單鍵或2價的連接基，選自單鍵或可以經氟原子取代的碳數1～10的脂肪族烴基、-O-、-CO-、-S-、-SO 2-及-NHCO-以及該等組合中之基團為較佳，選自單鍵、可以經氟原子取代的碳數1～3的伸烷基、-O-、-CO-、-S-及-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-之群組中的2價的基團為進一步較佳。 R 115 in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group including an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable. In formula (5) or formula (6), * each independently represents a bonding site with another structure. [Chemical formula 9]
Figure 02_image016
In formula (5), R 112 is a single bond or a divalent linking group, selected from a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, which may be substituted by a fluorine atom , -SO 2 - and -NHCO- and the groups in these combinations are preferably selected from single bonds, alkylene groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -CO-, The groups in -S- and -SO 2 - are more preferably selected from the group consisting of -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -O-, -CO-, The divalent group in the group of -S- and -SO 2 - is more preferable.

關於R 115，具體而言，可以舉出從四羧酸二酐去除酐基之後所殘存之四羧酸殘基等。作為與R 115對應之結構，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。 四羧酸二酐由下述式（O）表示為較佳。 [化學式10]

Figure 02_image018
式（O）中，R 115表示4價的有機基。R 115的較佳範圍與式（2）中之R 115的含義相同，較佳範圍亦相同。 Specific examples of R 115 include the tetracarboxylic acid residue remaining after removing the anhydride group from the 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 10]
Figure 02_image018
In formula (O), R 115 represents a tetravalent organic group. The preferred range of R 115 is the same as that of R 115 in formula (2), and the preferred range is also the same.

作為四羧酸二酐的具體例，可以舉出均苯四甲酸二酐（PMDA）、3,3’,4,4’-聯苯四羧酸二酐、3,3’,4,4’-二苯硫醚四羧酸二酐、3,3’,4,4’-二苯基碸四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、3,3’,4,4’-二苯基甲烷四羧酸二酐、2,2’,3,3’-二苯基甲烷四羧酸二酐、2,3,3’,4’-聯苯四羧酸二酐、2,3,3’,4’-二苯甲酮四羧酸二酐、4,4’-氧二鄰苯二甲酸二酐、2,3,6,7-萘四羧酸二酐、1,4,5,7-萘四羧酸二酐、2,2-雙（3,4-二羧基苯基）丙烷二酐、2,2-雙（2,3-二羧基苯基）丙烷二酐、2,2-雙（3,4-二羧基苯基）六氟丙烷二酐、1,3-二苯基六氟丙烷-3,3,4,4-四羧酸二酐、1,4,5,6-萘四羧酸二酐、2,2’,3,3’-二苯基四羧酸二酐、3,4,9,10-苝四羧酸二酐、1,2,4,5-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、1,8,9,10-菲四羧酸二酐、1,1-雙（2,3-二羧基苯基）乙烷二酐、1,1-雙（3,4-二羧基苯基）乙烷二酐、1,2,3,4-苯四羧酸二酐及該等碳數1～6的烷基及碳數1～6的烷氧基衍生物。Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4' -Diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride , 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4' - Biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7 -Naphthalenetetracarboxylic dianhydride, 1,4,5,7-Naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 3-Dicarboxyphenyl) propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4 -Tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylene Tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride , 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride and these alkyl groups having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

又，亦可以舉出國際公開第2017/038598號的0038段中所記載的四羧酸二酐（DAA-1）～（DAA-5）作為較佳例。Moreover, the tetracarboxylic dianhydride (DAA-1) - (DAA-5) described in the 0038 paragraph of International Publication No. WO 2017/038598 can also be mentioned as a preferable example.

式（2）中，R 111和R 115中的至少一者亦能夠具有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 also have an OH group. More specifically, as R 111 , a residue of a bisaminophenol derivative can be mentioned.

式（2）中之R 113及R 114分別獨立地表示氫原子或1價的有機基。作為1價的有機基，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中的至少一者包含聚合性基為較佳，兩者包含聚合性基為更佳。R 113及R 114中的至少一者包含2個以上的聚合性基亦較佳。作為聚合性基為能夠藉由熱、自由基等的作用而進行交聯反應的基團，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、羥甲基、醯氧基甲基、環氧基、氧環丁烷基、苯并㗁唑基、嵌段異氰酸酯基、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 polyalkoxy group. Moreover, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both of them contain a polymerizable group. It is also preferable that at least one of R 113 and R 114 contains two or more polymerizable groups. As the polymerizable group, a group capable of performing a crosslinking reaction by the action of heat, radicals, or the like, a radically polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an acyloxymethyl group, an epoxy group, an oxetanyl group, and a benzoxyl 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 preferable. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, 2-methallyl group, and a group having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl, etc.), (meth)acrylamido, (meth)acryloyloxy, groups represented by the following formula (III), etc., the group represented by the following formula (III) is better.

[化學式11]

Figure 02_image020
[Chemical formula 11]
Figure 02_image020

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。 式（III）中，*表示與其他結構的鍵結部位。 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。 較佳的R 201的例子可以舉出伸乙基、伸丙基、三亞甲基、四亞甲基、五亞甲基、六亞甲基、八亞甲基、十二亞甲基等伸烷基、1,2-丁二基、1,3-丁二基、-CH 2CH（OH）CH 2-、聚伸烷氧基，伸乙基、伸丙基等伸烷基、-CH 2CH（OH）CH 2-、環己基、聚伸烷氧基為更佳，伸乙基、伸丙基等伸烷基或聚伸烷氧基為進一步較佳。 在本發明中，聚伸烷氧基是指伸烷氧基直接鍵結2個以上之基團。聚伸烷氧基中所包含之複數個伸烷氧基中之伸烷基分別可以相同，亦可以不同。 在聚伸烷氧基包含伸烷基不同之複數種伸烷氧基之情況下，聚伸烷氧基中之伸烷氧基的排列可以為無規排列，亦可以為具有嵌段之排列，還可以為具有交替等圖案之排列。 上述伸烷基的碳數（在伸烷基具有取代基之情況下，包含取代基的碳數）為2以上為較佳，2～10為更佳，2～6為更佳，2～5為進一步較佳，2～4為更進一步較佳，2或3為特佳，2為最佳。 又，上述伸烷基可以具有取代基。作為較佳的取代基，可以舉出烷基、芳基、鹵素原子等。 又，聚伸烷氧基中所包含之伸烷氧基的數量（聚伸烷氧基的重複數）為2～20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、聚伸丙氧基、聚三亞甲氧基、聚四亞甲氧基或複數個乙烯氧基與複數個伸丙氧基鍵結而獲得之基團為較佳，聚乙烯氧基或聚伸丙氧基為更佳，聚乙烯氧基為進一步較佳。在上述複數個乙烯氧基與複數個伸丙氧基鍵結而獲得之基團中，乙烯氧基與伸丙氧基可以無規排列，亦可以形成嵌段而排列，還可以排列成交替等圖案狀。該等基團中之乙烯氧基等重複數個較佳態樣如上所述。 In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred. 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 polyalkeneoxy group. Preferred examples of R 201 include ethylidene, propylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, dodecane and the like. base, 1,2-butanediyl, 1,3-butanediyl, -CH 2 CH(OH) CH 2 -, polyalkyleneoxy, ethylidene, propylidene and other alkylene groups, -CH 2 CH(OH)CH 2 -, cyclohexyl, and polyalkeneoxy groups are more preferred, and alkylene groups such as ethylidene and propylidene groups or polyalkeneoxy groups are further preferred. In the present invention, the polyalkeneoxy group refers to a group in which two or more alkeneoxy groups are directly bonded. The alkylene groups in the plural alkyleneoxy groups contained in the polyalkeneoxy group may be the same or different, respectively. In the case where the polyalkeneoxy group contains a plurality of alkeneoxy groups with different alkylene groups, the arrangement of the alkeneoxy groups in the polyalkeneoxy group may be random, or may be a block arrangement, Arrangements with alternating patterns are also possible. The number of carbon atoms in the alkylene group (in the case where the alkylene group has a substituent, the number of carbon atoms including the substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, and 2 to 5 2 to 4 are still more preferable, 2 or 3 are particularly preferable, and 2 is the most preferable. Moreover, the said alkylene group may have a substituent. As a preferable substituent, an alkyl group, an aryl group, a halogen atom, etc. are mentioned. Moreover, it is preferable that the number of alkeneoxy groups contained in the polyalkeneoxy group (the number of repetitions of the polyalkeneoxy group) is 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoints of solvent solubility and solvent resistance, the polyalkeneoxy group includes polyvinyloxy group, polypropeneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, a plurality of vinyloxy groups and a plurality of A group obtained by bonding two propeneoxy groups is preferred, polyvinyloxy or polypropeneoxy is more preferred, and polyvinyloxy is further preferred. In the above-mentioned groups obtained by bonding a plurality of vinyloxy groups and a plurality of propeneoxy groups, the vinyloxy groups and the propeneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged alternately, etc. patterned. Several preferred aspects such as vinyloxy in these groups are repeated as described above.

式（2）中，在R 113為氫原子之情況或在R 114為氫原子之情況下，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鹼。作為該種具有乙烯性不飽和鍵之三級胺化合物的例子，可以舉出甲基丙烯酸N,N-二甲基胺基丙酯。 In formula (2), when R 113 is a hydrogen atom or when R 114 is a hydrogen atom, the polyimide precursor can form a conjugate base with a tertiary amine compound having an ethylenically unsaturated bond. As an example of the tertiary amine compound which has such an ethylenically unsaturated bond, N,N- dimethylamino propyl methacrylate is mentioned.

式（2）中，R 113及R 114中的至少一者可以為酸分解性基等極性轉換基。作為酸分解性基，只要為在酸的作用下分解而產生酚性羥基、羧基等鹼可溶性基者，則並無特別限定，但是縮醛基、縮酮基、甲矽烷基、甲矽烷基醚基、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。 作為酸分解性基的具體例，可以舉出第三丁氧基羰基、異丙氧基羰基、四氫吡喃基、四氫呋喃基、乙氧基乙基、甲氧基乙基、乙氧基甲基、三甲基甲矽烷基、第三丁氧基羰基甲基、三甲基甲矽烷基醚基等。從曝光靈敏度的觀點考慮，乙氧基乙基或四氫呋喃基為較佳。 In formula (2), at least one of R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group and a carboxyl group, but an acetal group, a ketal group, a silyl group, and a silyl ether A group, a tertiary alkyl ester group, etc. are preferable, and an acetal group or a ketal group is more preferable from the viewpoint of exposure sensitivity. Specific examples of acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, and ethoxymethyl. group, trimethylsilyl group, tertiary butoxycarbonyl methyl group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

又，聚醯亞胺前驅物在結構中具有氟原子亦較佳。聚醯亞胺前驅物中的氟原子含量為10質量%以上為較佳，並且20質量%以下為較佳。Moreover, it is also preferable that the polyimide precursor has a fluorine atom in the structure. The content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

又，為了提高與基板的密接性，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。Moreover, in order to improve the adhesiveness with a board|substrate, a polyimide precursor may be copolymerized with the aliphatic group which has a siloxane structure. Specifically, as the diamine, an aspect in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used can be mentioned.

式（2）所表示之重複單元為式（2-A）所表示之重複單元為較佳。亦即，本發明中所使用之聚醯亞胺前驅物中的至少1種為具有式（2-A）所表示之重複單元之前驅物為較佳。藉由使聚醯亞胺前驅物包含式（2-A）所表示之重複單元，能夠進一步加大曝光寬容度的寬度。 式（2-A） [化學式12]

Figure 02_image022
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價的有機基，R 113及R 114分別獨立地表示氫原子或1價的有機基，R 113及R 114中的至少一者為包含聚合性基之基團，兩者為包含聚合性基之基團為較佳。 Preferably, the repeating unit represented by the formula (2) is the repeating unit represented by the formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By making the polyimide precursor contain the repeating unit represented by the formula (2-A), the width of the exposure latitude can be further increased. Formula (2-A) [Chemical Formula 12]
Figure 02_image022
In formula (2-A), A 1 and A 2 represent an oxygen atom, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each 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 are preferably a group containing a polymerizable group.

A 1、A 2、R 111、R 113及R 114分別獨立地與式（2）中之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）中之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 meanings 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，亦可以包含式（2）所表示之重複單元的結構異構物。又，聚醯亞胺前驅物除了上述式（2）的重複單元以外，還可以包含其他種類的重複單元，這是不言而喻的。The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. In addition, structural isomers of the repeating unit represented by the formula (2) may also be included. In addition, it goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of the above formula (2).

作為本發明中之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。上述合計含量為70莫耳%以上為更佳，90莫耳%以上為進一步較佳，超過90莫耳%為特佳。上述合計含量的上限並無特別限定，除了末端以外的聚醯亞胺前驅物中之所有重複單元亦可以為式（2）所表示之重複單元。As an embodiment of the polyimide precursor in the present invention, the content of the repeating unit represented by the formula (2) is 50 mol % or more of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor other than the terminal 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無特別規定，例如為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，分子量的分散度為利用重量平均分子量/數量平均分子量計算出之值。 又，在樹脂組成物包含複數種聚醯亞胺前驅物作為特定樹脂之情況下，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內為較佳。又，將上述複數種聚醯亞胺前驅物作為1個樹脂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, and further preferably 15,000 to 40,000. Moreover, as for the number average molecular weight (Mn), 2,000-40,000 are preferable, 3,000-30,000 are more preferable, 4,000-20,000 are still more preferable. The dispersity of the molecular weight of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersity of the molecular weight 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 even more preferably 6.0 or less. In this specification, the dispersion degree of molecular weight is a value calculated by weight average molecular weight/number average molecular weight. Furthermore, when the resin composition includes a plurality of polyimide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight and dispersity of at least one polyimide precursor are within the above ranges. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the above-mentioned plural types of polyimide precursors as one resin are respectively within the above-mentioned ranges.

〔聚醯亞胺〕 本發明中所使用之聚醯亞胺可以為鹼可溶性聚醯亞胺，亦可以為可溶於以有機溶劑為主成分之顯影液中之聚醯亞胺。 在本說明書中，鹼可溶性聚醯亞胺是指相對於100g的2.38質量%四甲基銨水溶液在23℃下溶解0.1g以上之聚醯亞胺，從圖案形成性的觀點考慮，溶解0.5g以上之聚醯亞胺為較佳，溶解1.0g以上之聚醯亞胺為進一步較佳。上述溶解量的上限並無特別限定，但是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，聚醯亞胺為在主鏈上具有複數個醯亞胺結構之聚醯亞胺為較佳。 在本說明書中，“主鏈”是指在構成樹脂之高分子化合物的分子中相對最長的鍵結鏈，“側鏈”是指除此以外的鍵結鏈。 [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer whose main component is an organic solvent. In this specification, the alkali-soluble polyimide refers to 0.1 g or more of polyimide dissolved in 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23°C, and 0.5 g is dissolved from the viewpoint of pattern formation. The above polyimide is preferred, and it is further preferred to dissolve 1.0 g or more of the polyimide. The upper limit of the dissolved amount is not particularly limited, but is preferably 100 g or less. Moreover, from the viewpoint of the film strength and insulating properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain. In this specification, "main chain" means the relatively longest bond chain in the molecule of the polymer compound constituting the resin, and "side chain" means other bond chains.

-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較佳。 氟原子例如包含於後述式（4）所表示之重複單元中之R 132或後述式（4）所表示之重複單元中之R 131中為較佳，作為氟化烷基而包含於後述式（4）所表示之重複單元中之R 132或後述式（4）所表示之重複單元中之R 131中為更佳。 氟原子的量相對於聚醯亞胺的總質量為5質量%以上為較佳，並且20質量%以下為較佳。 -Fluorine Atom- It is also preferable that the polyimide has a fluorine atom from the viewpoint of the film strength of the obtained organic film. The fluorine atom is preferably included in, for example, R 132 in the repeating unit represented by the formula (4) described below or R 131 in the repeating unit represented by the formula (4) described below, and is included as a fluorinated alkyl group in the formula ( 4) R 132 in the repeating unit represented or R 131 in the repeating unit represented by the following formula (4) is more preferable. The amount of fluorine atoms is preferably 5% by mass or more and preferably 20% by mass or less with respect to the total mass of the polyimide.

-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較佳。 矽原子例如包含於後述式（4）所表示之重複單元中之R 131中為較佳，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之R 131中為更佳。 又，上述矽原子或上述有機改質（聚）矽氧烷結構亦可以包含於聚醯亞胺的側鏈上，但是包含於聚醯亞胺的主鏈上為較佳。 矽原子的量相對於聚醯亞胺的總質量為1質量%以上為較佳，20質量%以下為更佳。 -Silicon atom- From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide has a silicon atom. The silicon atom is preferably included in, for example, R 131 in the repeating unit represented by the following formula (4), and is included in the repeating unit represented by the following formula (4) as the organic modified (poly)siloxane structure described below. R 131 is better. In addition, the silicon atom or the organic modified (poly)siloxane structure may be included in the side chain of the polyimide, but it is preferably included in the main chain of the polyimide. The amount of silicon atoms is preferably 1% by mass or more, and more preferably 20% by mass or less, based on the total mass of the polyimide.

-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，亦可以在側鏈上具有乙烯性不飽和鍵，但是在側鏈上具有乙烯性不飽和鍵為較佳。 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之R 132或後述式（4）所表示之重複單元中之R 131中為較佳，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之R 132或後述式（4）所表示之重複單元中之R 131中為更佳。 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之R 131中為較佳，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之R 131中為更佳。 作為具有乙烯性不飽和鍵之基團，可以舉出乙烯基、烯丙基、乙烯基苯基等與芳香環直接鍵結且可以經取代之具有乙烯基之基團、（甲基）丙烯醯基、（甲基）丙烯醯氧基、下述式（IV）所表示之基團等。 -Ethylene 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 in the side chain, but it is preferable to have an ethylenically unsaturated bond in the side chain. It is preferable that the above-mentioned ethylenically unsaturated bond has radical polymerizability. The ethylenically unsaturated bond is preferably contained in R 132 in the repeating unit represented by the formula (4) described below or R 131 in the repeating unit represented by the formula (4) below, as a group having an ethylenically unsaturated bond. It is more preferable to be included in R 132 in the repeating unit represented by the formula (4) described below or R 131 in the repeating unit represented by the formula (4) described later. Among these, it is preferable that an ethylenically unsaturated bond is included in R 131 in the repeating unit represented by the following formula (4), and it is included in the following formula (4) as a group having an ethylenically unsaturated bond. R 131 in the represented repeating unit is more preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, and the like which are directly bonded to an aromatic ring and have a vinyl group which may be substituted, and (meth)acryloyl group. group, a (meth)acryloyloxy group, a group represented by the following formula (IV), and the like.

[化學式13]

Figure 02_image024
[Chemical formula 13]
Figure 02_image024

式（IV）中，R 20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 20 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred.

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）或將該等中的2個以上組合而成之基團。 又，作為上述碳數2～12的伸烷基，可以為直鏈狀、支鏈鎖狀、環狀或由該等組合表示之伸烷基中的任一個。 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) alkaneoxy group with 2-30 carbon atoms (the carbon number of the alkylene group is 2-12 is better, 2-6 is better, 2 or 3 is particularly preferred; the number of repetitions is 1-12 is Preferably, 1 to 6 are more preferred, 1 to 3 are particularly preferred) or a group formed by combining two or more of these. In addition, as the alkylene group having 2 to 12 carbon atoms, any of linear, branched, cyclic, and alkylene groups represented by these combinations may be used. As the above-mentioned alkylene group having 2 to 12 carbon atoms, an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.

在該等之中，R 21為下述式（R1）～式（R3）中的任一個所表示之基團為較佳，式（R1）所表示之基團為更佳。 [化學式14]

Figure 02_image026
式（R1）～（R3）中，L表示單鍵或碳數2～12的伸烷基、碳數2～30的（聚）伸烷氧基或將該等中的2個以上鍵結而成之基團，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。 式（R1）～（R3）中，L中之碳數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的R 21中之碳數2～12的伸烷基或碳數2～30的（聚）伸烷氧基的較佳態樣相同。 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）所表示之結構例如藉由使具有酚性羥基等羥基之聚醯亞胺與具有異氰酸酯基及乙烯性不飽和鍵之化合物（例如，甲基丙烯酸2-異氰酸酯基乙酯等）進行反應而獲得。 式（R2）所表示之結構例如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）進行反應而獲得。 式（R3）所表示之結構例如藉由使具有酚性羥基等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，甲基丙烯酸縮水甘油酯等）進行反應而獲得。 Among these, R 21 is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by the formula (R1). [Chemical formula 14]
Figure 02_image026
In the formulae (R1) to (R3), L represents a single bond, or an alkylene group having 2 to 12 carbon atoms, a (poly)alkaneoxy group having 2 to 30 carbon atoms, or two or more of these. The group formed, X represents an oxygen atom or a sulfur atom, * represents a bonding site with other structures, and ● represents a bonding site with the oxygen atom bonded to R 21 in formula (IV). In the formulae (R1) to (R3), the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkaneoxy group having 2 to 30 carbon atoms in L is the same as the carbon number in the above-mentioned R 21 . The preferable aspects of the alkylene group having 2 to 12 or the (poly)alkaneoxy 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) is obtained, for example, by combining a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate, etc.). obtained by the reaction. The structure represented by formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.). The structure represented by the formula (R3) is, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.) and obtained.

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 formula (IV), * represents a bonding site with other structures, and a bonding site with the main chain of polyimide is preferable.

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

-除了具有乙烯性不飽和鍵之基團以外的聚合性基- 聚醯亞胺可以具有除了具有乙烯性不飽和鍵之基團以外的聚合性基。 作為除了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、氧環丁烷基等環狀醚基、甲氧基甲基等烷氧基甲基、羥甲基等。 除了具有乙烯性不飽和鍵之基團以外的聚合性基例如包含於後述式（4）所表示之重複單元中之R 131中為較佳。 除了具有乙烯性不飽和鍵之基團以外的聚合性基的量相對於聚醯亞胺的總質量為0.0001～0.1mol/g為較佳，0.001～0.05mol/g為更佳。 -A polymerizable group other than a group having an ethylenically unsaturated bond - The polyimide may have a polymerizable group other than a group having an ethylenically unsaturated bond. Examples of polymerizable groups other than groups having an ethylenically unsaturated bond include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. Wait. It is preferable that the polymerizable group other than the group having an ethylenically unsaturated bond is contained in R 131 in the repeating unit represented by the formula (4) described later, for example. The amount of the polymerizable group other than the group having an ethylenically unsaturated bond is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g, relative to the total mass of the polyimide.

-極性轉換基- 聚醯亞胺可以具有酸分解性基等極性轉換基。聚醯亞胺中之酸分解性基與在上述式（2）中之R 113及R 114中所說明之酸分解性基相同，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之R 131、R 132、聚醯亞胺的末端等中。 -Polarity Conversion Group- The polyimide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable groups in the polyimide are the same as the acid-decomposable groups described for R 113 and R 114 in the above formula (2), and the preferred embodiments are also the same. The polarity switching group is contained in, for example, R 131 , R 132 , the terminal of polyimide, and the like in the repeating unit represented by the following formula (4).

-酸值- 在將聚醯亞胺供於鹼顯影之情況下，從提高顯影性之觀點考慮，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，在將聚醯亞胺供於使用了以有機溶劑為主成分之顯影液之顯影（例如，後述“溶劑顯影”）之情況下，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進行測定，例如藉由JIS K 0070：1992中所記載的方法進行測定。 又，作為聚醯亞胺中所包含之酸基，從兼顧保存穩定性及顯影性之觀點考慮，pKa為0～10的酸基為較佳，3～8的酸基為更佳。 pKa為考慮到從酸中釋放氫離子之解離反應而將其平衡常數Ka用其負的常用對數pKa表示者。在本說明書中，除非另有說明，則pKa設為基於ACD/ChemSketch（註冊商標）之計算值。或者，可以參閱日本化學會編“修訂第5版 化學手冊 基礎版”中所揭示的值。 又，在酸基例如為磷酸等多元酸之情況下，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的至少1種為較佳，包含酚性羥基為更佳。 -Acid value- When the polyimide is used for alkali development, 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 from the viewpoint of improving the developability for further better. Further, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. Moreover, when the polyimide is used for image development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is 1 to 35 mgKOH/g as Preferably, 2-30 mgKOH/g is more preferable, and 5-20 mgKOH/g is further preferable. The above 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 both storage stability and developability, an acid group with a pKa of 0 to 10 is preferable, and an acid group of 3 to 8 is more preferable. The pKa is expressed by the negative logarithm pKa of the equilibrium constant Ka taking into account the dissociation reaction releasing hydrogen ions from the acid. In this specification, unless otherwise specified, pKa is set as a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, refer to the values disclosed in "Revision 5th Edition Handbook of Chemistry Basic Edition" edited by the Chemical Society of Japan. In addition, when the acid group is, for example, a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant. As such an acid group, it is preferable that the polyimide contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and it is more preferable to contain a phenolic hydroxyl group.

-酚性羥基- 從使基於鹼顯影液之顯影速度成為適當者之觀點考慮，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，亦可以在側鏈上具有酚性羥基。 酚性羥基例如包含於後述式（4）所表示之重複單元中之R 132或後述式（4）所表示之重複單元中之R 131中為較佳。 酚性羥基的量相對於聚醯亞胺的總質量為0.1～30mol/g為較佳，1～20mol/g為更佳。 -Phenolic hydroxyl group- From the viewpoint of making the developing speed by an alkali developer suitable, it is preferable that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain, or may have a phenolic hydroxyl group at the side chain. The phenolic hydroxyl group is preferably contained in, for example, R 132 in the repeating unit represented by the formula (4) described below or R 131 in the repeating unit represented by the following formula (4). The amount of the phenolic hydroxyl groups is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g, relative to the total mass of the polyimide.

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，則並無特別限定，但是包含下述式（4）所表示之重複單元為較佳。 [化學式15]

Figure 02_image028
式（4）中，R 131表示2價的有機基，R 132表示4價的有機基。 在具有聚合性基之情況下，聚合性基可以位於R 131及R 132中的至少一者上，如下述式（4-1）或式（4-2）所示，亦可以位於聚醯亞胺的末端。 式（4-1） [化學式16]
Figure 02_image030
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17]
Figure 02_image032
R 134及R 135中的至少一者為聚合性基，在不是聚合性基之情況下為有機基，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 imide structure, but it is preferable to include a repeating unit represented by the following formula (4). [Chemical formula 15]
Figure 02_image028
In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group. In the case of having a polymerizable group, the polymerizable group may be located on at least one of R 131 and R 132 , as shown in the following formula (4-1) or formula (4-2), or may be located on a polyamide amine end. Formula (4-1) [Chemical Formula 16]
Figure 02_image030
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 17]
Figure 02_image032
At least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).

作為聚合性基，可以舉出上述包含乙烯性不飽和鍵之基團或上述除了具有乙烯性不飽和鍵之基團以外的交聯性基。 R 131表示2價的有機基。作為2價的有機基，可以例示與式（2）中之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之後殘存之二胺殘基。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。 As a polymerizable group, the group containing the said ethylenically unsaturated bond, and the said crosslinkable group other than the group which has an ethylenically unsaturated bond are mentioned. R 131 represents a divalent organic group. As a divalent organic group, the same thing as R 111 in formula (2) can be illustrated, and the preferable range is also the same. Moreover, as R131 , the diamine residue which remains after removing the amine group of a diamine is mentioned. As a diamine, an aliphatic, cycloaliphatic, or aromatic diamine etc. are mentioned. As a specific example, the example of R111 in Formula (2) of a polyimide precursor can be mentioned.

在更有效地抑制煅燒時產生翹曲之觀點上，R 131為在主鏈上具有至少2個伸烷基二醇單元之二胺殘基為較佳。更佳為在一分子中合計包含2個以上的乙二醇鏈、丙二醇鏈中的任一者或兩者之二胺殘基，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 calcination, R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain. More preferably, it is a diamine residue containing either or both of two or more ethylene glycol chains and propylene glycol chains in total in one molecule, and more preferably the above-mentioned diamine residues that do not contain an aromatic ring base.

作為在一分子中合計包含2個以上的乙二醇鏈、丙二醇鏈中的任一者或兩者之二胺，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（以上為產品名稱，HUNTSMAN公司製）、1-（2-（2-（2-胺基丙氧基）乙氧基）丙氧基）丙烷-2-胺、1-（1-（1-（2-胺基丙氧基）丙烷-2-基）氧基）丙烷-2-胺等，但是並不限定於該等。As a diamine containing in total two or more ethylene glycol chains and propylene glycol chains or both, 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 product names, manufactured by HUNTSMAN), 1-(2-(2-(2-amine) propoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine etc., but not limited to these.

R 132表示4價的有機基。作為4價的有機基，可以例示與式（2）中之R 115相同者，較佳範圍亦相同。 例如，作為R 115而例示之4價的有機基的4個鍵結子與上述式（4）中的4個-C（=O）-部分鍵結而形成縮合環。 R 132 represents a tetravalent organic group. As a tetravalent organic group, the same thing as R 115 in formula (2) can be illustrated, and the preferable range is also the same. For example, four bonders of the tetravalent organic group exemplified as R 115 are bonded to four -C(=O)- moieties in the above formula (4) to form a condensed ring.

又，R 132可以舉出從四羧酸二酐中去除酐基之後殘存之四羧酸殘基等。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, as R 132 , the tetracarboxylic acid residue etc. which remain after removing the anhydride group from the tetracarboxylic dianhydride are mentioned. As a specific example, the example of R 115 in the formula (2) of the polyimide precursor can be mentioned. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

R 131和R 132中的至少一者具有OH基亦較佳。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 preferable that at least one of R 131 and R 132 has an OH group. More specifically, as R 131 , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 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 preferable example, as R 132 , the above-mentioned (DAA-1) to (DAA-5) can be mentioned as more preferable examples.

又，聚醯亞胺在結構中具有氟原子亦較佳。聚醯亞胺中的氟原子的含量為10質量%以上為較佳，並且20質量%以下為較佳。Moreover, it is also preferable that the polyimide has a fluorine atom in the structure. The content of the fluorine atoms in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.

又，為了提高與基板的密接性，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。Moreover, in order to improve the adhesiveness with a board|substrate, polyimide may be copolymerized with the aliphatic group which has a siloxane structure. Specifically, as a diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are mentioned.

又，為了提高樹脂組成物的保存穩定性，藉由單胺、酸酐、單羧酸、單氯化物化合物、單活性酯化合物等封端劑密封聚醯亞胺的主鏈末端為較佳。在該等之中，使用單胺為更佳，作為單胺的較佳化合物，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-羥基喹啉、1-羥基-7-胺基萘、1-羥基-6-胺基萘、1-羥基-5-胺基萘、1-羥基-4-胺基萘、2-羥基-7-胺基萘、2-羥基-6-胺基萘、2-羥基-5-胺基萘、1-羧基-7-胺基萘、1-羧基-6-胺基萘、1-羧基-5-胺基萘、2-羧基-7-胺基萘、2-羧基-6-胺基萘、2-羧基-5-胺基萘、2-胺基苯甲酸、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-胺基酚、3-胺基酚、4-胺基酚、2-胺基苯硫酚、3-胺基苯硫酚、4-胺基苯硫酚等。該等可以使用2種以上，藉由使複數種封端劑進行反應，可以導入複數個不同之末端基。In addition, in order to improve the storage stability of the resin composition, it is preferable to seal the main chain ends of the polyimide with end-capping agents such as monoamine, acid anhydride, monocarboxylic acid, monochloride compound, and monoactive ester compound. Among these, it is more preferable to use a monoamine, and preferable compounds of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, and 5-amino-8 -Hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7 -aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 -aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4 -aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminosalicylic acid Benzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol , 4-aminothiophenol, etc. Two or more of these can be used, and a plurality of different terminal groups can be introduced by reacting a plurality of terminal blocking agents.

-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無特別限定，只要為100%以下即可。 上述醯亞胺化率例如藉由下述方法來進行測定。 測定聚醯亞胺的紅外吸收光譜，求出作為源自醯亞胺結構之吸收峰值之1377cm -1左右的峰值強度P1。接著，將該聚醯亞胺在350℃下進行1小時的熱處理之後，再次測定紅外吸收光譜，求出1377cm -1左右的峰值強度P2。使用所獲得之峰值強度P1、P2，依據下述式能夠求出聚醯亞胺的醯亞胺化率。 醯亞胺化率（%）=（峰值強度P1/峰值強度P2）×100 - Imidization rate (ring closure rate) - From the viewpoints of film strength, insulating properties, etc. of the obtained organic film, the imidization rate (also referred to as "ring closure rate") of polyimide is 70% or more It is more preferable, more than 80% is more preferable, and more than 90% is more preferable. The upper limit of the above-mentioned imidization rate is not particularly limited, as long as it is 100% or less. The said imidization rate is measured by the following method, for example. The infrared absorption spectrum of the polyimide was measured, and the peak intensity P1 at about 1377 cm −1 was determined as the absorption peak derived from the imide structure. Next, after heat-treating this polyimide at 350 degreeC for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity P2 of about 1377 cm< -1 > was calculated|required. Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be determined according to the following formula. Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

聚醯亞胺可以全部都含有包含1種R 131或R 132之上述式（4）所表示之重複單元，亦可以含有包含2個以上的不同種類的R 131或R 132之上述式（4）所表示之重複單元。又，聚醯亞胺除了上述式（4）所表示之重複單元以外，還可以包含其他種類的重複單元。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 all contain repeating units represented by the above formula (4) containing one type of R 131 or R 132 , or may contain the above formula (4) containing two or more different types of R 131 or R 132 Represented repeating unit. In addition, the polyimide may contain other types of repeating units in addition to the repeating unit represented by the above formula (4). As another kind of repeating unit, the repeating unit etc. which are represented by said formula (2) are mentioned, for example.

聚醯亞胺例如能夠利用如下方法來進行合成：在低溫下使四羧酸二酐與二胺（將一部分取代為單胺之封端劑）進行反應之方法；在低溫下使四羧酸二酐（將一部分取代為酸酐或單氯化物化合物或單活性酯化合物之封端劑）與二胺進行反應之方法；藉由四羧酸二酐和醇來獲得二酯，然後使其與二胺（將一部分取代為單胺之封端劑）在縮合劑的存在下進行反應之方法；利用藉由四羧酸二酐和醇獲得二酯，然後使其餘的二羧酸進行氯化物化，並使其與二胺（將一部分取代為單胺之封端劑）進行反應之方法等方法獲得聚醯亞胺前驅物，並且使用已知的醯亞胺化反應法使其完全醯亞胺化之方法；或者，在中途停止醯亞胺化反應，導入一部分醯亞胺結構之方法；以及藉由混合完全醯亞胺化之聚合物和該聚醯亞胺前驅物而導入一部分醯亞胺結構之方法。又，亦能夠適用其他公知的聚醯亞胺的合成方法。The polyimide can be synthesized, for example, by a method of reacting tetracarboxylic dianhydride and diamine (an end-capping agent in which a part of monoamine is substituted) at low temperature; Anhydride (a part of which is substituted with an acid anhydride or a monochloride compound or a monoactive ester compound) is reacted with a diamine; a diester is obtained by tetracarboxylic dianhydride and an alcohol, which is then reacted with the diamine A method of reacting in the presence of a condensing agent (a part of which is replaced by a monoamine end-capping agent); using tetracarboxylic dianhydride and alcohol to obtain a diester, and then chlorinating the remaining dicarboxylic acid, and The polyimide precursor is obtained by a method such as a method of reacting it with a diamine (an end-capping agent that partially replaces a monoamine), and it is completely imidized using a known imidization reaction method. method; alternatively, a method of stopping the imidization reaction in the middle, and introducing a part of the imide structure; and introducing a part of the imide structure by mixing the fully imidized polymer and the polyimide precursor. method. In addition, other known methods for synthesizing polyimide 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。聚醯亞胺的分子量的分散度的上限值並無特別規定，例如為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，在樹脂組成物包含複數種聚醯亞胺作為特定樹脂之情況下，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內為較佳。又，將上述複數種聚醯亞胺作為1個樹脂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 making the weight average molecular weight into 5,000 or more, the folding endurance of the film after hardening can be improved. In order to obtain an organic film excellent in mechanical properties (eg, elongation at break), a weight average molecular weight of 15,000 or more is particularly preferred. Moreover, 2,000-40,000 are preferable, as for the number average molecular weight (Mn) of polyimide, 3,000-30,000 are more preferable, 4,000-20,000 are still more preferable. The dispersity of the molecular weight of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the degree of dispersion of the molecular weight of the polyimide is not particularly limited, but, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In addition, 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 dispersity of at least one polyimide are within the above-mentioned ranges. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated using the above-mentioned plural types of polyimides as one resin are respectively within the above-mentioned ranges.

〔聚苯并㗁唑前驅物〕 關於本發明中所使用之聚苯并㗁唑前驅物的結構等，並無特別規定，但是較佳為包含下述式（3）所表示之重複單元。 [化學式18]

Figure 02_image034
式（3）中，R 121表示2價的有機基，R 122表示4價的有機基，R 123及R 124分別獨立地表示氫原子或1價的有機基。 [Polybenzoxazole Precursor] The structure and the like of the polybenzoxazole precursor used in the present invention are not particularly limited, but it is preferable to include a repeating unit represented by the following formula (3). [Chemical formula 18]
Figure 02_image034
In 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.

式（3）中，R 123及R 124分別與式（2）中之R 113的含義相同，較佳範圍亦相同。亦即，至少一者為聚合性基為較佳。 式（3）中，R 121表示2價的有機基。作為2價的有機基，包含脂肪族基及芳香族基中的至少一者之基團為較佳。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 formula (3), R 123 and R 124 have the same meanings as R 113 in formula (2), respectively, and the preferred ranges are also the same. That is, at least one of them is preferably a polymerizable group. In formula (3), R 121 represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. As the aliphatic group, a straight-chain aliphatic group is preferable. 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.

作為二羧酸殘基，包含脂肪族基之二羧酸及包含芳香族基之二羧酸殘基為較佳，包含芳香族基之二羧酸殘基為更佳。 作為包含脂肪族基之二羧酸，包含直鏈或支鏈（較佳為直鏈）脂肪族基之二羧酸為較佳，包括直鏈或支鏈（較佳為直鏈）脂肪族基和2個-COOH之二羧酸為更佳。直鏈或支鏈（較佳為直鏈）的脂肪族基的碳數為2～30為較佳，2～25為更佳，3～20為進一步較佳，4～15為更進一步較佳，5～10為特佳。直鏈的脂肪族基為伸烷基為較佳。 作為包含直鏈的脂肪族基之二羧酸，可以舉出丙二酸、二甲基丙二酸、乙基丙二酸、異丙基丙二酸、二正丁基丙二酸、丁二酸、四氟丁二酸、甲基丁二酸、2,2-二甲基丁二酸、2,3-二甲基丁二酸、二甲基甲基丁二酸、戊二酸、六氟戊二酸、2-甲基戊二酸、3-甲基戊二酸、2,2-二甲基戊二酸、3,3-二甲基戊二酸、3-乙基-3-甲基戊二酸、己二酸、八氟己二酸、3-甲基己二酸、庚二酸、2,2,6,6-四甲基庚二酸、辛二酸、十二氟辛二酸、壬二酸、癸二酸、十六氟癸二酸、1,9-壬二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十七烷二酸、十八烷二酸、十九烷二酸、二十烷二酸、二十一烷二酸、二十二烷二酸、二十三烷二酸、二十四烷二酸、二十五烷二酸、二十六烷二酸、二十七烷二酸、二十八烷二酸、二十九烷二酸、三十烷二酸、三十一烷二酸、三十二烷二酸、二乙醇酸（diglycolic acid）以及下述式所表示之二羧酸等。 As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable. As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group is preferred, including a linear or branched (preferably linear) aliphatic group and 2 -COOH dicarboxylic acids are more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, more preferably 3 to 20, and even more preferably 4 to 15 , 5 to 10 is particularly good. The straight-chain aliphatic group is preferably an alkylene group. Examples of the dicarboxylic acid containing a straight-chain aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, and succinic acid. acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexanoic acid Fluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3- Methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluoroic acid Suberic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9- azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid , hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, tridecanedioic acid acid, tetracosanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacosanedioic acid, Tridecanedioic acid, tridecanedioic acid, diglycolic acid, dicarboxylic acid represented by the following formula, and the like.

[化學式19]

Figure 02_image036
（式中，Z為碳數1～6的烴基，n為1～6的整數。） [Chemical formula 19]
Figure 02_image036
(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.)

作為包含芳香族基之二羧酸，以下具有芳香族基之二羧酸為較佳，以下僅包括具有芳香族基之基團和2個-COOH之二羧酸為更佳。As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acid having an aromatic group is preferred, and the following dicarboxylic acid including only a group having an aromatic group and two -COOH is more preferred.

[化學式20]

Figure 02_image038
式中，A表示選自包括-CH 2-、-O-、-S-、-SO 2-、-CO-、-NHCO-、-C（CF 3） 2-及-C（CH 3） 2-之群組中的2價的基團，*分別獨立地表示與其他結構的鍵結部位。 [Chemical formula 20]
Figure 02_image038
In the formula, A represents selected from the group consisting of -CH 2 -, -O-, -S-, -SO 2 -, -CO-, -NHCO-, -C(CF 3 ) 2 - and -C(CH 3 ) 2 For a divalent group in the group of -, * each independently represents a bonding site with other structures.

作為包含芳香族基之二羧酸的具體例，可以舉出4,4’-羰基二苯甲酸及4,4’-二羧基二苯醚、鄰苯二甲酸。Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and phthalic acid.

式（3）中，R 122表示4價的有機基。作為4價的有機基，與上述式（2）中之R 115的含義相同，較佳範圍亦相同。 R 122為源自雙胺基苯酚衍生物之基團亦較佳，作為源自雙胺基苯酚衍生物之基團，例如可以舉出3,3’-二胺基-4,4’-二羥基聯苯、4,4’-二胺基-3,3’-二羥基聯苯、3,3’-二胺基-4,4’-二羥基二苯碸、4,4’-二胺基-3,3’-二羥基二苯碸、雙-（3-胺基-4-羥基苯基）甲烷、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、2,2-雙-（4-胺基-3-羥基苯基）六氟丙烷、雙-（4-胺基-3-羥基苯基）甲烷、2,2-雙-（4-胺基-3-羥基苯基）丙烷、4,4’-二胺基-3,3’-二羥基二苯甲酮、3,3’-二胺基-4,4’-二羥基二苯甲酮、4,4’-二胺基-3,3’-二羥基二苯醚、3,3’-二胺基-4,4’-二羥基二苯醚、1,4-二胺基-2,5-二羥基苯、1,3-二胺基-2,4-二羥基苯、1,3-二胺基-4,6-二羥基苯等。該等雙胺基苯酚可以單獨使用或者混合使用。 In formula (3), R 122 represents a tetravalent organic group. The tetravalent organic group has the same meaning as that of R 115 in the above formula (2), and the preferred range is also the same. R 122 is also preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-diaminophenol. Hydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl, 4,4'-diamine bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane 2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino- 3-Hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3 ,3'-Diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4 ,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino- 4,6-Dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

在雙胺基苯酚衍生物中，下述具有芳香族基之雙胺基苯酚衍生物為較佳。Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferable.

[化學式21]

Figure 02_image040
式中，X 1表示-O-、-S-、-C（CF 3） 2-、-CH 2-、-SO 2-、-NHCO-，*及#分別表示與其他結構的鍵結部位。R表示氫原子或1價的取代基，氫原子或烴基為較佳，氫原子或烷基為更佳。又，R 122為上述式所表示之結構亦較佳。在R 122為上述式所表示之結構之情況下，在共計4個*及#中，任意2個為與式（3）中的R 122所鍵結之氮原子的鍵結部位且其他2個為與式（3）中的R 122所鍵結之氧原子的鍵結部位為較佳，2個*為與式（3）中的R 122所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R 122所鍵結之氮原子的鍵結部位，或者2個*為與式（3）中的R 122所鍵結之氮原子的鍵結部位且2個#為與式（3）中的R 122所鍵結之氧原子的鍵結部位為更佳，2個*為與式（3）中的R 122所鍵結之氧原子的鍵結部位且2個#為與式（3）中的R 122所鍵結之氮原子的鍵結部位為進一步較佳。 [Chemical formula 21]
Figure 02_image040
In the formula, X 1 represents -O-, -S-, -C(CF 3 ) 2 -, -CH 2 -, -SO 2 -, -NHCO-, and * and # represent the bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Moreover, it is also preferable that R 122 is a structure represented by the above formula. In the case where R 122 is a structure represented by the above formula, among the total of 4 * and #, any two are the bonding site to the nitrogen atom to which R 122 in the formula (3) is bonded, and the other two are Preferably, it is the bonding site of the oxygen atom bonded to R 122 in the formula (3), and two * are the bonding sites of the oxygen atom bonded to R 122 in the formula (3), and 2 # is the bonding site with the nitrogen atom bonded to R 122 in the formula (3), or two * are the bonding sites with the nitrogen atom bonded with R 122 in the formula (3) and two # More preferably, it is the bonding site of the oxygen atom bonded to R 122 in the formula (3), and 2 * are the bonding sites of the oxygen atom bonded to R 122 in the formula (3), and 2 It is more preferable that # is the bonding site to the nitrogen atom bonded to R 122 in the formula (3).

雙胺基苯酚衍生物為式（A-s）所表示之化合物亦較佳。 [化學式22]

Figure 02_image042
It is also preferable that the bisaminophenol derivative is a compound represented by the formula (As). [Chemical formula 22]
Figure 02_image042

式（A-s）中，R 1為選自氫原子、伸烷基、取代伸烷基、-O-、-S-、-SO 2-、-CO-、-NHCO-、單鍵或下述式（A-sc）之群組中的有機基。R 2為氫原子、烷基、烷氧基、醯氧基、環狀烷基中的任一個，其可以相同亦可以不同。R 3為氫原子、直鏈或支鏈烷基、烷氧基、醯氧基、環狀烷基中的任一個，其可以相同亦可以不同。 In formula (As), R 1 is selected from hydrogen atom, alkylene group, substituted alkylene group, -O-, -S-, -SO 2 -, -CO-, -NHCO-, single bond or the following formula Organic groups in the group of (A-sc). R 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, which may be the same or different. R 3 is any one of a hydrogen atom, a straight-chain or branched-chain alkyl group, an alkoxy group, an aryloxy group, and a cyclic alkyl group, which may be the same or different.

[化學式23]

Figure 02_image044
（式（A-sc）中，*表示與上述式（A-s）所表示之雙胺基苯酚衍生物的胺基苯酚基的芳香環鍵結。） [Chemical formula 23]
Figure 02_image044
(In the formula (A-sc), * represents a bond with the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

上述式（A-s）中，認為在酚性羥基的鄰位亦即在R 3上亦具有取代基會使醯胺鍵的羰基碳與羥基的距離更靠近，在進一步提高在低溫下硬化時成為高環化率之效果之方面而言為特佳。 In the above formula (As), it is considered that having a substituent at the ortho position of the phenolic hydroxyl group, that is, also on R 3 will make the distance between the carbonyl carbon of the amide bond and the hydroxyl group closer, and it will be higher when hardening at a low temperature is further improved. It is particularly preferable in terms of the effect of the cyclization rate.

又，上述式（A-s）中，R 2為烷基且R 3為烷基時能夠維持對i射線的高透明性和在低溫下硬化時為高環化率之效果，因此為較佳。 In addition, in the above formula (As), when R 2 is an alkyl group and R 3 is an alkyl group, the effect of maintaining high transparency to i-rays and high cyclization rate during curing at low temperature is preferable.

又，上述式（A-s）中，R 1為伸烷基或取代伸烷基為進一步較佳。作為R 1之伸烷基及取代伸烷基的具體例，可以舉出碳數1～8的直鏈狀或支鏈狀烷基，其中，在一邊維持對i射線的高透明性和在低溫下硬化時為高環化率之效果一邊能夠獲得對溶劑具有充分的溶解性之平衡優異之聚苯并㗁唑前驅物之方面而言，-CH 2-、-CH（CH 3）-、-C（CH 3） 2-為更佳。 In addition, in the above formula (As), it is more preferable that R 1 is an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group for R 1 include straight-chain or branched alkyl groups having 1 to 8 carbon atoms, wherein high transparency to i-rays and low temperature are maintained while maintaining high transparency. -CH 2 -, -CH(CH 3 )-, - -CH 2 -, -CH(CH 3 )-, - -CH 2 -, -CH(CH 3 )-, - C(CH 3 ) 2 - is better.

作為上述式（A-s）所表示之雙胺基苯酚衍生物之製造方法，例如能夠參閱日本特開2013-256506號公報的0085～0094段及實施例1（0189～0190段），並將該等內容編入本說明書中。As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A No. 2013-256506, and these The contents are incorporated into this manual.

作為上述式（A-s）所表示之雙胺基苯酚衍生物的結構的具體例，可以舉出日本特開2013-256506號公報的0070～0080段中所記載者，並將該等內容編入本說明書中。當然，並不限定於該等，這是不言而喻的。Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of Japanese Patent Laid-Open No. 2013-256506, which are incorporated into the present specification. middle. Of course, it is not limited to these, it goes without saying.

聚苯并㗁唑前驅物除了上述式（3）的重複單元以外，還可以包含其他種類的重複單元。 在能夠抑制伴隨閉環而產生翹曲之方面而言，聚苯并㗁唑前驅物包含下述式（SL）所表示之二胺殘基作為其他種類的重複單元為較佳。 In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor may contain other types of repeating units. It is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of repeating unit in terms of suppressing the occurrence of warpage accompanying ring closure.

[化學式24]

Figure 02_image046
式（SL）中，Z具有a結構和b結構，R 1s為氫原子或碳數1～10的烴基，R 2s為碳數1～10的烴基，R 3s、R 4s、R 5s、R 6s中的至少1個為芳香族基，其餘為氫原子或碳數1～30的有機基，其分別可以相同亦可以不同。a結構及b結構的聚合可以為嵌段聚合，亦可以為無規聚合。關於Z部分的莫耳%，a結構為5～95莫耳%、b結構為95～5莫耳%，a+b為100莫耳%。 [Chemical formula 24]
Figure 02_image046
In formula (SL), Z has a structure and b structure, R 1s is a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms, R 2s is a hydrocarbon group with 1 to 10 carbon atoms, R 3s , R 4s , R 5s , R 6s At least one of them is an aromatic group, and the rest are a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. Regarding the mol % of the Z part, the a structure is 5 to 95 mol %, the b structure is 95 to 5 mol %, and a+b is 100 mol %.

式（SL）中，作為較佳的Z，可以舉出b結構中的R 5s及R 6s為苯基者。又，式（SL）所示之結構的分子量為400～4,000為較佳，500～3,000為更佳。藉由將上述分子量設在上述範圍內，能夠更有效地減小聚苯并㗁唑前驅物在脫水閉環後的彈性模數，能夠兼顧能夠抑制翹曲之效果和提高溶劑溶解性之效果。 In the formula (SL), as preferable Z, those in which R 5s and R 6s in the structure b are phenyl groups can be mentioned. Moreover, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the above molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be more effectively reduced, and both the effect of suppressing warpage and the effect of improving solvent solubility can be achieved.

在包含式（SL）所表示之二胺殘基作為其他種類的重複單元之情況下，進一步包含從四羧酸二酐中去除酐基之後殘存之四羧酸殘基作為重複單元亦較佳。作為該種四羧酸殘基的例子，可以舉出式（2）中的R 115的例子。 When the diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferable to further include the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride as the repeating unit. Examples of such tetracarboxylic acid residues include R 115 in the formula (2).

聚苯并㗁唑前驅物的重量平均分子量（Mw）例如較佳為18,000～30,000，更佳為20,000～29,000，進一步較佳為22,000～28,000。又，數量平均分子量（Mn）較佳為7,200～14,000，更佳為8,000～12,000，進一步較佳為9,200～11,200。 上述聚苯并㗁唑前驅物的分子量的分散度為1.4以上為較佳，1.5以上為更佳，1.6以上為進一步較佳。聚苯并㗁唑前驅物的分子量的分散度的上限值並無特別規定，例如2.6以下為較佳，2.5以下為更佳，2.4以下為進一步較佳，2.3以下為更進一步較佳，2.2以下為又更進一步較佳。 又，在樹脂組成物包含複數種聚苯并㗁唑前驅物作為特定樹脂之情況下，至少1種聚苯并㗁唑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內為較佳。又，將上述複數種聚苯并㗁唑前驅物作為1個樹脂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較佳。 The weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and still more preferably 22,000 to 28,000. Moreover, as for the number average molecular weight (Mn), 7,200-14,000 are preferable, 8,000-12,000 are more preferable, 9,200-11,200 are still more preferable. The dispersity of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly specified, for example, 2.6 or less is preferred, 2.5 or less is more preferred, 2.4 or less is further preferred, 2.3 or less is further preferred, and 2.2 or less is more preferred. The following are still further preferred. Also, in the case where the resin composition contains a plurality of polybenzoxazole precursors as the specific resin, the weight average molecular weight, number average molecular weight and dispersion degree of at least one polybenzoxazole precursor are within the above-mentioned ranges. good. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight and the degree of dispersion calculated by using the above-mentioned plural types of polybenzoxazole precursors as one resin are respectively within the above-mentioned ranges.

〔聚苯并㗁唑〕 作為聚苯并㗁唑，只要為具有苯并㗁唑環之高分子化合物，則並無特別限定，但是下述式（X）所表示之化合物為較佳，由下述式（X）表示且具有聚合性基之化合物為更佳。作為上述聚合性基，自由基聚合性基為較佳。又，亦可以為由下述式（X）表示且具有酸分解性基等極性轉換基之化合物。 [化學式25]

Figure 02_image048
式（X）中，R 133表示2價的有機基，R 134表示4價的有機基。 在具有聚合性基或酸分解性基等極性轉換基之情況下，聚合性基或酸分解性基等極性轉換基可以位於R 133及R 134中的至少一者上，如下述式（X-1）或式（X-2）所示，亦可以位於聚苯并㗁唑的末端。 式（X-1） [化學式26]
Figure 02_image050
式（X-1）中，R 135及R 136中的至少一者為聚合性基或酸分解性基等極性轉換基，在不是聚合性基或酸分解性基等極性轉換基之情況下為有機基，其他基團與式（X）的含義相同。 式（X-2） [化學式27]
Figure 02_image052
式（X-2）中，R 137為聚合性基或酸分解性基等極性轉換基，其他為取代基，其他基團與式（X）的含義相同。 [Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but a compound represented by the following formula (X) is preferable, and the following The compound represented by the above formula (X) and having a polymerizable group is more preferable. As the above-mentioned polymerizable group, a radically polymerizable group is preferable. Moreover, it may be a compound represented by the following formula (X) and having a polarity converting group such as an acid-decomposable group. [Chemical formula 25]
Figure 02_image048
In formula (X), R 133 represents a divalent organic group, and R 134 represents a tetravalent organic group. In the case of having a polar conversion group such as a polymerizable group or an acid decomposable group, the polar conversion group such as a polymerizable group or an acid decomposable group may be located on at least one of R 133 and R 134 , as shown in the following formula (X- 1) or represented by formula (X-2), it may be located at the end of polybenzoxazole. Formula (X-1) [Chemical Formula 26]
Figure 02_image050
In formula (X-1), at least one of R 135 and R 136 is a polar conversion group such as a polymerizable group or an acid-decomposable group, and when it is not a polar conversion group such as a polymerizable group or an acid-decomposable group, it is Organic group, other groups have the same meanings as formula (X). Formula (X-2) [Chemical Formula 27]
Figure 02_image052
In the formula (X-2), R 137 is a polar conversion group such as a polymerizable group or an acid-decomposable group, the other groups are substituent groups, and the other groups have the same meanings as those of the formula (X).

聚合性基或酸分解性基等極性轉換基與在上述聚醯亞胺前驅物所具有之聚合性基中敘述之聚合性基的含義相同。The polarity conversion group such as a polymerizable group or an acid-decomposable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group of the polyimide precursor.

R 133表示2價的有機基。作為2價的有機基，可以舉出脂肪族基或芳香族基。作為具體例，可以舉出聚苯并㗁唑前驅物的式（3）中的R 121的例子。又，其較佳例與R 121相同。 R 133 represents a divalent organic group. As a divalent organic group, an aliphatic group or an aromatic group is mentioned. As a specific example, the example of R121 in Formula (3) of a polybenzoxazole precursor is mentioned. In addition, its preferable example is the same as that of R121 .

R 134表示4價的有機基。作為4價的有機基，可以舉出聚苯并㗁唑前驅物的式（3）中的R 122的例子。又，其較佳例與R 122相同。 例如，作為R 122而例示之4價的有機基的4個鍵結子與上述式（X）中的氮原子、氧原子鍵結而形成縮合環。例如，在R 134為下述有機基之情況下，形成下述結構。下述結構中，*分別表示與式（X）中的氮原子或氧原子的鍵結部位。 [化學式28]

Figure 02_image054
R 134 represents a tetravalent organic group. Examples of the tetravalent organic group include R 122 in the formula (3) of the polybenzoxazole precursor. In addition, its preferable example is the same as that of R 122 . For example, four bonders of the tetravalent organic group exemplified as R 122 are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R 134 is the following organic group, the following structure is formed. In the following structures, * represents a bonding site to a nitrogen atom or an oxygen atom in the formula (X), respectively. [Chemical formula 28]
Figure 02_image054

聚苯并㗁唑的㗁唑化率為85%以上為較佳，90%以上為更佳。上限並無特別限定，可以為100%。藉由㗁唑化率為85%以上，由藉由加熱而㗁唑化時所產生之閉環引起之膜收縮減少，從而能夠更有效地抑制產生翹曲。 上述㗁唑化率例如藉由下述方法來進行測定。 測定聚苯并㗁唑的紅外吸收光譜，求出作為源自前驅物的醯胺結構之吸收峰值之1650cm -1左右的峰值強度Q1。接著，以在1490cm -1左右發現之芳香環的吸收強度進行標準化。將該聚苯并㗁唑在350℃下進行1小時的熱處理之後，再次測定紅外吸收光譜，求出1650cm -1左右的峰值強度Q2，並且以在1490cm -1左右發現之芳香環的吸收強度進行標準化。使用所獲得之峰值強度Q1、Q2的標準值，依據下述式能夠求出聚苯并㗁唑的㗁唑化率。 㗁唑化率（%）=（峰值強度Q1的標準值/峰值強度Q2的標準值）×100 The oxazole ratio of the polybenzoxazole is preferably 85% or more, more preferably 90% or more. The upper limit is not particularly limited, and may be 100%. When the oxazolylization ratio is 85% or more, film shrinkage due to ring closure generated when oxazolylization by heating is reduced, and the occurrence of warpage can be suppressed more effectively. The said oxazolation rate is measured by the following method, for example. The infrared absorption spectrum of the polybenzoxazole was measured, and the peak intensity Q1 at about 1650 cm −1 which was the absorption peak derived from the amide structure of the precursor was obtained. Next, normalization was performed by the absorption intensity of the aromatic ring found around 1490 cm −1 . After heat-treating the polybenzoxazole at 350° C. for 1 hour, the infrared absorption spectrum was measured again, and the peak intensity Q2 at about 1650 cm −1 was obtained, and the absorption intensity of the aromatic ring found at about 1490 cm −1 was measured. standardization. Using the obtained standard values of the peak intensities Q1 and Q2, the oxazolylization rate of polybenzoxazole can be determined according to the following formula. Azolization rate (%) = (standard value of peak intensity Q1 / standard value of peak intensity Q2) × 100

聚苯并㗁唑可以全部都含有包含1種R 131或R 132之上述式（X）的重複單元，亦可以含有包含2個以上的不同種類的R 131或R 132之上述式（X）的重複單元。又，聚苯并㗁唑除了上述式（X）的重複單元以外，還可以包含其他種類的重複單元。 The polybenzoxazoles may all contain repeating units of the above formula (X) containing one kind of R 131 or R 132, or may contain two or more different kinds of R 131 or R 132 The repeating units of the above formula (X) repeating unit. Moreover, in addition to the repeating unit of the said formula (X), a polybenzoxazole may contain another kind of repeating unit.

關於聚苯并㗁唑，例如藉由使雙胺基苯酚衍生物與包含R 133之二羧酸或選自上述二羧酸的二羧酸二氯化物（dicarboxylic acid dichloride）及二羧酸衍生物等中之化合物進行反應而獲得聚苯并㗁唑前驅物，並利用已知的㗁唑化反應法使其㗁唑化而獲得。 再者，在二羧酸的情況下，為了提高反應產率等，可以使用使1-羥基-1,2,3-苯并三唑等預先反應而獲得之活性酯型二羧酸衍生物。 Regarding polybenzoxazoles, for example, by combining a bisaminophenol derivative with a dicarboxylic acid comprising R 133 or a dicarboxylic acid dichloride and a dicarboxylic acid derivative selected from the group consisting of the above-mentioned dicarboxylic acids A polybenzoxazole precursor is obtained by reacting the compounds in the above, and it is obtained by oxazoleization by a known oxazole method. In addition, in the case of a dicarboxylic acid, in order to improve the reaction yield and the like, an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance can be used.

聚苯并㗁唑的重量平均分子量（Mw）為5,000～70,000為較佳，8,000～50,000為更佳，10,000～30,000為進一步較佳。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性。為了獲得機械特性優異之有機膜，重量平均分子量為20,000以上為特佳。又，在含有2種以上的聚苯并㗁唑之情況下，至少1種聚苯并㗁唑的重量平均分子量在上述範圍內為較佳。 又，聚苯并㗁唑的數量平均分子量（Mn）較佳為7,200～14,000，更佳為8,000～12,000，進一步較佳為9,200～11,200。 上述聚苯并㗁唑的分子量的分散度為1.4以上為較佳，1.5以上為更佳，1.6以上為進一步較佳。聚苯并㗁唑的分子量的分散度的上限值並無特別規定，例如2.6以下為較佳，2.5以下為更佳，2.4以下為進一步較佳，2.3以下為進一步較佳，2.2以下為更進一步較佳。 又，在樹脂組成物包含複數種聚苯并㗁唑作為特定樹脂之情況下，至少1種聚苯并㗁唑的重量平均分子量、數量平均分子量及分散度在上述範圍內為較佳。又，將上述複數種聚苯并㗁唑作為1個樹脂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較佳。 The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight average molecular weight into 5,000 or more, the folding endurance of the film after hardening can be improved. In order to obtain an organic film excellent in mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. Moreover, when containing two or more types of polybenzoxazoles, it is preferable that the weight average molecular weight of at least one type of polybenzoxazoles is in the said range. Moreover, as for the number average molecular weight (Mn) of polybenzoxazole, 7,200-14,000 are preferable, 8,000-12,000 are more preferable, 9,200-11,200 are still more preferable. The dispersity of the molecular weight of the polybenzoxazole is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of polybenzoxazole is not particularly specified, for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, 2.3 or less is further preferable, and 2.2 or less is even more preferable. Further preferred. Moreover, when the resin composition contains a plurality of polybenzoxazoles as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight and dispersion degree of at least one polybenzoxazole are within the above-mentioned ranges. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated using the above-mentioned plural types of polybenzoxazoles as one resin are respectively within the above-mentioned ranges.

〔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29]

Figure 02_image056
式（PAI-2）中，R 117表示3價的有機基，R 111表示2價的有機基，A 2表示氧原子或-NH-，R 113表示氫原子或1價的有機基。 [Polyamide imide precursor] It is preferable that the polyamide imide precursor contains a repeating unit represented by the following formula (PAI-2). [Chemical formula 29]
Figure 02_image056
In 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.

式（PAI-2）中，R 117可以例示直鏈狀或支鏈狀的脂肪族基、環狀的脂肪族基及芳香族基、雜芳族基團或者單鍵或藉由連接基將該等連接2個以上而獲得之基團，碳數2～20的直鏈的脂肪族基、碳數3～20的支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族基或者單鍵或藉由連接基將該等組合2個以上而獲得之基團為較佳，碳數6～20的芳香族基或者單鍵或藉由連接基將碳數6～20的芳香族基組合2個以上而獲得之基團為更佳。 作為上述連接基，-O-、-S-、-C（=O）-、-S（=O） 2-、伸烷基、鹵化伸烷基、伸芳基或該等鍵結2個以上而形成之連接基為較佳，-O-、-S-、伸烷基、鹵化伸烷基、伸芳基或該等鍵結2個以上而形成之連接基為更佳。 作為上述伸烷基，碳數1～20的伸烷基為較佳，碳數1～10的伸烷基為更佳，碳數1～4的伸烷基為進一步較佳。 作為上述鹵化伸烷基，碳數1～20的鹵化伸烷基為較佳，碳數1～10的鹵化伸烷基為更佳，碳數1～4的鹵化伸烷基為更佳。又，作為上述鹵化伸烷基中之鹵素原子，可以舉出氟原子、氯原子、溴原子、碘原子等，氟原子為較佳。上述鹵化伸烷基可以具有氫原子，亦可以使所有氫原子經鹵素原子取代，但是所有氫原子經鹵素原子取代為較佳。作為較佳的鹵化伸烷基的例子，可以舉出（二三氟甲基）亞甲基等。 作為上述伸芳基，伸苯基或伸萘基為較佳，伸苯基為更佳，1,3-伸苯基或1,4-伸苯基為進一步較佳。 In the formula (PAI-2), R 117 can be exemplified by linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups or single bonds or through linking groups. A group obtained by linking two or more groups, such as a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, Preferably, an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms or a single bond or a linking group is preferred. A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferred. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) 2 -, alkylene, halogenated alkylene, arylidene, or two or more of these bonds The linking group formed is preferably, -O-, -S-, alkylene, halogenated alkylene, arylidene, or the linking group formed by bonding two or more of these is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms be substituted with halogen atoms. As an example of a preferable halogenated alkylene group, a (ditrifluoromethyl)methylene group etc. are mentioned. As the above-mentioned arylidene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

又，R 117從至少1個羧基可以被鹵化的三羧酸化合物衍生為較佳。作為上述鹵化，氯化為較佳。 在本發明中，將具有3個羧基之化合物稱為三羧酸化合物。 上述三羧酸化合物的3個羧基中的2個羧基可以被酸酐化。 作為用於聚醯胺醯亞胺前驅物的製造中之可以被鹵化的三羧酸化合物，可以舉出支鏈狀的脂肪族、環狀的脂肪族或芳香族的三羧酸化合物等。 該等三羧酸化合物可以僅使用1種，亦可以使用2種以上。 Further, R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. As the above-mentioned halogenation, chlorination is preferable. In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two carboxyl groups among the three carboxyl groups of the above-mentioned tricarboxylic acid compound may be acid anhydrided. As the tricarboxylic acid compound which may be halogenated to be used in the production of the polyamide imide precursor, a branched aliphatic, cyclic, or aromatic tricarboxylic acid compound, etc. can be mentioned. Only one type of these tricarboxylic acid compounds may be used, or two or more types may be used.

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

又，作為三羧酸化合物的具體例，可以舉出藉由單鍵、-O-、-CH 2-、-C（CH 3） 2-、-C（CF 3） 2-、-SO 2-或伸苯基連接1,2,3-丙烷三羧酸、1,3,5-戊烷三羧酸、檸檬酸、偏苯三甲酸、2,3,6-萘三羧酸、鄰苯二甲酸（或者，鄰苯二甲酸酐）與苯甲酸之化合物等。 該等化合物可以為2個羧基被酐化之化合物（例如，偏苯三甲酸酐），亦可以為至少1個羧基被鹵化之化合物（例如，偏苯三酸酐醯氯）。 In addition, specific examples of the tricarboxylic acid compound include single bond, -O-, -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -SO 2 - Or phenylene to connect 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalene tricarboxylic acid, phthalate Compounds of formic acid (or, phthalic anhydride) and benzoic acid, etc. These compounds may be compounds in which two carboxyl groups are anhydrided (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride ammonium chloride).

式（PAI-2）中，R 111、A 2、R 113分別與上述式（2）中之R 111、A 2、R 113的含義相同，較佳態樣亦相同。 In formula (PAI-2), R 111 , A 2 , and R 113 have the same meanings as R 111 , A 2 , and R 113 in the above formula (2), respectively, and the preferred embodiments are also the same.

聚醯胺醯亞胺前驅物可以進一步包含其他重複單元。 作為其他重複單元，可以舉出上述式（2）所表示之重複單元、下述式（PAI-1）所表示之重複單元等。 [化學式30]

Figure 02_image058
The polyamidoimide precursor may further comprise other repeating units. As another repeating unit, the repeating unit represented by said formula (2), the repeating unit represented by following formula (PAI-1), etc. are mentioned. [Chemical formula 30]
Figure 02_image058

式（PAI-1）中，R 116表示2價的有機基，R 111表示2價的有機基。 式（PAI-1）中，R 116可以例示直鏈狀或支鏈狀的脂肪族基、環狀的脂肪族基及芳香族基、雜芳族基團或者單鍵或藉由連接基將該等連接2個以上而獲得之基團，碳數2～20的直鏈的脂肪族基、碳數3～20的支鏈的脂肪族基、碳數3～20的環狀的脂肪族基、碳數6～20的芳香族基或者單鍵或藉由連接基將該等組合2個以上而獲得之基團為較佳，碳數6～20的芳香族基或者單鍵或藉由連接基將碳數6～20的芳香族基組合2個以上而獲得之基團為更佳。 作為上述連接基，-O-、-S-、-C（=O）-、-S（=O） 2-、伸烷基、鹵化伸烷基、伸芳基或該等鍵結2個以上而形成之連接基為較佳，-O-、-S-、伸烷基、鹵化伸烷基、伸芳基或該等鍵結2個以上而形成之連接基為更佳。 作為上述伸烷基，碳數1～20的伸烷基為較佳，碳數1～10的伸烷基為更佳，碳數1～4的伸烷基為進一步較佳。 作為上述鹵化伸烷基，碳數1～20的鹵化伸烷基為較佳，碳數1～10的鹵化伸烷基為更佳，碳數1～4的鹵化伸烷基為更佳。又，作為上述鹵化伸烷基中之鹵素原子，可以舉出氟原子、氯原子、溴原子、碘原子等，氟原子為較佳。上述鹵化伸烷基可以具有氫原子，亦可以使所有氫原子經鹵素原子取代，但是所有氫原子經鹵素原子取代為較佳。作為較佳的鹵化伸烷基的例子，可以舉出（二三氟甲基）亞甲基等。 作為上述伸芳基，伸苯基或伸萘基為較佳，伸苯基為更佳，1,3-伸苯基或1,4-伸苯基為進一步較佳。 In formula (PAI-1), R 116 represents a divalent organic group, and R 111 represents a divalent organic group. In formula (PAI-1), R 116 can be exemplified by linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, heteroaromatic groups, or single bonds or through linking groups. A group obtained by linking two or more groups, such as a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, Preferably, an aromatic group having 6 to 20 carbon atoms or a single bond or a group obtained by combining two or more of these through a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms or a single bond or a linking group is preferred. A group obtained by combining two or more aromatic groups having 6 to 20 carbon atoms is more preferred. As the above-mentioned linking group, -O-, -S-, -C(=O)-, -S(=O) 2 -, alkylene, halogenated alkylene, arylidene, or two or more of these bonds The linking group formed is preferably, -O-, -S-, alkylene, halogenated alkylene, arylidene, or the linking group formed by bonding two or more of these is more preferred. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable. As the above-mentioned halogenated alkylene group, a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable. Moreover, as a halogen atom in the said halogenated alkylene group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted with halogen atoms, but it is preferable that all hydrogen atoms be substituted with halogen atoms. As an example of a preferable halogenated alkylene group, a (ditrifluoromethyl)methylene group etc. are mentioned. As the above-mentioned arylidene group, a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is still more preferable.

又，R 116從二羧酸化合物或二羧酸二鹵化物衍生為較佳。 在本發明中，將具有2個羧基之化合物稱為二羧酸化合物，且將具有2個被鹵化之羧基之化合物稱為二羧酸二鹵化物。 二羧酸二鹵化物中之羧基只要被鹵化即可，例如被氯化為較佳。亦即，二羧酸二鹵化物為二羧酸二氯化物化合物為較佳。 作為用於聚醯胺醯亞胺前驅物的製造中之可以被鹵化的二羧酸化合物或二羧酸二鹵化物，可以舉出直鏈狀或支鏈狀的脂肪族、環狀的脂肪族或芳香族二羧酸化合物或二羧酸二鹵化物等。 該等二羧酸化合物或二羧酸二鹵化物可以僅使用1種，亦可以使用2種以上。 Further, R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide. In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide. The carboxyl group in the dicarboxylic acid dihalide may be halogenated, for example, it is preferably chlorinated. That is, it is preferable that the dicarboxylic acid dihalide is a dicarboxylic acid dichloride compound. Examples of dicarboxylic acid compounds or dicarboxylic acid dihalides that may be halogenated to be used in the production of polyamide imide precursors include linear or branched aliphatic and cyclic aliphatic Or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides, etc. Only one type of these dicarboxylic acid compounds or dicarboxylic acid dihalides may be used, or two or more types may be used.

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

又，作為二羧酸化合物的具體例，可以舉出丙二酸、二甲基丙二酸、乙基丙二酸、異丙基丙二酸、二正丁基丙二酸、琥珀酸、四氟琥珀酸、甲基琥珀酸、2,2-二甲基琥珀酸、2,3-二甲基琥珀酸、二甲基甲基琥珀酸、戊二酸、六氟戊二酸、2-甲基戊二酸、3-甲基戊二酸、2,2-二甲基戊二酸、3,3-二甲基戊二酸、3-乙基-3-甲基戊二酸、己二酸、八氟己二酸、3-甲基己二酸、庚二酸、2,2,6,6-四甲基庚二酸、辛二酸、十二氟辛二酸、壬二酸、癸二酸、十六氟癸二酸、1,9-壬二酸、十二烷二酸、十三烷二酸、十四烷二酸、十五烷二酸、十六烷二酸、十七烷二酸、十八烷二酸、十九烷二酸、二十烷二酸、二十一烷二酸、二十二烷二酸、二十三烷二酸、二十四烷二酸、二十五烷二酸、二十六烷二酸、二十七烷二酸、二十八烷二酸、二十九烷二酸、三十烷二酸、三十一烷二酸、三十二烷二酸、二乙醇酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、4,4’-聯苯羧酸、4,4’-聯苯羧酸、4,4’-二羧基二苯醚、二苯甲酮-4,4’-二羧酸等。 作為二羧酸二鹵化物的具體例，可以舉出將上述二羧酸化合物的具體例中之2個羧基進行鹵化而形成之結構的化合物。 Further, specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetra Fluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylsuccinic acid Glutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, hexanedioic acid acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, tenanedioic acid Heptanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid, behenanedioic acid, tetracosanedioic acid, tetracosanedioic acid , Pentadecanedioic acid, Hexadecanedioic acid, Heptacosanedioic acid, Hecosanedioic acid, Nonacosanedioic acid, Triacosanedioic acid, Triacosanedioic acid, Triacosanedioic acid Dodecanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'- Dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. As a specific example of a dicarboxylic acid dihalide, the compound of the structure formed by halogenating two carboxyl groups in the specific example of the said dicarboxylic acid compound is mentioned.

式（PAI-1）中，R 111與上述式（2）中之R 111的含義相同，較佳態樣亦相同。 In formula (PAI-1), R 111 has the same meaning as R 111 in the above formula (2), and the preferred aspects are also the same.

又，聚醯胺醯亞胺前驅物在結構中具有氟原子亦較佳。聚醯胺醯亞胺前驅物中的氟原子含量為10質量%以上為較佳，並且20質量%以下為較佳。Moreover, it is also preferable that the polyamide imide precursor has a fluorine atom in the structure. The content of fluorine atoms in the polyimide imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

又，為了提高與基板的密接性，聚醯胺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，作為二胺成分，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。Moreover, in order to improve the adhesiveness with a board|substrate, the aliphatic group which has a siloxane structure may be copolymerized with a polyamide imide precursor. Specifically, as the diamine component, an aspect in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used can be mentioned.

作為本發明中之聚醯胺醯亞胺前驅物的一實施形態，可以舉出式（PAI-2）所表示之重複單元、式（PAI-1）所表示之重複單元及式（2）所表示之重複單元的合計含量為所有重複單元的50莫耳%以上之態樣。上述合計含量為70莫耳%以上為更佳，90莫耳%以上為進一步較佳，超過90莫耳%為特佳。上述合計含量的上限並無特別限定，除了末端以外的聚醯胺醯亞胺前驅物中之所有重複單元可以為式（PAI-2）所表示之重複單元、式（PAI-1）所表示之重複單元及式（2）所表示之重複單元中的任一個。 又，作為本發明中之聚醯胺醯亞胺前驅物的另一實施形態，可以舉出式（PAI-2）所表示之重複單元及式（PAI-1）所表示之重複單元的合計含量為所有重複單元的50莫耳%以上之態樣。上述合計含量為70莫耳%以上為更佳，90莫耳%以上為進一步較佳，超過90莫耳%為特佳。上述合計含量的上限並無特別限定，除了末端以外的聚醯胺醯亞胺前驅物中之所有重複單元可以為式（PAI-2）所表示之重複單元或式（PAI-1）所表示之重複單元中的任一個。 As one embodiment of the polyamide imide precursor in the present invention, the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1), and the repeating unit represented by the formula (2) can be mentioned. The total content of the indicated repeating units is 50 mol % or more of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all repeating units in the polyamide imide precursor except the terminal may be repeating units represented by formula (PAI-2), and formula (PAI-1). Any one of the repeating unit and the repeating unit represented by formula (2). Moreover, as another embodiment of the polyamide imide precursor in the present invention, the total content of the repeating unit represented by the formula (PAI-2) and the repeating unit represented by the formula (PAI-1) can be mentioned In the form of more than 50 mol% of all repeating units. The above-mentioned total content is more preferably 70 mol % or more, more preferably 90 mol % or more, and particularly preferably more than 90 mol %. The upper limit of the above-mentioned total content is not particularly limited, and all the repeating units in the polyamide imide precursor except the terminal may be the repeating units represented by the formula (PAI-2) or the formula (PAI-1). Any of the repeating units.

聚醯胺醯亞胺前驅物的重量平均分子量（Mw）較佳為2,000～500,000，更佳為5,000～100,000，進一步較佳為10,000～50,000。又，數量平均分子量（Mn）較佳為800～250,000，更佳為2,000～50,000，進一步較佳為4,000～25,000。 聚醯胺醯亞胺前驅物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。聚醯胺醯亞胺前驅物的分子量的分散度的上限值並無特別規定，例如為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，在樹脂組成物包含複數種聚醯胺醯亞胺前驅物作為特定樹脂之情況下，至少1種聚醯胺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內為較佳。又，將上述複數種聚醯胺醯亞胺前驅物作為1個樹脂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較佳。 The weight average molecular weight (Mw) of the polyamide imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, further preferably 10,000 to 50,000. Moreover, as for the number average molecular weight (Mn), 800-250,000 are preferable, 2,000-50,000 are more preferable, 4,000-25,000 are still more preferable. The molecular weight of the polyamide imide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersion degree of the molecular weight of the polyamide imide precursor is not particularly limited, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Moreover, in the case where the resin composition contains a plurality of polyamide imide precursors as a specific resin, the weight average molecular weight, number average molecular weight and degree of dispersion of at least one polyamide imide precursor are within the above-mentioned ranges is better. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight and the degree of dispersion calculated by using the above-mentioned plural types of polyamide imide precursors as one resin are respectively within the above ranges.

〔聚醯胺醯亞胺〕 本發明中所使用之聚醯胺醯亞胺可以為鹼可溶性聚醯胺醯亞胺，亦可以為可溶於以有機溶劑為主成分之顯影液中之聚醯胺醯亞胺。 在本說明書中，鹼可溶性聚醯胺醯亞胺是指相對於100g的2.38質量%四甲基銨水溶液在23℃下溶解0.1g以上之聚醯胺醯亞胺，從圖案形成性的觀點考慮，溶解0.5g以上之聚醯胺醯亞胺為較佳，溶解1.0g以上之聚醯胺醯亞胺為進一步較佳。上述溶解量的上限並無特別限定，但是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，聚醯胺醯亞胺為在主鏈上具有複數個醯胺鍵及複數個醯亞胺結構之聚醯胺醯亞胺為較佳。 [Polyamide imide] The polyamide imide used in the present invention may be an alkali-soluble polyamide imide, and may also be a polyamide imide soluble in a developer whose main component is an organic solvent. In this specification, the alkali-soluble polyimide imide means that 0.1 g or more of polyimide imide is dissolved at 23° C. with respect to 100 g of a 2.38 mass % tetramethylammonium aqueous solution, from the viewpoint of pattern formation. , it is better to dissolve more than 0.5g of polyamide imide, and it is more preferred to dissolve more than 1.0 g of polyamide imide. The upper limit of the dissolved amount is not particularly limited, but is preferably 100 g or less. In addition, from the viewpoint of film strength and insulating properties of the obtained organic film, polyamide imide is a polyamide imide having a plurality of amide bonds and a plurality of amide imide structures in the main chain. better.

-氟原子- 從所獲得之有機膜的膜強度的觀點考慮，聚醯胺醯亞胺具有氟原子為較佳。 氟原子例如包含於後述式（PAI-3）所表示之重複單元中之R 117或R 111中為較佳，作為氟化烷基包含於後述式（PAI-3）所表示之重複單元中之R 117或R 111中為更佳。 氟原子的量相對於聚醯胺醯亞胺的總質量為5質量%以上為較佳，並且20質量%以下為較佳。 -Fluorine Atom- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyamide imide has a fluorine atom. Preferably, the fluorine atom is contained in, for example, R 117 or R 111 in the repeating unit represented by the formula (PAI-3) described below, and is contained in the repeating unit represented by the formula (PAI-3) described later as a fluorinated alkyl group. R 117 or R 111 is more preferable. The amount of fluorine atoms is preferably 5% by mass or more and preferably 20% by mass or less with respect to the total mass of the polyamide imide.

-乙烯性不飽和鍵- 從所獲得之有機膜的膜強度的觀點考慮，聚醯胺醯亞胺可以具有乙烯性不飽和鍵。 聚醯胺醯亞胺可以在主鏈末端具有乙烯性不飽和鍵，亦可以在側鏈上具有乙烯性不飽和鍵，但是在側鏈上具有乙烯性不飽和鍵為較佳。 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（PAI-3）所表示之重複單元中之R 117或R 111中為較佳，作為具有乙烯性不飽和鍵之基團包含於後述式（PAI-3）所表示之重複單元中之R 117或R 111中為更佳。 具有乙烯性不飽和鍵之基團的較佳態樣與上述聚醯亞胺中之具有乙烯性不飽和鍵之基團的較佳態樣相同。 -Ethylene unsaturated bond- From the viewpoint of the film strength of the obtained organic film, the polyimide imide may have an ethylenically unsaturated bond. The polyamide imide may have an ethylenically unsaturated bond at the end of the main chain or may have an ethylenically unsaturated bond in the side chain, but it is preferable to have an ethylenically unsaturated bond in the side chain. It is preferable that the above-mentioned ethylenically unsaturated bond has radical polymerizability. The ethylenically unsaturated bond is preferably included in R 117 or R 111 in the repeating unit represented by the following formula (PAI-3), and is included in the following formula (PAI-3) as a group having an ethylenically unsaturated bond R 117 or R 111 in the represented repeating unit is more preferable. The preferable aspect of the group having an ethylenically unsaturated bond is the same as the preferable aspect of the group having an ethylenically unsaturated bond in the above-mentioned polyimide.

乙烯性不飽和鍵的量相對於聚醯胺醯亞胺的總質量為0.0001～0.1mol/g為較佳，0.001～0.05mol/g為更佳。The amount of ethylenically unsaturated bonds is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g, relative to the total mass of the polyamide imide.

-除了乙烯性不飽和鍵以外的聚合性基- 聚醯胺醯亞胺可以具有除了乙烯性不飽和鍵以外的聚合性基。 作為聚醯胺醯亞胺中之除了乙烯性不飽和鍵以外的聚合性基，可以舉出與上述聚醯亞胺中之除了乙烯性不飽和鍵以外的聚合性基相同的基團。 除了乙烯性不飽和鍵以外的聚合性基例如包含於後述式（PAI-3）所表示之重複單元中之R 111中為較佳。 除了乙烯性不飽和鍵以外的聚合性基的量相對於聚醯胺醯亞胺的總質量為0.05～10mol/g為較佳，0.1～5mol/g為更佳。 -Polymerizable group other than ethylenically unsaturated bond - The polyamide imide may have a polymerizable group other than the ethylenically unsaturated bond. Examples of the polymerizable group other than the ethylenically unsaturated bond in the polyimide imide include the same groups as the polymerizable group other than the ethylenically unsaturated bond in the above-mentioned polyimide. It is preferable that the polymerizable group other than the ethylenically unsaturated bond is contained in R 111 in the repeating unit represented by the following formula (PAI-3), for example. The amount of the polymerizable groups other than the ethylenically unsaturated bond is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g, relative to the total mass of the polyamide imide.

-極性轉換基- 聚醯胺醯亞胺可以具有酸分解性基等極性轉換基。聚醯胺醯亞胺中之酸分解性基與在上述式（2）中之R 113及R 114中所說明之酸分解性基相同，較佳態樣亦相同。 -Polarity Conversion Group- The polyamide imide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamide imide is the same as the acid-decomposable group described for R 113 and R 114 in the above formula (2), and the preferred embodiments are also the same.

-酸值- 在將聚醯胺醯亞胺供於鹼顯影之情況下，從提高顯影性之觀點考慮，聚醯胺醯亞胺的酸值為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，在將聚醯胺醯亞胺供於使用了以有機溶劑為主成分之顯影液之顯影（例如，後述“溶劑顯影”）之情況下，聚醯胺醯亞胺的酸值為2～35mgKOH/g為較佳，3～30mgKOH/g為更佳，5～20mgKOH/g為進一步較佳。 上述酸值藉由公知的方法進行測定，例如藉由JIS K 0070：1992中所記載的方法進行測定。 又，作為聚醯胺醯亞胺中所包含之酸基，可以舉出與上述聚醯亞胺中之酸基相同的基團，較佳態樣亦相同。 -Acid value- When the polyamide imide is used for alkali development, the acid value of the polyamide imide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, from the viewpoint of improving the developability. 70 mgKOH/g or more is more preferable. Further, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. Moreover, when using polyimide imide for development (for example, "solvent development" described later) using a developer containing an organic solvent as a main component, the acid value of polyimide imide is 2 to 2 35 mgKOH/g is preferable, 3-30 mgKOH/g is more preferable, and 5-20 mgKOH/g is further preferable. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Moreover, as an acid group contained in a polyimide imide, the same group as the acid group in the above-mentioned polyimide can be mentioned, and the preferable aspect is also the same.

-酚性羥基- 從使基於鹼顯影液之顯影速度成為適當者之觀點考慮，聚醯胺醯亞胺具有酚性羥基為較佳。 聚醯胺醯亞胺可以在主鏈末端具有酚性羥基，亦可以在側鏈上具有酚性羥基。 酚性羥基例如包含於後述式（PAI-3）所表示之重複單元中之R 117或R 111中為較佳。 酚性羥基的量相對於聚醯胺醯亞胺的總質量為0.1～30mol/g為較佳，1～20mol/g為更佳。 -Phenolic hydroxyl group- From the viewpoint of making the developing speed by an alkali developer suitable, it is preferable that the polyimide imide has a phenolic hydroxyl group. The polyamide imide may have a phenolic hydroxyl group at the end of the main chain, or may have a phenolic hydroxyl group at the side chain. The phenolic hydroxyl group is preferably contained in, for example, R 117 or R 111 in the repeating unit represented by the following formula (PAI-3). The amount of the phenolic hydroxyl groups is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g, relative to the total mass of the polyamide imide.

作為本發明中所使用之聚醯胺醯亞胺，只要為具有醯亞胺結構及醯胺鍵之高分子化合物，則並無特別限定，但是包含下述式（PAI-3）所表示之重複單元為較佳。 [化學式31]

Figure 02_image060
式（PAI-3）中，R 111及R 117分別與式（PAI-2）中的R 111及R 117的含義相同，較佳態樣亦相同。 在具有聚合性基之情況下，聚合性基可以位於R 111及R 117中的至少一者上，亦可以位於聚醯胺醯亞胺的末端。 The polyimide imide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an imide bond, but includes a repeating formula represented by the following formula (PAI-3). unit is preferred. [Chemical formula 31]
Figure 02_image060
In formula (PAI-3), R 111 and R 117 have the same meanings as R 111 and R 117 in formula (PAI-2), respectively, and the preferred embodiments are also the same. In the case of having a polymerizable group, the polymerizable group may be located on at least one of R 111 and R 117 , or may be located at the terminal of the polyimide imide.

又，為了提高樹脂組成物的保存穩定性，用單胺、酸酐、單羧酸、單氯化物化合物、單活性酯化合物等封端劑密封聚醯胺醯亞胺的主鏈末端為較佳。封端劑的較佳態樣與上述聚醯亞胺中之封端劑的較佳態樣相同。Furthermore, in order to improve the storage stability of the resin composition, it is preferable to seal the main chain ends of the polyamide imide with a blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monochloride compound, and monoactive ester compound. The preferred aspect of the blocking agent is the same as the preferred aspect of the blocking agent in the above-mentioned polyimide.

-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，聚醯胺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無特別限定，只要為100%以下即可。 上述醯亞胺化率藉由與上述聚醯亞胺的閉環率相同的方法進行測定。 -imidization rate (ring closure rate)- From the viewpoints of film strength, insulating properties, etc. of the obtained organic film, the imidization rate (also referred to as "ring closure rate") of the polyamide imide is preferably 70% or more, and more preferably 80% or more. Good, more than 90% is better. The upper limit of the above-mentioned imidization rate is not particularly limited, as long as it is 100% or less. The said imidization rate is measured by the same method as the ring closure rate of the said polyimide.

聚醯胺醯亞胺可以全部都含有包含1種R 111或R 117之上述式（PAI-3）所表示之重複單元，亦可以含有包含2個以上的不同種類的R 131或R 132之上述式（PAI-3）所表示之重複單元。又，聚醯胺醯亞胺除了上述式（PAI-3）所表示之重複單元以外，還可以包含其他種類的重複單元。作為其他種類的重複單元，可以舉出上述式（PAI-1）或式（PAI-2）所表示之重複單元等。 The polyamide imide may all contain the repeating unit represented by the above formula (PAI-3) containing one type of R 111 or R 117 , or may contain two or more different types of R 131 or R 132 . The repeating unit represented by formula (PAI-3). Moreover, in addition to the repeating unit represented by the said formula (PAI-3), the polyamide imide may contain other kinds of repeating units. As another kind of repeating unit, the repeating unit etc. which are represented by the said formula (PAI-1) or formula (PAI-2) are mentioned.

聚醯胺醯亞胺例如能夠利用如下方法來進行合成：藉由公知的方法而獲得聚醯胺醯亞胺前驅物，並且使用已知的醯亞胺化反應法使其完全醯亞胺化之方法；或者，在中途停止醯亞胺化反應，導入一部分醯亞胺結構之方法；以及藉由混合完全醯亞胺化之聚合物和該聚醯胺醯亞胺前驅物而導入一部分醯亞胺結構之方法。Polyamidoimide can be synthesized, for example, by a method that obtains a polyamidoimide precursor by a known method, and completely imidizes it using a known imidization reaction method. method; alternatively, a method of stopping the imidization reaction in the middle and introducing a part of the imide structure; and introducing a part of the imide by mixing the fully imidized polymer and the polyimide precursor method of structure.

聚醯胺醯亞胺的重量平均分子量（Mw）為5,000～70,000為較佳，8,000～50,000為更佳，10,000～30,000為進一步較佳。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性。為了獲得機械特性優異之有機膜，重量平均分子量為20,000以上為特佳。 又，聚醯胺醯亞胺的數量平均分子量（Mn）較佳為800～250,000，更佳為2,000～50,000，進一步較佳為4,000～25,000。 聚醯胺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。聚醯胺醯亞胺的分子量的分散度的上限值並無特別規定，例如為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，在樹脂組成物包含複數種聚醯胺醯亞胺作為特定樹脂之情況下，至少1種聚醯胺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內為較佳。又，將上述複數種聚醯胺醯亞胺作為1個樹脂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較佳。 The weight average molecular weight (Mw) of the polyamide imide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight average molecular weight into 5,000 or more, the folding endurance of the film after hardening can be improved. In order to obtain an organic film excellent in mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. Furthermore, the number average molecular weight (Mn) of the polyamide imide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000. The dispersity of the molecular weight of the polyamide imide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the dispersity of the molecular weight of the polyamide imide is not particularly limited, but, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Moreover, when the resin composition contains a plurality of polyamide imides as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight and dispersion degree of at least one type of polyamide imide are within the above-mentioned ranges. Moreover, it is also preferable that the weight average molecular weight, the number average molecular weight, and the degree of dispersion calculated by using the above-mentioned plural types of polyamide imides as one resin are respectively within the above-mentioned ranges.

〔聚醯亞胺前驅物等之製造方法〕 聚醯亞胺前驅物等例如能夠利用如下方法而獲得：在低溫下使四羧酸二酐和二胺進行反應之方法、在低溫下使四羧酸二酐和二胺進行反應而獲得聚醯胺酸並使用縮合劑或烷化劑使其酯化之方法、藉由四羧酸二酐和醇而獲得二酯，之後在二胺和縮合劑的存在下使其進行反應之方法、藉由四羧酸二酐和醇而獲得二酯，之後使用鹵化劑使其餘的二羧酸鹵化，並使其與二胺進行反應之方法等。在上述製造方法中，藉由四羧酸二酐和醇而獲得二酯，之後使用鹵化劑使其餘的二羧酸鹵化，並使其與二胺進行反應之方法為更佳。 作為上述縮合劑，例如可以舉出二環己基碳二醯亞胺、二異丙基碳二醯亞胺、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’-二琥珀醯亞胺基碳酸酯（Disuccinimidyl carbonate）、三氟乙酸酐等。 作為上述烷化劑，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，可以舉出硫醯氯、草醯氯、氧氯化磷等。 在聚醯亞胺前驅物等之製造方法中，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，能夠依據原料適當設定，但是可以例示吡啶、二乙二醇二甲醚（二甘二甲醚）、N-甲基吡咯啶酮、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之製造方法中，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。 鹼性化合物能夠依據原料適當設定，但是可以例示三乙胺、二異丙基乙胺、吡啶、1,8-二氮雜雙環[5.4.0]十一碳-7-烯、N,N-二甲基-4-胺基吡啶等。 [Method for producing polyimide precursor, etc.] The polyimide precursor and the like can be obtained, for example, by a method of reacting tetracarboxylic dianhydride and diamine at low temperature, and by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamide A method of esterifying an amine acid with a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it in the presence of a diamine and a condensing agent, by A method in which tetracarboxylic dianhydride and alcohol are used to obtain a diester, and the remaining dicarboxylic acid is halogenated using a halogenating agent, followed by a method of reacting it with a diamine. In the above-mentioned production method, a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is halogenated using a halogenating agent and reacted with a diamine is more preferable. As the above-mentioned condensing agent, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-Carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, trifluoroacetic anhydride, etc. As said alkylating agent, N,N- dimethylformamide dimethyl acetal, N,N- dimethylformamide diethyl acetal, N,N-dialkylformamide can be mentioned Amine dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. As said halogenating agent, thionyl chloride, oxalyl chloride, phosphorus oxychloride, etc. are mentioned. In the production method of a polyimide precursor or the like, it is preferable to use an organic solvent when the reaction is carried out. The organic solvent may be one type or two or more types. The organic solvent can be appropriately set depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl propionate. , dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the production method of a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately set depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N- Dimethyl-4-aminopyridine and the like.

-封端劑- 在聚醯亞胺前驅物等之製造方法中，為了進一步提高保存穩定性，密封殘存於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。在密封殘存於樹脂末端之羧酸酐及酸酐衍生物時，作為封端劑，可以舉出一元醇、酚、硫醇、苯硫酚、單胺等，從反應性、膜的穩定性的觀點考慮，使用一元醇、酚類或單胺為更佳。作為一元醇的較佳化合物，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、第三丁醇、金剛烷醇等三級醇。作為酚類的較佳化合物，可以舉出酚、甲氧基苯酚、甲基酚、萘-1-醇、萘-2-醇、羥基苯乙烯等酚類等。又，作為單胺的較佳化合物，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-羥基喹啉、1-羥基-7-胺基萘、1-羥基-6-胺基萘、1-羥基-5-胺基萘、1-羥基-4-胺基萘、2-羥基-7-胺基萘、2-羥基-6-胺基萘、2-羥基-5-胺基萘、1-羧基-7-胺基萘、1-羧基-6-胺基萘、1-羧基-5-胺基萘、2-羧基-7-胺基萘、2-羧基-6-胺基萘、2-羧基-5-胺基萘、2-胺基苯甲酸、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-胺基酚、3-胺基酚、4-胺基酚、2-胺基苯硫酚、3-胺基苯硫酚、4-胺基苯硫酚等。該等可以使用2種以上，藉由使複數種封端劑進行反應，可以導入複數個不同之末端基。 又，在密封樹脂末端的胺基時，能夠用具有能夠與胺基進行反應的官能基之化合物進行密封。對胺基之較佳的密封劑為羧酸酐、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化合物，可以舉出乙醯氯、丙烯醯氯、丙醯氯、甲基丙烯醯氯、三甲基乙醯氯、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、硬脂酸醯氯、苯甲醯氯等。 -Capping agent- In the production method of the polyimide precursor or the like, in order to further improve the storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative or amine group remaining at the resin end of the polyimide precursor or the like. When sealing carboxylic acid anhydrides and acid anhydride derivatives remaining at the resin end, examples of the blocking agent include monohydric alcohols, phenols, thiols, thiophenols, monoamines, and the like, from the viewpoint of reactivity and film stability. , it is better to use monohydric alcohols, phenols or monoamines. Preferable compounds of monohydric alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloroethanol Primary alcohols such as methanol and furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol, and tertiary alcohols such as tertiary butanol and adamantanol alcohol. Preferable compounds of phenols include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Moreover, as preferable compound of monoamine, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7- aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6- aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7- aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminowater Sylic 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 of these can be used, and a plurality of different terminal groups can be introduced by reacting a plurality of terminal blocking agents. Moreover, when sealing the amine group of a resin terminal, it can seal with the compound which has a functional group which can react with an amine group. The preferred sealants for amine groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., carboxylic acid anhydrides, carboxylic acid chlorides are more preferred . Preferable compounds of the carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-di Carboxylic acid anhydride, etc. In addition, as a preferable compound of the carboxylic acid chloride, acetyl chloride, acryl chloride, acryl chloride, methacryloyl chloride, trimethyl acetyl chloride, cyclohexane methyl chloride, 2-ethyl chloride can be mentioned. Hexyl chloride, cinnamon chloride, 1-adamantanecarboxy chloride, heptafluorobutane chloride, stearate chloride, benzyl chloride, etc.

-固體析出- 在製造聚醯亞胺前驅物等時，可以包括使固體析出之步驟。具體而言，依據需要過濾出在反應液中共存之脫水縮合劑的吸水副產物之後，向水、脂肪族低級醇或其混合液等的不良溶劑投入所獲得之聚合物成分，使聚合物成分析出以作為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，可以重複將聚醯亞胺前驅物等再溶解、再沉澱、乾燥等的操作。進而，可以包括使用離子交換樹脂來去除離子性雜質之步驟。 -Solid Precipitation- When producing a polyimide precursor or the like, a step of precipitating a solid may be included. Specifically, after filtering out the water-absorbing by-product of the dehydration condensing agent coexisting in the reaction liquid as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixed solution thereof to make the polymer into a It is possible to obtain a polyimide precursor or the like by precipitation as a solid by analysis and drying. In order to improve the degree of purification, operations such as redissolving, reprecipitating, and drying the polyimide precursor and the like may be repeated. Further, a step of removing ionic impurities using an ion exchange resin may be included.

〔含量〕 本發明的樹脂組成物中之特定樹脂的含量相對於樹脂組成物的總固體成分為20質量%以上為較佳，30質量%以上為更佳，40質量%以上為進一步較佳，50質量%以上為更進一步較佳。又，本發明的樹脂組成物中之樹脂的含量相對於樹脂組成物的總固體成分為99.5質量%以下為較佳，99質量%以下為更佳，98質量%以下為進一步較佳，97質量%以下為更進一步較佳，95質量%以下為又更進一步較佳。 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種以上之情況下，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 % with respect to the total solid content of the resin composition. The above is further preferred. Moreover, the content of the resin in the resin composition of the present invention is preferably 99.5 mass % or less, more preferably 99 mass % or less, more preferably 98 mass % or less, and 97 mass % or less with respect to the total solid content of the resin composition. % or less is still more preferable, and 95 mass % or less is still more preferable. The resin composition of this invention may contain only 1 type of specific resin, and may contain 2 or more types. When two or more kinds 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種樹脂亦較佳。 具體而言，本發明的樹脂組成物可以合計包含2種以上的特定樹脂和後述其他樹脂，亦可以包含2種以上的特定樹脂，但是包含2種以上的特定樹脂為較佳。 在本發明的樹脂組成物包含2種以上的特定樹脂之情況下，例如包含為聚醯亞胺前驅物且源自二酐的結構（上述式（2）中所述之R 115）不同之2種以上的聚醯亞胺前驅物為較佳。 Moreover, it is also preferable that the resin composition of this invention contains at least 2 types of resin. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described later, or may contain two or more specific resins, but preferably contains two or more specific resins. When the resin composition of the present invention contains two or more kinds of specific resins, for example, it contains 2 different from the structure (R 115 described in the above formula (2)) derived from the dianhydride which is a polyimide precursor. More than one polyimide precursor is preferred.

＜其他樹脂＞ 本發明的樹脂組成物可以包含上述特定樹脂和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、包含聚矽氧烷、矽氧烷結構之樹脂、（甲基）丙烯酸樹脂、（甲基）丙烯酸醯胺樹脂、胺酯樹脂、丁醛樹脂、苯乙烯樹脂、聚醚樹脂、聚酯樹脂等。 例如，藉由進一步加入（甲基）丙烯酸樹脂，可以獲得塗佈性優異之樹脂組成物，並且可以獲得耐溶劑性優異之圖案（硬化物）。 例如，代替後述聚合性化合物或除了後述聚合性化合物以外，將重量平均分子量為20,000以下的聚合性基值高的（例如，樹脂1g中之聚合性基的含有莫耳量為1×10 -3莫耳/g以上）（甲基）丙烯酸樹脂添加至樹脂組成物中，從而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 resins and other resins different from the specific resins (hereinafter, also simply referred to as “other resins”). Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylic acid amide resins, and urethane resins , butyraldehyde resin, styrene resin, polyether resin, polyester resin, etc. For example, by further adding a (meth)acrylic resin, a resin composition excellent in coatability can be obtained, and a pattern (hardened product) excellent in solvent resistance can be obtained. For example, in place of or in addition to the polymerizable compound described later, a polymerizable group having a weight average molecular weight of 20,000 or less with a high value of polymerizable groups (for example, the molar content of the polymerizable group in 1 g of resin is 1×10 -3 ) molar/g or more) (meth)acrylic resin is added to the resin composition to improve the coatability of the resin composition, the solvent resistance of the pattern (hardened product), and the like.

在本發明的樹脂組成物包含其他樹脂之情況下，其他樹脂的含量相對於樹脂組成物的總固體成分為0.01質量%以上為較佳，0.05質量%以上為更佳，1質量%以上為進一步較佳，2質量%以上為更進一步較佳，5質量%以上為又更進一步較佳，10質量%以上為再更進一步較佳。 又，本發明的樹脂組成物中之其他樹脂的含量相對於樹脂組成物的總固體成分為80質量%以下為較佳，75質量%以下為更佳，70質量%以下為進一步較佳，60質量%以下為更進一步較佳，50質量%以下為又更進一步較佳。 又，作為本發明的樹脂組成物的較佳的一態樣，亦能夠設為其他樹脂的含量為低含量之態樣。在上述態樣中，其他樹脂的含量相對於樹脂組成物的總固體成分為20質量%以下為較佳，15質量%以下為更佳，10質量%以下為進一步較佳，5量%以下為更進一步較佳，1質量%以下為又更進一步較佳。上述含量的下限並無特別限定，只要為0質量%以上即可。 本發明的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種以上之情況下，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% by mass or more, more preferably 0.05% by mass or more, and more preferably 1% by mass or more with respect to the total solid content of the resin composition. Preferably, 2 mass % or more is still more preferable, 5 mass % or more is still more preferable, and 10 mass % or more is still further preferable. 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, more preferably 70 mass % or less, and 60 mass % or less with respect to the total solid content of the resin composition. It is still more preferable that it is not more than 50 mass %, and it is still more preferable that it is not more than 50 mass %. Moreover, as a preferable aspect of the resin composition of this invention, the aspect in which content of another resin is a low content can also be used. In the above aspect, the content of other resins is preferably 20 mass % or less, more preferably 15 mass % or less, more preferably 10 mass % or less, and 5 mass % or less with respect to the total solid content of the resin composition. It is still more preferable, and 1 mass % or less is still more preferable. The lower limit of the content is not particularly limited, as long as it is 0 mass % or more. The resin composition of this invention may contain only 1 type of other resin, and may contain 2 or more types. When two or more kinds are included, the total amount is preferably within the above range.

＜特定聚合性化合物＞ 本發明的樹脂組成物包含具有經由連接基相互鍵結之聚合性基和醯胺鍵之聚合性化合物（特定聚合性化合物）。 <Specific polymerizable compound> The resin composition of the present invention contains a polymerizable compound (specific polymerizable compound) having a polymerizable group and an amide bond mutually bonded via a linking group.

〔醯胺鍵〕 特定聚合性化合物中之醯胺鍵除了所謂之（*-C（=O）NH-#）所表示之醯胺鍵以外，還包含所謂之（*-C（=O）NR-#）所表示之取代醯胺鍵。上述*及#分別表示與其他結構的鍵結部位。 取代醯胺鍵中之取代基（上述R）並無特別限定，能夠使用公知的取代基，例如可以舉出烷基、芳香族烴基或該等組合所表示之基團等烴基。上述烴基可以進一步經鹵素原子、烷氧基、芳氧基、烷基羰基、芳基羰基、羥基、下述式（R-1）所表示之基團等取代。 [化學式32]

Figure 02_image062
式（R-1）中，R a表示1價的有機基，R b表示2價的有機基，n表示1以上的整數，m表示0或1，*表示與其他結構的鍵結部位。 式（R-1）中，R a為烴基為較佳，烷基為更佳，碳數1～10的烷基為進一步較佳。 式（R-1）中，R b為烴基為較佳，伸烷基為更佳，碳數2～10的伸烷基為進一步較佳，碳數2～4的伸烷基為特佳，伸乙基或伸丙基為最佳。在n為2以上之情況下，式（R-1）中存在n個之Rb可以分別相同，亦可以不同。 n表示1以上的整數，1～10的整數為較佳。 m為1為較佳。 又，上述烴基可以與上述取代醯胺鍵中之氮原子及和#的部位鍵結之結構中的至少一者鍵結而形成環結構。作為所形成之環結構，例如可以舉出以上述醯胺鍵中所包含之氮原子為環員之哌啶環、嗎啉環等。該等環結構可以進一步具有取代基。作為取代基，可以舉出與上述烴基中之取代基相同的基團。 在該等之中，從所產生之鹼的鹼性高且容易提高斷裂伸長率、耐藥品性的觀點考慮，特定聚合性化合物中之醯胺鍵為取代醯胺鍵為較佳，具有烴基作為取代基之取代醯胺鍵為更佳。 特定聚合性化合物可以僅具有1個醯胺鍵，亦可以具有2個以上。 又，從耐藥品性的觀點考慮，特定聚合性化合物在結構內不具有聚伸烷氧基為較佳。 [Amide bond] The amide bond in the specific polymerizable compound includes so-called (*-C(=O)NR) in addition to the amide bond represented by the so-called (*-C(=O)NH-#). -#) represents the substituted amide bond. The above-mentioned * and # represent the bonding sites with other structures, respectively. The substituent (the above-mentioned R) in the substituted amide bond is not particularly limited, and known substituents can be used, and examples thereof include hydrocarbon groups such as alkyl groups, aromatic hydrocarbon groups, or groups represented by these combinations. The above-mentioned hydrocarbon group may be further substituted with a halogen atom, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, a hydroxyl group, a group represented by the following formula (R-1), and the like. [Chemical formula 32]
Figure 02_image062
In formula (R-1), R a represents a monovalent organic group, R b represents a divalent organic group, n represents an integer of 1 or more, m represents 0 or 1, and * represents a bonding site with other structures. In the formula (R-1), R a is preferably a hydrocarbon group, more preferably an alkyl group, and even more preferably an alkyl group having 1 to 10 carbon atoms. In the formula (R-1), R b is preferably a hydrocarbon group, more preferably an alkylene group, further preferably an alkylene group having 2 to 10 carbon atoms, and particularly preferably an alkylene group having 2 to 4 carbon atoms, Ethylene or propylidene is the best. When n is 2 or more, the n Rbs in the formula (R-1) may be the same or different, respectively. n represents an integer of 1 or more, and an integer of 1 to 10 is preferable. m is preferably 1. In addition, the above-mentioned hydrocarbon group may form a ring structure by bonding to at least one of the nitrogen atom in the above-mentioned substituted amide bond and the structure bonded to the part of #. Examples of the ring structure to be formed include a piperidine ring, a morpholine ring, and the like whose ring members are the nitrogen atoms contained in the amide bond. These ring structures may further have a substituent. As a substituent, the same group as the substituent in the said hydrocarbon group is mentioned. Among these, it is preferable that the amide bond in the specific polymerizable compound is a substituted amide bond from the viewpoint of the high basicity of the generated base and the easiness to improve the elongation at break and chemical resistance, and it has a hydrocarbon group as a The substituted amide bond of the substituent is more preferable. The specific polymerizable compound may have only one amide bond, or may have two or more. In addition, from the viewpoint of chemical resistance, it is preferable that the specific polymerizable compound does not have a polyalkeneoxy group in the structure.

〔聚合性基〕 特定聚合性化合物中之聚合性基並無特別限定，例如可以舉出自由基聚合性基、陽離子聚合性基等，但是從膜收縮降低之觀點考慮，自由基聚合性基為較佳。 作為聚合性基的例子，可以舉出具有乙烯性不飽和鍵之基團、烷氧基甲基、羥甲基、醯氧基甲基、環氧基、氧環丁烷基、苯并㗁唑基、嵌段異氰酸酯基等。 在該等之中，從反應性優異且膜收縮容易降低的觀點考慮，具有乙烯性不飽和鍵之基團、環氧基或氧環丁烷基為較佳。 [Polymerizable group] Although the polymerizable group in a specific polymerizable compound is not specifically limited, For example, a radical polymerizable group, a cationic polymerizable group, etc. are mentioned, However, a radical polymerizable group is preferable from a viewpoint of film shrinkage reduction. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a methylol group, an acyloxymethyl group, an epoxy group, an oxetanyl group, and a benzoxazole. group, blocked isocyanate group, etc. Among these, a group having an ethylenically unsaturated bond, an epoxy group, or an oxetanyl group is preferable from the viewpoint of excellent reactivity and easy reduction of film shrinkage.

作為具有上述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、順丁烯二醯亞胺基等，從反應性優異且膜收縮容易降低的觀點考慮，具有與乙烯基直接鍵結之芳香環之基團、（甲基）丙烯醯胺基或（甲基）丙烯醯氧基為較佳，具有與乙烯基直接鍵結之芳香環之基團或（甲基）丙烯醯氧基為更佳。Examples of the group having the above-mentioned ethylenically unsaturated bond include vinyl group, allyl group, isoallyl group, 2-methallyl group, and group having an aromatic ring directly bonded to vinyl group (for example, , vinylphenyl, etc.), (meth)acrylamido, (meth)acryloyloxy, maleimide, etc., from the viewpoint of excellent reactivity and easy reduction of film shrinkage, have A group of an aromatic ring directly bonded to a vinyl group, a (meth)acrylamido group or a (meth)acryloyloxy group is preferable, and a group of an aromatic ring directly bonded to a vinyl group or (methyl) group) acryloxy is more preferred.

又，上述環氧基可以構成非環式環氧基（例如，環氧丙基、氧化苯乙烯結構等），亦可以構成脂環式環氧基（例如，3,4-環氧環己基結構等）。In addition, the above epoxy group may constitute an acyclic epoxy group (eg, glycidyl, styrene oxide structure, etc.), or may constitute an alicyclic epoxy group (eg, 3,4-epoxycyclohexyl structure) Wait).

特定聚合性化合物可以僅具有1個聚合性基，亦可以具有2個以上。從能夠實現適當的交聯密度之觀點考慮，特定聚合性化合物僅具有1個聚合性基之態樣亦為本發明的較佳態樣之一。 在特定聚合性化合物具有2個以上的聚合性基之情況下，特定聚合性化合物例如可以具有2個以上的具有乙烯性不飽和鍵之基團，亦可以合計具有2個以上的具有乙烯性不飽和鍵之基團和環氧基等不同種類的聚合性基。 The specific polymerizable compound may have only one polymerizable group, or may have two or more. From the viewpoint of realizing an appropriate crosslinking density, the aspect in which the specific polymerizable compound has only one polymerizable group is also one of the preferred aspects of the present invention. When the specific polymerizable compound has two or more polymerizable groups, the specific polymerizable compound may have, for example, two or more groups having an ethylenically unsaturated bond, or may have a total of two or more groups having an ethylenically unsaturated bond. Various types of polymerizable groups such as saturated bond groups and epoxy groups.

〔連接基〕 作為連接基，並無特別限定，但是烴基或1個以上的烴基與選自包括、-O-、-S-、-C（=O）-、-S（=O） 2-及-NR N-之群組中的至少1種結構的鍵結所表示之基團為較佳。R N表示氫原子或1價的取代基，氫原子或烴基為較佳，氫原子、烷基或芳香族烴基為更佳。 作為上述烴基，飽和脂肪族烴基、芳香族烴基或該等鍵結所表示之基團為較佳。 作為上述飽和脂肪族烴基，碳數1～20的飽和脂肪族烴基為較佳，碳數1～10的飽和脂肪族烴基為更佳。又，在本發明中，除非另有說明，則在飽和脂肪族烴基、烷基、伸烷基等的記載中均包含直鏈狀、支鏈狀、環狀或該等組合所表示之結構中的任一個。 作為上述芳香族烴基，可以舉出碳數6～20的芳香族烴基，從苯環或萘環去除複數個氫原子而獲得之基團為較佳，從苯環去除複數個氫原子而獲得之基團為更佳。 從所獲得之硬化物的斷裂伸長率及耐藥品性的觀點考慮，連接基包含脂肪族烴環基或芳香族烴基作為上述烴基為較佳，包含芳香族烴基為更佳，包含從苯環去除複數個氫原子而獲得之基團為進一步較佳。 作為上述脂肪族烴環基，並無特別限定，但是可以舉出從二環戊烷環、冰片烯（bornene）環、異冰片烯環或金剛烷環去除複數個氫原子而獲得之基團等。 作為上述芳香族烴基，可以舉出碳數6～20的芳香族烴基，從苯環或萘環去除複數個氫原子而獲得之基團為較佳，從苯環去除複數個氫原子而獲得之基團為更佳。 又，上述芳香族烴基或上述脂肪族烴環基可以與其他環縮合。作為該種態樣的例子，可以舉出從鄰苯二甲醯亞胺環去除複數個氫原子而獲得之基團等。 又，上述烴基可以具有取代基。作為取代基，在可以獲得本發明的效果之範圍內並無特別限定，能夠使用公知的取代基，例如可以較佳地舉出羥基、羧基等。 [Linking group] The linking group is not particularly limited, but a hydrocarbon group or one or more hydrocarbon groups and a group selected from the group consisting of, -O-, -S-, -C(=O)-, -S(=O) 2 - The group represented by the bond of at least one structure in the group of -NR N - is preferable. R N represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by these bonds are preferable. As the above-mentioned saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferable. Moreover, in the present invention, unless otherwise specified, the descriptions of saturated aliphatic hydrocarbon groups, alkyl groups, alkylene groups, etc. all include linear, branched, cyclic, or structures represented by these combinations. any of the . Examples of the above-mentioned aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms, preferably a group obtained by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring, and a group obtained by removing a plurality of hydrogen atoms from a benzene ring group is better. From the viewpoints of elongation at break and chemical resistance of the cured product obtained, it is preferable that the linking group contains an aliphatic hydrocarbon ring group or an aromatic hydrocarbon group as the hydrocarbon group, more preferably an aromatic hydrocarbon group, including those removed from the benzene ring. A group obtained by a plurality of hydrogen atoms is further preferred. The aliphatic hydrocarbon ring group is not particularly limited, and examples thereof include groups obtained by removing a plurality of hydrogen atoms from a dicyclopentane ring, a bornene ring, an isobornene ring, or an adamantane ring. . Examples of the above-mentioned aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms, preferably a group obtained by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring, and a group obtained by removing a plurality of hydrogen atoms from a benzene ring group is better. In addition, the above-mentioned aromatic hydrocarbon group or the above-mentioned aliphatic hydrocarbon ring group may be condensed with another ring. As an example of this aspect, the group etc. obtained by removing a some hydrogen atom from a phthalimide ring are mentioned. Moreover, the said hydrocarbon group may have a substituent. The substituent is not particularly limited as long as the effects of the present invention can be obtained, and known substituents can be used, for example, a hydroxyl group, a carboxyl group, and the like can be preferably used.

在該等之中，作為連接基，經羥基取代之烴基或經羧基取代之烴基為更佳。 連接基中之烴基的較佳態樣如上所述。 Among these, as the linking group, a hydrocarbon group substituted with a hydroxyl group or a hydrocarbon group substituted with a carboxyl group is more preferable. Preferred aspects of the hydrocarbyl group in the linking group are as described above.

〔鍵結位置〕 特定聚合性化合物中之上述醯胺鍵與上述連接基在羰基側鍵結。 特定聚合性化合物中之醯胺鍵的羰基側是指上述（*-C（=O）NH-#）或（*-C（=O）NR-#）中之*側。 又，從所獲得之硬化物的斷裂伸長率的觀點考慮，特定聚合性化合物在醯胺鍵的胺基側（上述（*-C（=O）NH-#）或（*-C（=O）NR-#）中之#側）不具有聚合性基為較佳。 [bonding position] The above-mentioned amide bond in the specific polymerizable compound and the above-mentioned linking group are bonded on the carbonyl side. The carbonyl side of the amide bond in the specific polymerizable compound refers to the * side in the above (*-C(=O)NH-#) or (*-C(=O)NR-#). In addition, from the viewpoint of the elongation at break of the obtained cured product, the specific polymerizable compound is on the amine group side of the amide bond (the above-mentioned (*-C(=O)NH-#) or (*-C(=O) It is preferable that the # side) in ) NR-#) does not have a polymerizable group.

〔鹼產生能〕 在使用特定聚合性化合物合成了單聚物的情況下，上述單聚物顯示藉由在250℃下進行加熱而產生從主鏈游離之鹼之性質。 具體而言，在特定聚合性化合物具有自由基聚合性基之情況下，使用V-601（二甲基 2,2'-偶氮雙（2-甲基丙酸酯））作為聚合起始劑，在溶劑環己酮中進行聚合反應，從而合成分子量為10,000左右的單聚物。 在特定聚合性化合物具有陽離子聚合性基之情況下，使用對甲苯磺酸作為聚合起始劑，在溶劑環己酮中進行聚合反應，從而合成分子量為10,000左右的單聚物。 之後，在將所獲得之單聚物藉由過濾而獲取並在密封容器中1氣壓、250℃、3小時的條件下進行加熱之情況下，在源自特定聚合性化合物之醯胺鍵中的1個數%以上產生鹼時，上述單聚物顯示藉由在250℃下進行加熱而產生從主鏈游離之鹼之性質。 上述個數%為10個數%以上為較佳，30個數%以上為更佳。上限並無特別限定，可以為100個數%。 又，與藉由上述加熱而產生鹼之後殘存酸酐基者相比，特定聚合性化合物為在上述樹脂中殘存內酯結構者為較佳。 [Alkali generating energy] When a monomer is synthesized using a specific polymerizable compound, the above-mentioned monomer exhibits a property of generating a base free from the main chain by heating at 250°C. Specifically, when the specific polymerizable compound has a radical polymerizable group, V-601 (dimethyl 2,2'-azobis(2-methylpropionate)) is used as a polymerization initiator , polymerized in the solvent cyclohexanone to synthesize a monomer with a molecular weight of about 10,000. When the specific polymerizable compound has a cationically polymerizable group, a monomer having a molecular weight of about 10,000 is synthesized by performing a polymerization reaction in a solvent cyclohexanone using p-toluenesulfonic acid as a polymerization initiator. Then, in the case where the obtained monomer was obtained by filtration and heated in a sealed container under the conditions of 1 atmosphere, 250° C., and 3 hours, in the amide bond derived from the specific polymerizable compound When 1 several% or more of the base is generated, the above-mentioned monomer exhibits the property of generating the base free from the main chain by heating at 250°C. The above number % is preferably 10 number % or more, and more preferably 30 number % or more. The upper limit is not particularly limited, and may be 100 several %. Moreover, it is preferable that the specific polymerizable compound has a lactone structure which remains in the said resin, rather than the thing which an acid anhydride group remains after generating an alkali by the said heating.

〔鹼〕 從所獲得之硬化物的斷裂伸長率等觀點考慮，從特定聚合性化合物產生之鹼為胺為較佳，二級胺為更佳。 又，在從特定聚合性化合物產生胺之情況下，胺可以為脂肪族胺，亦可以為芳香族胺，但是從抑制硬化膜的收縮之觀點考慮，具有芳香環結構之胺為較佳。作為上述芳香環結構，並無特別限定，但是芳香族烴環結構為較佳，苯環結構為更佳。 所產生之鹼的分子量為70～500為較佳，80～300為更佳，90～220為進一步較佳。 所產生之鹼為共軛酸的pKa為0以上之鹼為較佳，3以上之鹼為更佳，6以上之鹼為更佳。上述共軛酸的pKa的下限並無特別限定，但是30以下為較佳。 pKa為考慮到從酸中釋放氫離子之解離反應而將其平衡常數Ka用其負的常用對數pKa表示者。在本說明書中，除非另有說明，則pKa設為基於ACD/ChemSketch（註冊商標）之計算值。 在存在複數個上述共軛酸的pKa之情況下，至少1個在上述範圍內為較佳。 (alkali) From the viewpoints of elongation at break of the obtained cured product, etc., the base derived from the specific polymerizable compound is preferably an amine, and more preferably a secondary amine. Moreover, when generating an amine from a specific polymerizable compound, an aliphatic amine may be sufficient as an amine, and an aromatic amine may be sufficient, but the amine which has an aromatic ring structure is preferable from a viewpoint of suppressing the shrinkage of a cured film. Although it does not specifically limit as said aromatic ring structure, An aromatic hydrocarbon ring structure is preferable, and a benzene ring structure is more preferable. The molecular weight of the generated base is preferably 70-500, more preferably 80-300, and further preferably 90-220. The resulting base is preferably a conjugate acid with a pKa of 0 or more, more preferably a base of 3 or more, and more preferably a base of 6 or more. The lower limit of the pKa of the conjugate acid is not particularly limited, but 30 or less is preferable. The pKa is expressed by the negative logarithm pKa of the equilibrium constant Ka taking into account the dissociation reaction releasing hydrogen ions from the acid. In this specification, unless otherwise specified, pKa is set as a calculated value based on ACD/ChemSketch (registered trademark). When there are plural pKas of the above conjugated acids, at least one is preferably within the above range.

作為所產生之鹼的具體例，並無特別限定，但是例如可以舉出下述結構的鹼等。 [化學式33]

Figure 02_image064
又，在上述結構中之二甲基哌啶環中存在順式和反式，但是可以為任一個。其中，從所獲得之硬化物的斷裂伸長率的觀點考慮，順式為較佳。 與順式相比，反式在氮原子周圍數量稍微增加。藉此，順式更容易使基質化合物接近活性部位的氮原子，從而提高醯亞胺化促進效果，斷裂伸長率優異。另一方面，即使為順式，亦具有難以與樹脂進行反應程度之數量。依據以上理由，與反式相比，順式在維持其他性能的同時，斷裂伸長率優異。 Although it does not specifically limit as a specific example of the base to generate|occur|produce, For example, the base of the following structure etc. are mentioned. [Chemical formula 33]
Figure 02_image064
Moreover, in the dimethylpiperidine ring in the above-mentioned structure, there are cis and trans, but either of them may be used. Among them, the cis-form is preferred from the viewpoint of the elongation at break of the obtained cured product. Compared to cis, trans has a slightly increased number around nitrogen atoms. As a result, the cis-form can more easily bring the matrix compound closer to the nitrogen atom of the active site, thereby enhancing the imidization promoting effect, and being excellent in elongation at break. On the other hand, even if it is a cis-form, it has a quantity which is difficult to react with a resin. For the above reasons, the cis-form is superior in elongation at break while maintaining other properties than the trans-form.

〔式（1-1）所表示之化合物〕 特定聚合性化合物為下述式（1-1）所表示之化合物為較佳。 [化學式34]

Figure 02_image066
式（1-1）中，R 1分別獨立地為氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，R 2分別獨立地為氫原子、鹵素原子或1價的有機基，至少2個R 2可以鍵結而形成環結構，L 1表示3價的有機基。 [Compound Represented by Formula (1-1)] The specific polymerizable compound is preferably a compound represented by the following formula (1-1). [Chemical formula 34]
Figure 02_image066
In formula (1-1), R 1 is independently a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, and R 2 is independently a hydrogen atom, a halogen atom or a monovalent organic group. In the organic group, at least two R 2 can be bonded to form a ring structure, and L 1 represents a trivalent organic group.

-R 1- 從提高斷裂伸長率的觀點考慮，式（1-1）中，R 1分別獨立地為1價的有機基為較佳。 R 1為烴基為較佳，烷基、芳香族烴基或該等組合所表示之基團為更佳，碳數1～10的烷基、碳數6～20的芳香族烴基或該等組合所表示之基團為進一步較佳，碳數1～10的烷基為特佳。 作為上述烷基，可以為直鏈狀、支鏈狀、環狀中的任一個，但是從提高斷裂伸長率的觀點考慮，支鏈狀的烷基（例如，異丙基、異丁基、第三丁基、2-乙基己基等）或環狀的烷基（例如，環己基等）為較佳。 R 1可以具有取代基，作為取代基，可以舉出鹵素原子、烷氧基、芳氧基、烷基羰基、芳基羰基、羥基、上述式（R-1）所表示之基團等。 作為2個R 1鍵結而形成之環結構，例如可以舉出以上述醯胺鍵中所包含之氮原子為環員之哌啶環、嗎啉環等。該等環結構可以進一步具有取代基。作為取代基，可以舉出與上述烴基中之取代基相同的基團。 -R 1 - In the formula (1-1), R 1 is preferably a monovalent organic group independently from the viewpoint of improving the elongation at break. R 1 is preferably a hydrocarbon group, preferably an alkyl group, an aromatic hydrocarbon group or a group represented by these combinations, an alkyl group with 1 to 10 carbon atoms, an aromatic hydrocarbon group with 6 to 20 carbon atoms or a combination of these groups. The group represented is further preferable, and an alkyl group having 1 to 10 carbon atoms is particularly preferable. The above-mentioned alkyl group may be linear, branched, or cyclic, but from the viewpoint of improving the elongation at break, branched alkyl groups (for example, isopropyl, isobutyl, tributyl, 2-ethylhexyl, etc.) or cyclic alkyl groups (eg, cyclohexyl, etc.) are preferred. R 1 may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, a hydroxyl group, a group represented by the above formula (R-1), and the like. As a ring structure formed by two R 1 bonds, for example, a piperidine ring, a morpholine ring, etc., in which the nitrogen atom contained in the above-mentioned amide bond is a ring member, can be mentioned. These ring structures may further have a substituent. As a substituent, the same group as the substituent in the said hydrocarbon group is mentioned.

作為R 1的較佳態樣的例子，可以舉出下述結構。下述具體例的結構中所包含之氮原子表示式（1-1）中的醯胺鍵中所包含之氮原子。在下述具體例中，*表示與羰基的鍵結部位。 [化學式35]

Figure 02_image068
在上述結構中之二甲基哌啶環中存在順式和反式，但是可以為任一個。其中，從所獲得之硬化物的斷裂伸長率的觀點考慮，順式為較佳。順式為較佳的理由如上所述。 As an example of a preferable aspect of R< 1 >, the following structures are mentioned. The nitrogen atom contained in the structure of the following specific example represents the nitrogen atom contained in the amide bond in Formula (1-1). In the following specific examples, * represents a bonding site with a carbonyl group. [Chemical formula 35]
Figure 02_image068
Cis and trans are present in the dimethylpiperidine ring in the above structure, but may be either. Among them, the cis-form is preferred from the viewpoint of the elongation at break of the obtained cured product. The reason why cis is preferred is as described above.

-R 2- R 2分別獨立地為氫原子、鹵素原子或1價的有機基，氫原子或1價的有機基為較佳，氫原子、甲基、乙基或羥甲基為更佳，氫原子或甲基為特佳。 在R 2為鹵素原子之情況下，氟原子、氯原子、溴原子或碘原子為較佳，氟原子或氯原子為更佳。 尤其，與和L 1相鄰之碳原子鍵結之R 2為氫原子、甲基、乙基或羥甲基且其他2個R 2為氫原子為較佳，與和L 1相鄰之碳原子鍵結之R 2為氫原子或甲基且其他2個R 2為氫原子為更佳。 -R 2 - R 2 are independently a hydrogen atom, a halogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group, more preferably a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, A hydrogen atom or a methyl group is particularly preferred. When R 2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom is preferable, and a fluorine atom or a chlorine atom is more preferable. In particular, R 2 bonded to the carbon atom adjacent to L 1 is a hydrogen atom, methyl, ethyl or hydroxymethyl, and the other two R 2 are preferably hydrogen atoms, and the carbon atom adjacent to L 1 is preferably More preferably, R 2 of atomic bonding is a hydrogen atom or a methyl group and the other two R 2 are hydrogen atoms.

-L 1- L 1並無特別限定，但是烴基或1個以上的烴基與選自包括、-O-、-S-、-C（=O）-、-S（=O） 2-及-NR N-之群組中的至少1種結構的鍵結所表示之基團為較佳。R N如上所述。 作為上述烴基，飽和脂肪族烴基、芳香族烴基或該等鍵結所表示之基團為較佳。 作為上述飽和脂肪族烴基，碳數1～20的飽和脂肪族烴基為較佳，碳數1～10的飽和脂肪族烴基為更佳。 作為上述芳香族烴基，可以舉出碳數6～20的芳香族烴基，從苯環或萘環去除複數個氫原子而獲得之基團為較佳，從苯環去除複數個氫原子而獲得之基團為更佳。 作為上述脂肪族烴基，可以使用脂肪族烴環基。作為脂肪族烴環基，並無特別限定，但是可以舉出從二環戊烷環、冰片烯（bornene）環、異冰片烯環或金剛烷環去除複數個氫原子而獲得之基團等。 作為上述芳香族烴基，可以舉出碳數6～20的芳香族烴基，從苯環或萘環去除複數個氫原子而獲得之基團為較佳，從苯環去除複數個氫原子而獲得之基團為更佳。 又，上述芳香族烴基或上述脂肪族烴環基可以與其他環縮合。作為該種態樣的例子，可以舉出從鄰苯二甲醯亞胺環去除複數個氫原子而獲得之基團等。 從所獲得之硬化物的斷裂伸長率及耐藥品性的觀點考慮，L 1包含芳香族烴基作為上述烴基為較佳，包含從苯環去除複數個氫原子而獲得之基團為更佳。 又，從鹼的產生效率的觀點考慮，在L 1包含芳香族烴基之情況下，L 1中之芳香族烴基與式（1-1）中的OH基直接鍵結、僅經由1個亞甲基鍵結或僅經由1個羰基鍵結為較佳，直接鍵結為更佳。在L 1中之芳香族烴基與式（1-1）中的羥基直接鍵結之情況下，上述羥基和L 1中之芳香族烴基與醯胺鍵直接或經由連接基連接之部位存在於L 1中之芳香族烴基中之鄰接位置上為較佳。鄰接位置表示在芳香族烴基中某個取代基所鍵結之環員和另一個取代基所鍵結之環員為在芳香族烴基中之相鄰之環員，在芳香族烴基為苯環之情況下，表示鄰位。 -L 1 - L 1 is not particularly limited, but a hydrocarbon group or one or more hydrocarbon groups and a hydrocarbon group selected from the group consisting of, -O-, -S-, -C(=O)-, -S(=O) 2 - and - The group represented by the bond of at least one structure in the group of NR N - is preferable. R N is as described above. As the above-mentioned hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by these bonds are preferable. As the above-mentioned saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferable. Examples of the above-mentioned aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms, preferably a group obtained by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring, and a group obtained by removing a plurality of hydrogen atoms from a benzene ring group is better. As the above-mentioned aliphatic hydrocarbon group, an aliphatic hydrocarbon ring group can be used. The aliphatic hydrocarbon ring group is not particularly limited, and examples thereof include groups obtained by removing a plurality of hydrogen atoms from a dicyclopentane ring, a bornene ring, an isobornene ring, or an adamantane ring. Examples of the above-mentioned aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 20 carbon atoms, preferably a group obtained by removing a plurality of hydrogen atoms from a benzene ring or a naphthalene ring, and a group obtained by removing a plurality of hydrogen atoms from a benzene ring group is better. In addition, the above-mentioned aromatic hydrocarbon group or the above-mentioned aliphatic hydrocarbon ring group may be condensed with another ring. As an example of this aspect, the group etc. obtained by removing a some hydrogen atom from a phthalimide ring are mentioned. From the viewpoints of elongation at break and chemical resistance of the cured product obtained, it is preferable that L 1 contains an aromatic hydrocarbon group as the above-mentioned hydrocarbon group, and it is more preferable that it contains a group obtained by removing a plurality of hydrogen atoms from a benzene ring. In addition, from the viewpoint of the efficiency of generating the base, when L 1 contains an aromatic hydrocarbon group, the aromatic hydrocarbon group in L 1 is directly bonded to the OH group in the formula (1-1) through only one methylene group. It is preferable to bond with a radical or to bond via only one carbonyl group, and it is more preferable to bond directly. In the case where the aromatic hydrocarbon group in L 1 is directly bonded to the hydroxyl group in the formula (1-1), the site where the above-mentioned hydroxyl group and the aromatic hydrocarbon group in L 1 and the amide bond are connected directly or via a linking group is present in L The adjoining position in the aromatic hydrocarbon group in 1 is preferable. The adjacent position means that the ring member bonded to a substituent in an aromatic hydrocarbon group and the ring member bonded to another substituent are the adjacent ring members in the aromatic hydrocarbon group, and in the aromatic hydrocarbon group, it is the ring member between the benzene ring. case, indicates the adjacent position.

作為L 1的較佳態樣的例子，可以舉出下述結構。下述具體例的結構中所包含之與*鍵結之羰基表示式（1-1）中的醯胺鍵中所包含之羰基。在下述具體例中，*表示與式（1-1）中的羰基的鍵結部位，#表示與式（1-1）中的R 2所鍵結之碳原子的鍵結部位。 [化學式36]

Figure 02_image070
As an example of a preferable aspect of L1, the following structures can be mentioned. The carbonyl group bonded to * included in the structure of the following specific example represents the carbonyl group included in the amide bond in the formula (1-1). In the following specific examples, * represents the bonding site to the carbonyl group in the formula (1-1), and # represents the bonding site to the carbon atom to which R 2 in the formula (1-1) is bonded. [Chemical formula 36]
Figure 02_image070

〔式（1-2）所表示之化合物〕 特定聚合性化合物為下述式（1-2）所表示之化合物亦較佳。 [化學式37]

Figure 02_image072
式（1-2）中，R 1分別獨立地表示氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，L 2表示單鍵或2價的連接基，Cy表示環結構，L 3表示單鍵或2價的連接基，R 2分別獨立地表示氫原子、鹵素原子或1價的有機基，至少2個R 2可以鍵結而形成環結構。 [Compound Represented by Formula (1-2)] It is also preferable that the specific polymerizable compound is a compound represented by the following formula (1-2). [Chemical formula 37]
Figure 02_image072
In formula (1-2), R 1 independently represents a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, L 2 represents a single bond or a divalent linking group, and Cy represents a ring Structure, L 3 represents a single bond or a divalent linking group, R 2 independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and at least two R 2 can be bonded to form a ring structure.

-R 1、R 2- 式（1-2）中，R 1及R 2分別與式（1-1）中的R 1及R 2的含義相同，較佳態樣亦相同。 -R 1 , R 2 - In the formula (1-2), R 1 and R 2 have the same meanings as R 1 and R 2 in the formula (1-1), respectively, and the preferred embodiments are also the same.

-L 2- 式（1-2）中，L 2表示單鍵或2價的連接基，單鍵或者烴基或1個以上的烴基與選自包括-O-、-S-、-C（=O）-、-S（=O） 2-及-NR N-之群組中的至少1種結構的鍵結所表示之基團為較佳，單鍵或者烴基或1個以上的烴基與選自包括-O-及-C（=O）-之群組中的至少1種結構的鍵結所表示之基團為更佳。R N如上所述。 作為上述烴基，伸烷基、2價的芳香族烴基或該等鍵結所表示之基團為較佳。 作為上述伸烷基，碳數1～20的伸烷基為較佳，碳數1～10的伸烷基為更佳。 作為上述2價的芳香族烴基，可以舉出碳數6～20的芳香族烴基，伸苯基或伸萘基為較佳，伸苯基為更佳。 -L 2 - In formula (1-2), L 2 represents a single bond or a divalent linking group, a single bond or a hydrocarbon group or one or more hydrocarbon groups and is selected from the group consisting of -O-, -S-, -C (= The group represented by the bond of at least one structure in the group of O)-, -S(=O) 2 - and -NR N - is preferably, a single bond or a hydrocarbon group or one or more hydrocarbon groups and optional The group represented by the bond of at least one structure from the group including -O- and -C(=O)- is more preferable. R N is as described above. As the above-mentioned hydrocarbon group, an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by these bonds are preferable. As the above-mentioned alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable. As the above-mentioned divalent aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is mentioned, a phenylene group or a naphthylene group is preferable, and a phenylene group is more preferable.

-Cy- 式（1-2）中，Cy表示環結構。 作為環結構，可以為脂肪族環結構和芳香族環結構中的任一個，但是芳香族環結構為較佳。 又，可以為烴環結構和雜環結構中的任一個，但是烴環結構為較佳。作為上述雜環結構中所包含之雜原子，可以舉出氧原子、硫原子、氮原子等。又，作為上述雜環結構，可以舉出芳香族雜環結構，可以較佳地舉出吡咯、吲哚、呋喃、苯并呋喃、噻吩、苯并噻吩等。 從鹼的產生效率的觀點考慮，在該等之中，Cy為脂肪族烴環結構或芳香族烴環結構為較佳。 作為上述脂肪族烴環結構，可以舉出二環戊烷環、冰片烯環、異冰片烯環、金剛烷環等，二環戊烷環為較佳。 作為上述芳香族烴環結構，碳數6～20的芳香族烴環結構為較佳，苯環結構或萘環結構為更佳，苯環結構為進一步較佳。 又，上述芳香族烴環結構或上述脂肪族烴環結構可以與其他環縮合。作為該種態樣的例子，可以舉出鄰苯二甲醯亞胺環結構等。 從鹼的產生效率的觀點考慮，在該等之中，Cy為二環戊烷環結構或苯環結構為較佳，苯環結構為更佳。 又，Cy可以具有取代基。 作為Cy中之取代基，可以舉出羥基、羧基、腈基、羥甲基等，從鹼的產生效率的觀點考慮，羥基為較佳。 在Cy為芳香環（較佳為，芳香族烴環）且具有取代基之情況下，從鹼的產生效率的觀點考慮，Cy中之取代基的位置為Cy中之與L 2鄰接之位置為較佳。 例如，在Cy為苯環之情況下，相對於L 2在鄰位具有羥基等取代基為較佳。 -Cy- In formula (1-2), Cy represents a ring structure. The ring structure may be either an aliphatic ring structure or an aromatic ring structure, but an aromatic ring structure is preferred. Moreover, any of a hydrocarbon ring structure and a heterocyclic structure may be sufficient, but a hydrocarbon ring structure is preferable. As a hetero atom contained in the said heterocyclic structure, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Moreover, as said heterocyclic structure, an aromatic heterocyclic structure is mentioned, Preferably, a pyrrole, an indole, a furan, a benzofuran, a thiophene, a benzothiophene, etc. are mentioned. Among these, Cy is preferably an aliphatic hydrocarbon ring structure or an aromatic hydrocarbon ring structure from the viewpoint of the generation efficiency of the base. As said aliphatic hydrocarbon ring structure, a dicyclopentane ring, a bornene ring, an isobornene ring, an adamantane ring, etc. are mentioned, A dicyclopentane ring is preferable. As the above-mentioned aromatic hydrocarbon ring structure, an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms is preferable, a benzene ring structure or a naphthalene ring structure is more preferable, and a benzene ring structure is further preferable. In addition, the above-mentioned aromatic hydrocarbon ring structure or the above-mentioned aliphatic hydrocarbon ring structure may be condensed with another ring. As an example of this aspect, a phthalimide ring structure etc. are mentioned. Among these, Cy is preferably a dicyclopentane ring structure or a benzene ring structure, and more preferably a benzene ring structure, from the viewpoint of the efficiency of generating the base. In addition, Cy may have a substituent. Examples of the substituent in Cy include a hydroxyl group, a carboxyl group, a nitrile group, a methylol group, and the like, and a hydroxyl group is preferred from the viewpoint of the generation efficiency of the base. When Cy is an aromatic ring (preferably, an aromatic hydrocarbon ring) and has a substituent, the position of the substituent in Cy is the position adjacent to L 2 in Cy from the viewpoint of the generation efficiency of the base. better. For example, when Cy is a benzene ring, it is preferable to have a substituent such as a hydroxyl group at the ortho position with respect to L 2 .

-L 3- 式（1-2）中，L 3表示單鍵或2價的連接基，單鍵或者烴基或1個以上的烴基與選自包括-O-、-S-、-C（=O）-、-S（=O） 2-及-NR N-之群組中的至少1種結構的鍵結所表示之基團為較佳，單鍵或者烴基或1個以上的烴基與選自包括-O-及-C（=O）-之群組中的至少1種結構的鍵結所表示之基團為更佳。R N如上所述。 作為上述烴基，伸烷基、芳香族烴基或該等鍵結所表示之基團為較佳，碳數1～20的伸烷基、碳數6～20的芳香族烴基或該等鍵結所表示之基團為更佳，碳數1～10的伸烷基為進一步較佳。 在該等之中，L 3為單鍵或-C（=O）O-R-、-C（=O）NR N-R-、伸烷基、（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）或該等鍵結2個以上而表示之基團為較佳。上述R表示2價的烴基，伸烷基為較佳，碳數1～10的伸烷基為更佳。又，上述-C（=O）O-R-或-C（=O）NR N-R-的方向並無特別限定，但是從反應性的觀點考慮，均在R側與Cy鍵結為較佳。 -L 3 - In formula (1-2), L 3 represents a single bond or a divalent linking group, a single bond or a hydrocarbon group or one or more hydrocarbon groups and is selected from the group consisting of -O-, -S-, -C (= The group represented by the bond of at least one structure in the group of O)-, -S(=O) 2 - and -NR N - is preferably, a single bond or a hydrocarbon group or one or more hydrocarbon groups and optional The group represented by the bond of at least one structure from the group including -O- and -C(=O)- is more preferable. R N is as described above. As the above-mentioned hydrocarbon group, alkylene groups, aromatic hydrocarbon groups, or groups represented by these bonds are preferable, and alkylene groups having 1 to 20 carbon atoms, aromatic hydrocarbon groups having 6 to 20 carbon atoms, or groups represented by these bonds are preferable. The group represented is more preferable, and the alkylene group having 1 to 10 carbon atoms is further preferable. Among these, L 3 is a single bond or -C(=O)OR-, -C(=O)NR N -R-, alkylene, (poly)alkaneoxy (carbon of the alkylene The number of repetitions is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3) or the like A group represented by two or more bonds is preferable. The above R represents a divalent hydrocarbon group, preferably an alkylene group, and more preferably an alkylene group having 1 to 10 carbon atoms. The direction of the above -C(=O)OR- or -C(=O)NR N -R- is not particularly limited, but from the viewpoint of reactivity, both are preferably bonded to Cy on the R side.

〔式（1-3）所表示之化合物〕 特定聚合性化合物為下述式（1-3）所表示之化合物亦較佳。 [化學式38]

Figure 02_image074
式（1-3）中，R 1分別獨立地表示氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，L 2表示2價的連接基，R 2分別獨立地表示氫原子、鹵素原子或1價的有機基，並且可以鍵結而形成環結構。 [Compound Represented by Formula (1-3)] It is also preferable that the specific polymerizable compound is a compound represented by the following formula (1-3). [Chemical formula 38]
Figure 02_image074
In formula (1-3), R 1 each independently represents a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, L 2 represents a divalent linking group, and R 2 each independently represents A hydrogen atom, a halogen atom or a monovalent organic group can be bonded to form a ring structure.

-R 1、R 2、L 2- 式（1-3）中，R 1及R 2分別與式（1-1）中的R 1及R 2的含義相同，較佳態樣亦相同。 式（1-3）中，L 2除了不包含單鍵以外，與式（1-2）中的L 2的含義相同，較佳態樣亦相同。 -R 1 , R 2 , L 2 - In formula (1-3), R 1 and R 2 have the same meanings as R 1 and R 2 in formula (1-1), respectively, and the preferred embodiments are also the same. In the formula (1-3), L 2 has the same meaning as L 2 in the formula (1-2) except that it does not contain a single bond, and the preferred aspects are also the same.

〔分子量〕 特定聚合性化合物的分子量為100～1,000為較佳，100～800為更佳，150～500為進一步較佳。 上述分子量只要為上述下限以上，則容易獲得斷裂伸長率優異之硬化膜。又，上述分子量只要為上述上限以下，則容易抑制硬化膜的膜收縮。 [Molecular weight] The molecular weight of the specific polymerizable compound is preferably 100 to 1,000, more preferably 100 to 800, and even more preferably 150 to 500. As long as the said molecular weight is more than the said minimum, it becomes easy to obtain the cured film which is excellent in the elongation at break. Moreover, as long as the said molecular weight is below the said upper limit, it becomes easy to suppress the film shrinkage of a cured film.

作為特定聚合性化合物的具體例，可以舉出下述化合物。 [化學式39]

Figure 02_image076
[化學式40]
Figure 02_image078
[化學式41]
Figure 02_image080
[化學式42]
Figure 02_image082
[化學式43]
Figure 02_image084
Specific examples of the specific polymerizable compound include the following compounds. [Chemical formula 39]
Figure 02_image076
[Chemical formula 40]
Figure 02_image078
[Chemical formula 41]
Figure 02_image080
[Chemical formula 42]
Figure 02_image082
[Chemical formula 43]
Figure 02_image084

（合成方法） 特定聚合性化合物例如能夠藉由後述實施例中所記載的方法來合成。 (resolve resolution) The specific polymerizable compound can be synthesized, for example, by the method described in the following Examples.

特定聚合性化合物的含量相對於本發明的樹脂組成物的總固體成分為0.5～20質量%為較佳。下限為1質量%以上為更佳。上限為15質量%以下為更佳，10質量%以下為進一步較佳。 特定聚合性化合物可以單獨使用1種，亦可以混合使用2種以上。在同時使用2種以上之情況下，其合計量在上述範圍內為較佳。 It is preferable that content of a specific polymerizable compound is 0.5-20 mass % with respect to the total solid content of the resin composition of this invention. The lower limit is more preferably 1 mass % or more. The upper limit is more preferably 15% by mass or less, and even more preferably 10% by mass or less. A specific polymerizable compound may be used individually by 1 type, and may be used in mixture of 2 or more types. When using 2 or more types simultaneously, it is preferable that the total amount is in the said range.

＜有機金屬錯合物＞ 從耐藥品性的觀點考慮，本發明的樹脂組成物可以包含有機金屬錯合物。 有機金屬錯合物只要為包含金屬原子之有機錯合物即可，但是包含金屬原子及有機基之錯合物為較佳，有機基對金屬原子進行配位之化合物為更佳，茂金屬化合物為進一步較佳。 在本發明中，茂金屬化合物是指具有2個可以具有取代基的環戊二烯基陰離子衍生物作為η5-配位體之有機金屬錯合物。 作為上述有機基，並無特別限定，但是烴基或由烴基與雜原子的組合形成之基團為較佳。作為雜原子，氧原子、硫原子及氮原子為較佳。 在本發明中，有機基中的至少1個為環狀基為較佳，至少2個為環狀基為更佳。 上述環狀基選自5員環的環狀基及6員環的環狀基為較佳，5員環的環狀基為更佳。 上述環狀基可以為烴環，亦可以為雜環，但是烴環為較佳。 作為5員環的環狀基，環戊二烯基為較佳。 又，本發明中所使用之有機金屬錯合物在1分子中包含2～4個環狀基為較佳。 <Organometallic complex> From the viewpoint of chemical resistance, the resin composition of the present invention may contain an organometallic complex. Organometallic complexes only need to be organic complexes containing metal atoms, but complexes containing metal atoms and organic groups are preferred, and compounds in which organic groups coordinate metal atoms are more preferred, and metallocene compounds are preferred. for further better. In the present invention, the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives which may have substituents as η5-ligands. The above-mentioned organic group is not particularly limited, but a hydrocarbon group or a group formed by a combination of a hydrocarbon group and a hetero atom is preferable. As the hetero atom, an oxygen atom, a sulfur atom and a nitrogen atom are preferable. In the present invention, at least one of the organic groups is preferably a cyclic group, and more preferably at least two of the organic groups are a cyclic group. The above-mentioned cyclic group is preferably selected from a 5-membered ring cyclic group and a 6-membered ring cyclic group, and more preferably a 5-membered ring cyclic group. The above-mentioned cyclic group may be a hydrocarbon ring or a heterocyclic ring, but a hydrocarbon ring is preferable. As the 5-membered cyclic group, a cyclopentadienyl group is preferable. In addition, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

作為有機金屬錯合物中所包含之金屬，並無特別限定，但是與第4族元素對應之金屬為較佳，選自包括鈦、鋯及鉿之群組中的至少1種金屬為更佳，選自包括鈦及鋯之群組中的至少1種金屬為進一步較佳，鈦為特佳。The metal contained in the organometallic complex is not particularly limited, but a metal corresponding to a Group 4 element is preferred, and at least one metal selected from the group consisting of titanium, zirconium and hafnium is more preferred , at least one metal selected from the group consisting of titanium and zirconium is further preferred, and titanium is particularly preferred.

有機金屬錯合物可以包含2個以上的金屬原子，亦可以僅包含1個金屬原子，但是僅包含1個金屬原子為較佳。在有機金屬錯合物包含2個以上的金屬原子之情況下，可以僅包含1種金屬原子，亦可以包含2種以上的金屬原子。The organometallic complex may contain two or more metal atoms, or may contain only one metal atom, but it is preferable to contain only one metal atom. When the organometallic complex contains two or more metal atoms, only one type of metal atom may be contained, or two or more types of metal atoms may be contained.

有機金屬錯合物為二茂鐵化合物、二茂鈦化合物、二茂鋯（Zirconocene）化合物或二茂鉿（Hafnocene）化合物為較佳，二茂鈦化合物、二茂鋯化合物或二茂鉿化合物為更佳，二茂鈦化合物或二茂鋯化合物為進一步較佳，二茂鈦化合物為特佳。The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, and a titanocene compound, a zirconocene compound or a hafnocene compound is More preferably, titanocene compounds or zirconocene compounds are further preferred, and titanocene compounds are particularly preferred.

有機金屬錯合物具有光自由基聚合起始能之態樣亦為本發明的較佳態樣之一。 在本發明中，具有光自由基聚合起始能表示能夠產生能夠藉由光的照射而開始自由基聚合之自由基（free radicals）。例如，在對包含自由基交聯劑和有機金屬錯合物之組成物照射了有機金屬錯合物吸收光且自由基交聯劑不吸收光的波長區域中的光時，能夠藉由確認自由基交聯劑有無消失來確認有無光自由基聚合起始能。在確認有無消失時，能夠依據自由基交聯劑的種類來選擇適當的方法，例如只要藉由IR測定（紅外分光測定）或HPLC測定（高效液相層析法）來確認即可。 在有機金屬錯合物具有光自由基聚合起始能之情況下，有機金屬錯合物為茂金屬化合物為較佳，二茂鈦化合物、二茂鋯化合物或二茂鉿化合物為更佳，二茂鈦化合物或二茂鋯化合物為進一步較佳，二茂鈦化合物為特佳。 在有機金屬錯合物不具有光自由基聚合起始能的情況下，有機金屬錯合物為選自包括二茂鈦化合物、四烷氧基鈦化合物、醯化鈦化合物、鈦螯合物、二茂鋯化合物及二茂鉿化合物之群組中的至少1種化合物為較佳，選自包括二茂鈦化合物、二茂鋯化合物及二茂鉿化合物之群組中的至少1種化合物為更佳，選自包括二茂鈦化合物及二茂鋯化合物之群組中的至少1種化合物為進一步較佳，二茂鈦化合物為特佳。 The aspect that the organometallic complex has the initiation energy of photo-radical polymerization is also one of the preferred aspects of the present invention. In the present invention, having photoradical polymerization initiation energy means generating free radicals capable of initiating radical polymerization by irradiation of light. For example, when a composition comprising a radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, it can be determined by The presence or absence of the radical crosslinking agent disappears to confirm the presence or absence of photoradical polymerization initiation energy. When confirming the disappearance or not, an appropriate method can be selected according to the type of the radical crosslinking agent. For example, it may be confirmed by IR measurement (infrared spectrometry) or HPLC measurement (high performance liquid chromatography). In the case that the organometallic complex has the initiation energy of photo-radical polymerization, it is preferred that the organometallic complex is a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnium compound, and two Titanocene compounds or zirconocene compounds are further preferred, and titanocene compounds are particularly preferred. In the case where the organometallic complex does not have the initiation energy of photo-radical polymerization, the organometallic complex is selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium halide compounds, titanium chelates, At least one compound selected from the group consisting of a zirconocene compound and a hafnocene compound is preferred, and at least one compound selected from the group consisting of a titanocene compound, a zirconocene compound and a hafnocene compound is more preferred. Preferably, at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds is further preferred, and titanocene compounds are particularly preferred.

有機金屬錯合物的分子量為50～2,000為較佳，100～1,000為更佳。The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

作為有機金屬錯合物，可以較佳地舉出下述式（P）所表示之化合物。 [化學式44]

Figure 02_image086
式（P）中，M為金屬原子，R分別獨立地為取代基。 上述R分別獨立地選自芳香族基、烷基、鹵素原子及烷基磺醯氧基為較佳。 As an organometallic complex, the compound represented by following formula (P) is mentioned preferably. [Chemical formula 44]
Figure 02_image086
In formula (P), M is a metal atom, and R is each independently a substituent. Preferably, the above Rs are each independently selected from an aromatic group, an alkyl group, a halogen atom and an alkylsulfonyloxy group.

式（P）中，作為M所表示之金屬原子，鐵原子、鈦原子、鋯原子或鉿原子為較佳，鈦原子、鋯原子或鉿原子為更佳，鈦原子或鋯原子為進一步較佳，鈦原子為特佳。 作為式（P）的R中之芳香族基，可以舉出碳數6～20的芳香族基，碳數6～20的芳香族烴基為較佳，可以舉出苯基、1-萘基或2-萘基等。 作為式（P）的R中之烷基，碳數1～20的烷基為較佳，碳數1～10的烷基為更佳，可以舉出甲基、乙基、丙基、辛基、異丙基、第三丁基、異戊基、2-乙基己基、2-甲基己基及環戊基等。 作為上述R中之鹵素原子，可以舉出F、Cl、Br及I。 作為構成上述R中之烷基磺醯氧基之烷基，碳數1～20的烷基為較佳，碳數1～10的烷基為更佳，可以舉出甲基、乙基、丙基、辛基、異丙基、第三丁基、異戊基、2-乙基己基、2-甲基己基及環戊基等。 上述R還可以具有取代基。作為取代基的例子，可以舉出鹵素原子（F、Cl、Br、I）、羥基、羧基、胺基、氰基、芳基、烷氧基、芳氧基、醯基、烷氧羰基、芳氧羰基、醯氧基、單烷基胺基、二烷基胺基、單芳胺基及二芳基胺基等。 In the formula (P), as the metal atom represented by M, an iron atom, a titanium atom, a zirconium atom or a hafnium atom is preferable, a titanium atom, a zirconium atom or a hafnium atom is more preferable, and a titanium atom or a zirconium atom is further preferable , titanium atoms are particularly good. Examples of the aromatic group in R of the formula (P) include aromatic groups having 6 to 20 carbon atoms, and preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenyl, 1-naphthyl or 2-naphthyl, etc. As the alkyl group in R of the formula (P), an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and methyl group, ethyl group, propyl group, and octyl group are mentioned. , isopropyl, tert-butyl, isoamyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl, etc. As the halogen atom in the above-mentioned R, F, Cl, Br and I can be mentioned. As the alkyl group constituting the alkylsulfonyloxy group in the above R, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and methyl, ethyl, and propyl groups are mentioned. base, octyl, isopropyl, tert-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl and cyclopentyl, etc. The above R may have a substituent. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryl Oxycarbonyl, acyloxy, monoalkylamine, dialkylamine, monoarylamine and diarylamine, etc.

作為有機金屬錯合物的具體例，並無特別限定，但是可以例示四異丙氧基鈦、四（2-乙基己氧基）鈦、二異丙氧基雙（乙醯乙酸乙酯）鈦、二異丙氧基雙（乙醯丙酮）鈦、雙（η5-2,4-環戊二烯-1-基）雙（2,6-二氟-3-（1H-吡咯-1-基）苯基）鈦、五甲基環戊二烯基三甲醇鈦、雙（η5-2,4-環戊二烯-1-基）雙（2,6-二氟苯基）鈦及下述化合物。 [化學式45]

Figure 02_image088
Specific examples of the organometallic complex are not particularly limited, but tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, and diisopropoxybis(ethylacetate) can be exemplified. Titanium, diisopropoxybis(acetoacetone)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl) base)phenyl)titanium, pentamethylcyclopentadienyltrimethoxide titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium and the following said compound. [Chemical formula 45]
Figure 02_image088

除此以外，亦能夠使用國際公開第2018/025738號的0078～0088段中所記載的化合物，但是並不限定於此。In addition to this, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but are not limited thereto.

有機金屬錯合物的含量相對於本發明的樹脂組成物的總固體成分為0.1～30質量%為較佳。下限為1.0質量%以上為更佳，1.5質量%以上為進一步較佳，3.0質量%以上為特佳。上限為25質量%以下為更佳。 有機金屬錯合物能夠使用1種或2種以上。在使用2種以上之情況下，合計量在上述範圍內為較佳。 The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 1.0 mass % or more, more preferably 1.5 mass % or more, and particularly preferably 3.0 mass % or more. The upper limit is more preferably 25% by mass or less. One type or two or more types of organometallic complexes can be used. When using 2 or more types, it is preferable that the total amount is in the said range.

＜其他聚合性化合物＞ 本發明的樹脂組成物進一步包含與上述特定聚合性化合物不同之聚合性化合物（以下，亦稱為“其他聚合性化合物”。）為較佳。 其他聚合性化合物為具有聚合性基之化合物，並且不對應於上述特定聚合性化合物。 具體而言，在其他聚合性化合物中，例如包含具有聚合性基而不具有醯胺鍵的化合物、聚合性基與醯胺鍵直接鍵結而不經由連接基之化合物、聚合性基與醯胺基經由連接基鍵結且醯胺鍵與連接基在胺基側鍵結之化合物及在使用聚合性化合物合成了單聚物的情況下單聚物不顯示藉由在250℃下進行加熱而產生從主鏈游離之鹼之性質的化合物。 作為其他聚合性化合物，可以舉出自由基交聯劑或其他交聯劑。 其他聚合性化合物為具有2個以上的聚合性基之化合物為較佳。 又，其他聚合性化合物具有聚伸烷氧基（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2～12為較佳，2～10為更佳，2～6為特佳）為較佳。 在該等之中，其他聚合性化合物為具有2個以上的聚合性基之化合物，並且具有聚伸烷氧基為較佳，其他聚合性化合物為具有2個以上的聚合性基之化合物，並且在聚合性基中的至少2個之間具有聚伸烷氧基為更佳。 <Other polymerizable compounds> The resin composition of the present invention preferably further contains a polymerizable compound (hereinafter, also referred to as "other polymerizable compound") different from the above-mentioned specific polymerizable compound. Other polymerizable compounds are compounds having a polymerizable group, and do not correspond to the above-mentioned specific polymerizable compounds. Specifically, among other polymerizable compounds, there are, for example, compounds having a polymerizable group but not having an amide bond, a compound having a polymerizable group and an amide bond directly bonded without going through a linking group, and a polymerizable group and an amide bond. A compound in which a group is bonded via a linking group and an amide bond and a linking group are bonded on the amine group side, and in the case of synthesizing a monomer using a polymerizable compound, the monomer does not appear to be generated by heating at 250°C A compound with the properties of a base free from the main chain. As another polymerizable compound, a radical crosslinking agent or another crosslinking agent is mentioned. The other polymerizable compound is preferably a compound having two or more polymerizable groups. In addition, the other polymerizable compound has a polyalkeneoxy group (the carbon number of the alkylene group is preferably 2-12, more preferably 2-6, particularly preferably 2 or 3; the number of repetitions is preferably 2-12 , 2 to 10 is better, 2 to 6 is particularly good) is better. Among these, the other polymerizable compound is a compound having two or more polymerizable groups, and preferably a polyalkaneoxy group, and the other polymerizable compound is a compound having two or more polymerizable groups, and It is more preferable to have a polyalkyleneoxy group between at least two of the polymerizable groups.

〔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。 自由基交聯劑為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。作為上述包含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，作為上述包含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。 [Radical crosslinking agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radically polymerizable group. The radically polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing the above-mentioned ethylenically unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acryloyl, maleimide, and (meth)acryloyl. Groups with ethylenically unsaturated bonds such as amine groups. Among these, as the above-mentioned group containing an ethylenically unsaturated bond, a (meth)acrylamide group, a (meth)acrylamido group, and a vinylphenyl group are preferable, and from the viewpoint of reactivity, (Meth)acryloyl groups are more preferred.

自由基交聯劑為具有1個以上的乙烯性不飽和鍵之化合物為較佳，但是具有2個以上之化合物為更佳。自由基交聯劑可以具有3個以上的乙烯性不飽和鍵。 作為上述具有2個以上的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上述具有3個以上的乙烯性不飽和鍵之化合物亦較佳。 The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the above-mentioned compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 15 ethylenically unsaturated bonds is more preferable. The compound of 6 is more preferable. In addition, from the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention may also include a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. better.

自由基交聯劑的分子量為2,000以下為較佳，1,500以下為更佳，900以下為進一步較佳。自由基交聯劑的分子量的下限為100以上為較佳。The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

作為自由基交聯劑的具體例，可以舉出不飽和羧酸（例如，丙烯酸、甲基丙烯酸、衣康酸、巴豆酸、異巴豆酸、順丁烯二酸等）或其酯類、醯胺類，較佳為不飽和羧酸與多元醇化合物的酯及不飽和羧酸與多元胺化合物的醯胺類。又，亦可以較佳地使用具有羥基或胺基、氫硫基等親和性取代基之不飽和羧酸酯或醯胺類與單官能或多官能異氰酸酯類或環氧類的加成反應物、與單官能或多官能羧酸的脫水縮合反應物等。又，具有異氰酸酯基或環氧基等親電子性取代基之不飽和羧酸酯或醯胺類與單官能或多官能醇類、胺類、硫醇類的加成反應物以及具有鹵素基或甲苯磺醯氧基等脫離性取代基之不飽和羧酸酯或醯胺類與單官能或多官能醇類、胺類、硫醇類的取代反應物亦較佳。又，作為另一例，亦能夠使用替換成不飽和膦酸、苯乙烯等乙烯基苯衍生物、乙烯醚、烯丙醚等之化合物群組來代替上述不飽和羧酸。作為具體例，能夠參閱日本特開2016-027357號公報的0113～0122段的記載，並將該等內容編入本說明書中。Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides The amines are preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with affinity substituents such as hydroxyl groups, amine groups, and hydrogen thiol groups and monofunctional or polyfunctional isocyanates or epoxides can also be preferably used, Dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. In addition, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and halogen groups or Substitution reaction products of unsaturated carboxylic acid esters or amides with releasable substituents such as tosyloxy and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, as another example, a compound group substituted with vinylbenzene derivatives such as unsaturated phosphonic acid, styrene, vinyl ether, and allyl ether can also be used instead of the above-mentioned unsaturated carboxylic acid. As a specific example, the description of paragraphs 0113 to 0122 of JP 2016-027357 A can be referred to, and these contents are incorporated into the present specification.

又，自由基交聯劑為在常壓下具有100℃以上的沸點之化合物亦較佳。作為其例，可以舉出聚乙二醇二（甲基）丙烯酸酯、三羥甲基乙烷三（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、新戊四醇四（甲基）丙烯酸酯、二新戊四醇五（甲基）丙烯酸酯、二新戊四醇六（甲基）丙烯酸酯、己二醇二（甲基）丙烯酸酯、三羥甲基丙烷三（丙烯醯氧基丙基）醚、三（丙烯醯氧基乙基）異三聚氰酸酯、丙三醇或三羥甲基乙烷等在多官能醇中加成環氧乙烷或環氧丙烷之後進行（甲基）丙烯酸酯化而獲得之化合物、如日本特公昭48-041708號公報、日本特公昭50-006034號公報、日本特開昭51-037193號各公報中所記載之（甲基）丙烯酸胺酯類、日本特開昭48-064183號、日本特公昭49-043191號、日本特公昭52-030490號各公報中所記載之聚酯丙烯酸酯類，作為環氧樹脂與（甲基）丙烯酸的反應產物之環氧丙烯酸酯類等多官能丙烯酸酯或甲基丙烯酸酯及該等混合物。又，日本特開2008-292970號公報的0254～0257段中所記載的化合物亦較佳。又，亦可以舉出使（甲基）丙烯酸環氧丙酯等具有環狀醚基及乙烯性不飽和鍵之化合物與多官能羧酸進行反應而獲得之多官能（甲基）丙烯酸酯等。Moreover, it is also preferable that the radical crosslinking agent is a compound which has a boiling point of 100 degreeC or more under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and neopentaerythritol tri(meth)acrylate. (Meth)acrylate, Neotaerythritol Tetra (meth)acrylate, Dipivalerythritol Penta (meth)acrylate, Dipivalerythritol Hexa (meth)acrylate, Hexylene Glycol Di( meth)acrylate, trimethylolpropane tris(acryloyloxypropyl) ether, tris(acryloyloxyethyl) isocyanurate, glycerol or trimethylolethane, etc. Compounds obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols and then (meth)acrylated Amino (meth)acrylates described in each publication of Sho 51-037193, Japanese Patent Publication No. Sho 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. Sho 52-030490 Polyester acrylates, polyfunctional acrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, or methacrylates, and mixtures thereof. In addition, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also preferred. Moreover, polyfunctional (meth)acrylate etc. obtained by making the compound which has a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, react with a polyfunctional carboxylic acid are also mentioned.

又，作為除了上述以外的較佳的自由基交聯劑物，亦能夠使用日本特開2010-160418號公報、日本特開2010-129825號公報、日本專利第4364216號公報等中所記載之具有茀環且具有2個以上的含有乙烯性不飽和鍵之基團之化合物或卡多（cardo）樹脂。Moreover, as preferable radical crosslinking agent substances other than the above, those described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, Japanese Patent No. 4364216 and the like can also be used. A compound having a perylene ring and having two or more ethylenically unsaturated bond-containing groups or a cardo resin.

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

除了上述以外，亦能夠較佳地使用日本特開2015-034964號公報的0048～0051段中所記載的化合物、國際公開第2015/199219號的0087～0131段中所記載的化合物，並將該等內容編入本說明書中。In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP 2015-034964 A and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the etc. are incorporated into this manual.

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

進而，亦能夠使用日本特開2015-187211號公報的0104～0131段中所記載的化合物作為自由基交聯劑，並將該等內容編入本說明書中。Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as the radical crosslinking agent, and these contents are incorporated in the present specification.

作為自由基交聯劑，二新戊四醇三丙烯酸酯（作為市售品為KAYARAD D-330（Nippon Kayaku Co.,Ltd.製））、二新戊四醇四丙烯酸酯（作為市售品為KAYARAD D-320（Nippon Kayaku Co.,Ltd.製）、A-TMMT（Shin-Nakamura Chemical Co.,Ltd.製））、二新戊四醇五（甲基）丙烯酸酯（作為市售品為KAYARAD D-310（Nippon Kayaku Co.,Ltd.製））、二新戊四醇六（甲基）丙烯酸酯（作為市售品為KAYARAD DPHA（Nippon Kayaku Co.,Ltd.製）、A-DPH（Shin-Nakamura Chemical Co.,Ltd.製））及該等（甲基）丙烯醯基經由乙二醇殘基或丙二醇殘基鍵結之結構為較佳。亦能夠使用該等寡聚物類型。As a radical crosslinking agent, dipeotaerythritol triacrylate (as a commercial item, KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipeotaerythritol tetraacrylate (as a commercial item It is KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), dipivalerythritol penta(meth)acrylate (available as a commercial item) These are KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.), dipivaloerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), A- A structure in which DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) and these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferable. These oligomer types can also be used.

作為自由基交聯劑的市售品，例如可以舉出Sartomer Company, Inc製的作為具有4個伸乙氧基鏈之4官能丙烯酸酯之SR-494、作為具有4個乙烯氧基鏈之2官能丙烯酸甲酯之Sartomer Company, Inc製SR-209、231、239、Nippon Kayaku Co.,Ltd.製的作為具有6個伸戊氧基鏈之6官能丙烯酸酯之DPCA-60、作為具有3個異伸丁氧基鏈之3官能丙烯酸酯之TPA-330、胺酯寡聚物UAS-10、UAB-140（NIPPON PAPER INDUSTRIES CO.,LTD.製）、NK酯M-40G、NK酯4G、NK酯M-9300、NK酯A-9300、UA-7200（Shin-Nakamura Chemical Co.,Ltd製）、DPHA-40H（Nippon Kayaku Co.,Ltd.製）、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600（Kyoeisha chemical Co.,Ltd.製）、BLEMMER PME400（NOF CORPORATION製）等。Commercially available products of the radical crosslinking agent include, for example, SR-494 produced by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy-extending chains, and SR-494 as a tetrafunctional acrylate having four vinyloxy chains Functional methyl acrylate SR-209, 231, 239 manufactured by Sartomer Company, Inc., DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, as DPCA-60 having 3 TPA-330 of trifunctional acrylate of isobutyloxy chain, urethane oligomer UAS-10, UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA -306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

作為自由基交聯劑，如日本特公昭48-041708號公報、日本特開昭51-037193號公報、日本特公平02-032293號公報、日本特公平02-016765號公報中所記載之胺酯丙烯酸酯類、日本特公昭58-049860號公報、日本特公昭56-017654號公報、日本特公昭62-039417號公報、日本特公昭62-039418號公報中所記載的具有環氧乙烷系骨架之胺酯化合物類亦較佳。進而，作為自由基交聯劑，亦能夠使用日本特開昭63-277653號公報、日本特開昭63-260909號公報、日本特開平01-105238號公報中所記載之在分子內具有胺基結構或硫化物結構之化合物。As the radical crosslinking agent, for example, the amine esters described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765 Acrylates, those described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 having an ethylene oxide-based skeleton The amine ester compounds are also preferred. Furthermore, as the radical crosslinking agent, those described in Japanese Patent Laid-Open No. 63-277653, Japanese Patent Laid-Open No. 63-260909, and Japanese Patent Laid-Open No. Hei 01-105238 having an amino group in the molecule can also be used. Compounds of structure or sulfide structure.

自由基交聯劑可以為具有羧基、磷酸基等酸基之自由基交聯劑。具有酸基之自由基交聯劑為脂肪族多羥基化合物與不飽和羧酸的酯為較佳，使非芳香族羧酸酐與脂肪族多羥基化合物的未反應的羥基進行反應而具有酸基之自由基交聯劑為更佳。特佳為在使非芳香族羧酸酐與脂肪族多羥基化合物的未反應的羥基進行反應而具有酸基之自由基交聯劑中，脂肪族多羥基化合物為新戊四醇或二新戊四醇之化合物。作為市售品，例如作為TOAGOSEI CO.,Ltd.製的多元酸改質丙烯酸類寡聚物，可以舉出M-510、M-520等。The free-radical cross-linking agent may be a free-radical cross-linking agent having an acid group such as a carboxyl group and a phosphoric acid group. The free-radical crosslinking agent with an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride reacts with the unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. Free radical crosslinking agents are more preferred. Particularly preferred is a free-radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, and the aliphatic polyhydroxy compound is neopentylerythritol or dipivostriol Alcohol compounds. As a commercial item, M-510, M-520 etc. are mentioned as a polybasic acid-modified acrylic oligomer by TOAGOSEI CO., Ltd., for example.

具有酸基之自由基交聯劑的較佳酸值為0.1～300mgKOH/g，特佳為1～100mgKOH/g。只要自由基交聯劑的酸值在上述範圍內，則製造上的操作性優異，進而顯影性優異。又，聚合性良好。關於上述酸值，依據JIS K 0070：1992的記載來測定。The preferred acid value of the radical crosslinking agent having an acid group is 0.1-300 mgKOH/g, and particularly preferably 1-100 mgKOH/g. As long as the acid value of the radical crosslinking agent is within the above-mentioned range, the workability in production is excellent, and furthermore, the developability is excellent. In addition, the polymerizability was good. The said acid value is measured based on the description of JISK0070:1992.

從圖案的解析性和膜的伸縮性的觀點考慮，樹脂組成物使用2官能的甲基丙烯酸酯或丙烯酸酯為較佳。 作為具體的化合物，能夠使用三乙二醇二丙烯酸酯、三乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、四乙二醇二丙烯酸酯、PEG（聚乙二醇）200二丙烯酸酯、PEG200二甲基丙烯酸酯、PEG600二丙烯酸酯、PEG600二甲基丙烯酸酯、聚四乙二醇二丙烯酸酯、聚四乙二醇二甲基丙烯酸酯、新戊二醇二丙烯酸酯、新戊二醇二甲基丙烯酸酯、3-甲基-1,5-戊二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,6己二醇二甲基丙烯酸酯、二羥甲基三環癸烷二丙烯酸酯、二羥甲基三環癸烷二甲基丙烯酸酯、雙酚A的EO（環氧乙烷）加成物二丙烯酸酯、雙酚A的EO加成物二甲基丙烯酸酯、雙酚A的PO（環氧丙烷）加成物二丙烯酸酯、雙酚A的PO加成物二甲基丙烯酸酯、2羥基-3-丙烯醯氧基丙基甲基丙烯酸酯、異三聚氰酸EO改質二丙烯酸酯、異三聚氰酸改質二甲基丙烯酸酯、具有其他胺酯鍵之2官能丙烯酸酯、具有胺酯鍵之2官能甲基丙烯酸酯。該等依據需要能夠混合使用2種以上。 再者，例如PEG200二丙烯酸酯是指為聚乙二醇二丙烯酸酯且聚乙二醇鏈的式量為200左右者。 關於本發明的樹脂組成物，從伴隨圖案（硬化物）的彈性模數控制而抑制翹曲的觀點考慮，能夠較佳地使用單官能自由基交聯劑作為自由基交聯劑。作為單官能自由基交聯劑，可以較佳地使用正丁基（甲基）丙烯酸酯、2-乙基己基（甲基）丙烯酸酯、2-羥乙基（甲基）丙烯酸酯、丁氧基乙基（甲基）丙烯酸酯、卡必醇（甲基）丙烯酸酯、環己基（甲基）丙烯酸酯、芐基（甲基）丙烯酸酯、苯氧基乙基（甲基）丙烯酸酯、N-羥甲基（甲基）丙烯醯胺、環氧丙基（甲基）丙烯酸酯、聚乙二醇單（甲基）丙烯酸酯、聚丙二醇單（甲基）丙烯酸酯等（甲基）丙烯酸衍生物、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺等N-乙烯基化合物類、烯基環氧丙醚等。作為單官能自由基交聯劑，為了抑制曝光前的揮發，在常壓下具有100℃以上的沸點之化合物亦較佳。 除此以外，作為2官能以上的自由基交聯劑，可以舉出鄰苯二甲酸二烯丙酯、偏苯三酸三烯丙酯等烯丙基化合物類。 From the viewpoints of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate for the resin composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) can be used 200 Diacrylate, PEG200 Dimethacrylate, PEG600 Diacrylate, PEG600 Dimethacrylate, Polytetraethylene Glycol Diacrylate, Polytetraethylene Glycol Dimethacrylate, Neopentyl Glycol Diacrylate Esters, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6hexanediol dimethacrylate , dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO of bisphenol A Adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2hydroxy-3-propenyloxypropane methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, bifunctional acrylate with other urethane bond, bifunctional methyl with urethane bond based acrylate. These can be mixed and used 2 or more types as needed. In addition, for example, PEG200 diacrylate refers to a polyethylene glycol diacrylate and the formula weight of the polyethylene glycol chain is about 200. Regarding the resin composition of the present invention, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the pattern (hardened product). As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxy Ethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-Methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, alkenyl glycidyl ether, and the like. As the monofunctional radical crosslinking agent, in order to suppress volatilization before exposure, a compound having a boiling point of 100° C. or higher under normal pressure is also preferred. In addition, as a bifunctional or more radical crosslinking agent, allyl compounds, such as diallyl phthalate and triallyl trimellitate, are mentioned.

在含有自由基交聯劑之情況下，其含量相對於本發明的樹脂組成物的總固體成分超過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, it is preferable that the content exceeds 0 mass % and 60 mass % or less with respect to the total solid content of the resin composition of this invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

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。在同時使用2種以上之情況下，其合計量在上述範圍內為較佳。A radical crosslinking agent may be used individually by 1 type, and may be used in mixture of 2 or more types. When using 2 or more types simultaneously, it is preferable that the total amount is in the said 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較佳。 在本發明中，其他交聯劑是指除了上述自由基交聯劑以外的交聯劑，在分子內具有複數個藉由上述光酸產生劑或光鹼產生劑的感光而促進在與組成物中的其他化合物或其反應產物之間形成共價鍵之反應之基團之化合物為較佳，在分子內具有複數個藉由酸或鹼的作用而促進在與組成物中的其他化合物或其反應產物之間形成共價鍵之反應之基團之化合物為較佳。 上述酸或鹼為在曝光步驟中從光酸產生劑或光鹼產生劑產生之酸或鹼為較佳。 作為其他交聯劑，具有選自包括醯氧基甲基、羥甲基及烷氧基甲基之群組中的至少1種基團之化合物為較佳，具有選自包括醯氧基甲基、羥甲基及烷氧基甲基之群組中的至少1種基團與氮原子直接鍵結之結構之化合物為更佳。 作為其他交聯劑，例如可以舉出具有使甲醛或甲醛和醇與三聚氰胺、甘脲、脲、伸烷基脲、苯并胍胺等含有胺基之化合物進行反應而經醯氧基甲基、羥甲基或烷氧基甲基取代上述胺基的氫原子之結構之化合物。該等化合物之製造方法並無特別限定，只要為具有與藉由上述方法製造的化合物相同之結構之化合物即可。又，亦可以為該等化合物的羥甲基彼此自縮合而成之寡聚物。 將作為上述含有胺基之化合物而使用了三聚氰胺之交聯劑稱為三聚氰胺系交聯劑，將使用了甘脲、脲或伸烷基脲之交聯劑稱為脲系交聯劑，將使用了伸烷基脲之交聯劑稱為伸烷基脲系交聯劑，將使用了苯并胍胺之交聯劑稱為苯并胍胺系交聯劑。 在該等之中，本發明的樹脂組成物包含選自包括脲系交聯劑及三聚氰胺系交聯劑之群組中的至少1種化合物為較佳，包含選自包括後述甘脲系交聯劑及三聚氰胺系交聯劑之群組中的至少1種化合物為更佳。 [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. In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and has a plurality of crosslinking agents in the molecule, which are promoted by the above-mentioned photoacid generator or photobase generator to facilitate interaction with the composition. The other compounds in the compound or the reaction products of the other compounds or the reaction products thereof are preferably the compounds of the group that form a covalent bond, and have a plurality of compounds in the molecule that are promoted by the action of acids or bases in the composition with the other compounds or their compounds. Compounds of reactive groups that form covalent bonds between the reaction products are preferred. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. As other cross-linking agents, compounds having at least one group selected from the group consisting of oxymethyl, methylol and alkoxymethyl are preferred, and compounds having at least one group selected from the group consisting of oxymethyl, hydroxymethyl and alkoxymethyl are preferred. A compound having a structure in which at least one group in the group of hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom is more preferable. Examples of other cross-linking agents include compounds having an amine group-containing compound such as formaldehyde or formaldehyde and alcohols, such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, to be reacted with an oxymethyl group, A compound in which a hydroxymethyl group or an alkoxymethyl group is substituted for the hydrogen atom of the above-mentioned amine group. The production method of these compounds is not particularly limited, as long as it is a compound having the same structure as the compound produced by the above-mentioned method. Moreover, the oligomer which the hydroxymethyl group of these compounds self-condenses may be sufficient. The cross-linking agent using melamine as the above-mentioned amine group-containing compound is called a melamine-based cross-linking agent, and the cross-linking agent using glycoluril, urea, or alkylene urea is called a urea-based cross-linking agent. The crosslinking agent using alkylene urea is called alkylene urea crosslinking agent, and the crosslinking agent using benzoguanamine is called benzoguanamine crosslinking agent. Among these, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and contains a compound selected from the group consisting of glycoluril-based crosslinking agents described below. At least one compound in the group of the agent and the melamine-based crosslinking agent is more preferable.

作為含有本發明中之烷氧基甲基及醯氧基甲基中的至少1個之化合物，可以舉出烷氧基甲基或醯氧基甲基直接在芳香族基或下述脲結構的氮原子上或三𠯤上取代之化合物作為結構例。 上述化合物所具有之烷氧基甲基或醯氧基甲基為碳數2～5為較佳，碳數2或3為較佳，碳數2為更佳。 上述化合物所具有之烷氧基甲基及醯氧基甲基的總數為1～10為較佳，更佳為2～8，特佳為3～6。 上述化合物的分子量較佳為1500以下，180～1200為較佳。 As a compound containing at least one of the alkoxymethyl group and the alkoxymethyl group in the present invention, the alkoxymethyl group or the alkoxymethyl group directly in the aromatic group or the following urea structure can be mentioned. Compounds substituted on a nitrogen atom or on a trisium are taken as structural examples. Preferably, the alkoxymethyl or alkoxymethyl group of the above compound has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of the alkoxymethyl group and the alkoxymethyl group contained in the above-mentioned compound is preferably 1-10, more preferably 2-8, particularly preferably 3-6. The molecular weight of the above-mentioned compound is preferably 1500 or less, more preferably 180-1200.

[化學式46]

Figure 02_image090
[Chemical formula 46]
Figure 02_image090

R 100表示烷基或醯基。 R 101及R 102分別獨立地表示1價的有機基，並且可以相互鍵結而形成環。 R 100 represents an alkyl group or an acyl group. R 101 and R 102 each independently represent a monovalent organic group, and may be bonded to each other to form a ring.

作為烷氧基甲基或醯氧基甲基直接在芳香族基上取代之化合物，例如可以舉出下述通式的各種化合物。Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted with an aromatic group include various compounds of the following general formula.

[化學式47]

Figure 02_image092
[Chemical formula 47]
Figure 02_image092

式中，X表示單鍵或2價的有機基，每個R 104分別獨立地表示烷基或醯基，R 103表示氫原子、烷基、烯基、芳基、芳烷基或藉由酸的作用進行分解而產生鹼可溶性基之基團（例如，藉由酸的作用進行脫離之基團、-C（R 4） 2COOR 5所表示之基團（R 4分別獨立地表示氫原子或碳數1～4的烷基，R 5表示藉由酸的作用進行脫離之基團。））。 R 105各自獨立地表示烷基或烯基，a、b及c各自獨立地為1～3，d為0～4，e為0～3，f為0～3，a+d為5以下，b+e為4以下，c+f為4以下。 關於藉由酸的作用進行分解而產生鹼可溶性基之基團、藉由酸的作用進行脫離之基團、-C（R 4） 2COOR 5所表示之基團中之R 5，例如可以舉出-C（R 36）（R 37）（R 38）、-C（R 36）（R 37）（OR 39）、-C（R 01）（R 02）（OR 39）等。 式中，R 36～R 39分別獨立地表示烷基、環烷基、芳基、芳烷基或烯基。R 36與R 37可以相互鍵結而形成環。 作為上述烷基，碳數1～10的烷基為較佳，碳數1～5的烷基為更佳。 上述烷基可以為直鏈狀、支鏈狀中的任一個。 作為上述環烷基，碳數3～12的環烷基為較佳，碳數3～8的環烷基為更佳。 上述環烷基可以為單環結構，亦可以為縮合環等多環結構。 上述芳基為碳數6～30的芳香族烴基為較佳，苯基為更佳。 作為上述芳烷基，碳數7～20的芳烷基為較佳，碳數7～16的芳烷基為更佳。 上述芳烷基是指經烷基取代之芳基，該等烷基及芳基的較佳態樣與上述烷基及芳基的較佳態樣相同。 上述烯基為碳數3～20的烯基為較佳，碳數3～16的烯基為更佳。 又，該等基團在可以獲得本發明的效果之範圍內還可以具有公知的取代基。 In the formula, X represents a single bond or a divalent organic group, each R 104 independently represents an alkyl group or an acyl group, and R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an acid A group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that is released by the action of an acid, a group represented by -C(R 4 ) 2 COOR 5 (R 4 independently represents a hydrogen atom or An alkyl group having 1 to 4 carbon atoms, R 5 represents a group that can be removed by the action of an acid.)). R 105 each independently represents an alkyl group or an alkenyl group, a, b and c are each independently 1-3, d is 0-4, e is 0-3, f is 0-3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Examples of R 5 in the group represented by -C(R 4 ) 2 COOR 5 include a group that is decomposed by the action of an acid to generate an alkali-soluble group, a group that is released by the action of an acid, and a group represented by -C(R 4 ) 2 COOR 5 . Out-C(R 36 )(R 37 )(R 38 ),-C(R 36 )(R 37 )(OR 39 ),-C(R 01 )(R 02 )(OR 39 ), etc. In the formula, R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 36 and R 37 may be bonded to each other to form a ring. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable. The above-mentioned alkyl group may be linear or branched. As the cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable. The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring. The above-mentioned aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable. The above-mentioned aralkyl group refers to an aryl group substituted with an alkyl group, and the preferred aspects of the alkyl group and the aryl group are the same as the preferred aspects of the above-mentioned alkyl group and the aryl group. The above-mentioned alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Moreover, these groups may have a well-known substituent within the range which can obtain the effect of this invention.

R 01及R 02分別獨立地表示氫原子、烷基、環烷基、芳基、芳烷基或烯基。 R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

作為藉由酸的作用進行分解而產生鹼可溶性基之基團或藉由酸的作用進行脫離之基團，較佳為三級烷基、縮醛基、枯基酯基、烯醇酯基等。進一步較佳為三級烷基酯基、縮醛基。As a group that is decomposed by the action of an acid to generate an alkali-soluble group or a group that is released by the action of an acid, a tertiary alkyl group, an acetal group, a cumyl ester group, an enol ester group, etc. are preferred. . Further preferred are tertiary alkyl ester groups and acetal groups.

作為具有烷氧基甲基之化合物，具體而言，可以舉出以下結構。關於具有醯氧基甲基之化合物，可以舉出將下述化合物的烷氧基甲基變更為醯氧基甲基之化合物。作為在分子內具有烷氧基甲基或醯氧基甲基之化合物，可以舉出以下各種化合物，但是並不限定於該等。As a compound which has an alkoxymethyl group, the following structures are mentioned specifically,. As a compound which has an acyloxymethyl group, the compound which changed the alkoxymethyl group of the following compounds to an acyloxymethyl group is mentioned. As a compound which has an alkoxymethyl group or an acyloxymethyl group in a molecule|numerator, the following various compounds are mentioned, However, It is not limited to these.

[化學式48]

Figure 02_image094
[Chemical formula 48]
Figure 02_image094

[化學式49]

Figure 02_image096
[Chemical formula 49]
Figure 02_image096

關於含有烷氧基甲基及醯氧基甲基中的至少1個之化合物，可以使用市售者，亦可以使用藉由公知的方法合成者。 從耐熱性的觀點考慮，烷氧基甲基或醯氧基甲基直接在芳香環或三𠯤環上取代之化合物為較佳。 As for the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available one may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an alkoxymethyl group is directly substituted on an aromatic ring or a tris-ring is preferable.

作為三聚氰胺系交聯劑的具體例，可以舉出六甲氧基甲基三聚氰胺、六乙氧基甲基三聚氰胺、六丙氧基甲基三聚氰胺、六丁氧基丁基三聚氰胺等。Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like.

作為脲系交聯劑的具體例，例如可以舉出單羥甲基化甘脲、二羥甲基化甘脲、三羥甲基化甘脲、四羥甲基化甘脲、單甲氧基甲基化甘脲、二甲氧基甲基化甘脲、三甲氧基甲基化甘脲、四甲氧基甲基化甘脲、單乙氧基甲基化甘脲、二乙氧基甲基化甘脲、三乙氧基甲基化甘脲、四乙氧基甲基化甘脲、單丙氧基甲基化甘脲、二丙氧基甲基化甘脲、三丙氧基甲基化甘脲、四丙氧基甲基化甘脲、單丁氧基甲基化甘脲、二丁氧基甲基化甘脲、三丁氧基甲基化甘脲或四丁氧基甲基化甘脲等甘脲系交聯劑； 雙甲氧基甲基脲、雙乙氧基甲基脲、雙丙氧基甲基脲、雙丁氧基甲基脲等脲系交聯劑、 單羥甲基化伸乙脲或二羥甲基化伸乙脲、單甲氧基甲基化伸乙脲、二甲氧基甲基化伸乙脲、單乙氧基甲基化伸乙脲、二乙氧基甲基化伸乙脲、單丙氧基甲基化伸乙脲、二丙氧基甲基化伸乙脲、單丁氧基甲基化伸乙脲或二丁氧基甲基化伸乙脲等伸乙脲系交聯劑、 單羥甲基化伸丙脲、二羥甲基化伸丙脲、單甲氧基甲基化伸丙脲、二甲氧基甲基化伸丙脲、單乙氧基甲基化伸丙脲、二乙氧基甲基化伸丙脲、單丙氧基甲基化伸丙脲、二丙氧基甲基化伸丙脲、單丁氧基甲基化伸丙脲或二丁氧基甲基化伸丙脲等伸丙脲系交聯劑、 1,3-二（甲氧基甲基）4,5-二羥基-2-咪唑啶酮、1,3-二（甲氧基甲基）-4,5-二甲氧基-2-咪唑啶酮等。 Specific examples of the urea-based crosslinking agent include monomethylolated glycoluril, dimethylolated glycoluril, trimethylolated glycoluril, tetramethylolated glycoluril, and monomethoxyl glycoluril. Methylated Glycoluril, Dimethoxymethylated Glycoluril, Trimethoxymethylated Glycoluril, Tetramethoxymethylated Glycoluril, Monoethoxymethylated Glycoluril, Diethoxymethyl Glycoluril methylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethyl Glycoluril Glycoluril based cross-linking agents such as glycoluril; Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, bisbutoxymethyl urea, etc., Monomethylolated ethyl urea or dimethylolated ethyl urea, monomethoxymethylated ethyl urea, dimethoxymethylated ethyl urea, monoethoxymethylated ethyl urea , diethoxymethylated ethyl urea, monopropoxymethylated ethyl urea, dipropoxymethylated ethyl urea, monobutoxymethylated ethyl urea or dibutoxymethyl ethyl urea Ethyl urea and other ethyl urea crosslinking agents, Monomethylolated Propylene Urea , diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethyl propylene urea Propylene urea based crosslinking agent such as propylene propylene urea, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazole pyridone etc.

作為苯并胍胺系交聯劑的具體例，例如可以舉出單羥甲基化苯并胍胺、二羥甲基化苯并胍胺、三羥甲基化苯并胍胺、四羥甲基化苯并胍胺、單甲氧基甲基化苯并胍胺、二甲氧基甲基化苯并胍胺、三甲氧基甲基化苯并胍胺、四甲氧基甲基化苯并胍胺、單乙氧基甲基化苯并胍胺、二乙氧基甲基化苯并胍胺、三乙氧基甲基化苯并胍胺、四乙氧基甲基化苯并胍胺、單丙氧基甲基化苯并胍胺、二丙氧基甲基化苯并胍胺、三丙氧基甲基化苯并胍胺、四丙氧基甲基化苯并胍胺、單丁氧基甲基化苯并胍胺、二丁氧基甲基化苯并胍胺、三丁氧基甲基化苯并胍胺、四丁氧基甲基化苯并胍胺等。Specific examples of the benzoguanamine-based crosslinking agent include, for example, monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, and tetramethylolated benzoguanamine. Methylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzene guanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine Amine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, Monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, etc.

除此以外，作為具有選自包括羥甲基及烷氧基甲基之群組中的至少1種基團之化合物，亦可以較佳地使用在芳香環（較佳為苯環）上直接鍵結有選自包括羥甲基及烷氧基甲基之群組中的至少1種基團之化合物。 作為該種化合物的具體例，可以舉出苯二甲醇、雙（羥甲基）甲酚、雙（羥甲基）二甲氧基苯、雙（羥甲基）二苯醚、雙（羥甲基）二苯甲酮、羥甲基苯甲酸羥甲基苯酯、雙（羥甲基）聯苯、二甲基雙（羥甲基）聯苯、雙（甲氧基甲基）苯、雙（甲氧基甲基）甲酚、雙（甲氧基甲基）二甲氧基苯、雙（甲氧基甲基）二苯醚、雙（甲氧基甲基）二苯甲酮、甲氧基甲基苯甲酸甲氧基甲基苯酯、雙（甲氧基甲基）聯苯、二甲基雙（甲氧基甲基）聯苯、4,4’,4’’-亞乙基三[2,6-雙（甲氧基甲基）苯酚]、5,5’-[2,2,2‐三氟‐1‐（三氟甲基）亞乙基]雙[2‐羥基‐1,3‐苯二甲醇]、3,3’,5,5’-四（甲氧基甲基）-1,1’-聯苯-4,4’-二醇等。 In addition, as a compound having at least one group selected from the group consisting of methylol and alkoxymethyl, a direct bond on an aromatic ring (preferably a benzene ring) can also be preferably used A compound having at least one group selected from the group consisting of methylol and alkoxymethyl. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl) base) benzophenone, hydroxymethyl phenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(hydroxymethyl)biphenyl (Methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methyl Methoxymethylphenyl oxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylene yltris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxyl -1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

作為其他交聯劑，亦可以使用市售品，作為較佳的市售品，可以舉出46DMOC、46DMOEP（以上為ASAHI YUKIZAI CORPORATION製）、DML-PC、DML-PEP、DML-OC、DML-OEP、DML-34X、DML-PTBP、DML-PCHP、DML-OCHP、DML-PFP、DML-PSBP、DML-POP、DML-MBOC、DML-MBPC、DML-MTrisPC、DML-BisOC-Z、DML-BisOCHP-Z、DML-BPC、DMLBisOC-P、DMOM-PC、DMOM-PTBP、DMOM-MBPC、TriML-P、TriML-35XL、TML-HQ、TML-BP、TML-pp-BPF、TML-BPE、TML-BPA、TML-BPAF、TML-BPAP、TMOM-BP、TMOM-BPE、TMOM-BPA、TMOM-BPAF、TMOM-BPAP、HML-TPPHBA、HML-TPHAP、HMOM-TPPHBA、HMOM-TPHAP（以上為Honshu Chemical Industry Co.,Ltd.製）、NIKARAC（註冊商標，以下相同）MX-290、NIKARAC MX-280、NIKARAC MX-270、NIKARAC MX-279、NIKARAC MW-100LM、NIKARAC MX-750LM（以上為Sanwa Chemical Co.,Ltd.製）等。Commercially available products can also be used as other crosslinking agents, and preferred commercialized products include 46DMOC, 46DMOEP (the above are manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML- OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML- BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, the same below) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (the above are Sanwa Chemical Co., Ltd.) and the like.

又，本發明的樹脂組成物包含選自包括環氧化合物、氧環丁烷化合物及苯并㗁𠯤化合物之群組中的至少1種化合物作為其他交聯劑亦較佳。Moreover, it is also preferable that the resin composition of this invention contains at least 1 compound chosen from the group which consists of an epoxy compound, an oxetane compound, and a benzodiazepine compound as another crosslinking agent.

-環氧化合物（具有環氧基之化合物）- 作為環氧化合物，在一分子中具有2個以上的環氧基之化合物為較佳。環氧基在200℃以下進行交聯反應，並且不會產生由交聯引起之脫水反應，因此不易引起膜收縮。因此，含有環氧化合物對抑制本發明的樹脂組成物的低溫硬化及翹曲係有效的。 -Epoxy compounds (compounds with epoxy groups)- As an epoxy compound, the compound which has two or more epoxy groups in one molecule is preferable. The epoxy group undergoes a cross-linking reaction below 200°C, and does not produce a dehydration reaction caused by cross-linking, so it is difficult to cause film shrinkage. Therefore, containing an epoxy compound is effective in suppressing low-temperature hardening and warpage of the resin composition of the present invention.

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

作為環氧化合物的例子，可以舉出雙酚A型環氧樹脂；雙酚F型環氧樹脂；丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、乙二醇二縮水甘油醚、丁二醇二縮水甘油醚、六亞甲基二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚等伸烷基二醇型環氧樹脂或多元醇烴型環氧樹脂；聚丙二醇二縮水甘油醚等聚伸烷基二醇型環氧樹脂；聚甲基（縮水甘油氧基丙基）矽氧烷等環氧環氧基之矽酮等，但是並不限定於該等。具體而言，可以舉出EPICLON（註冊商標）850-S、EPICLON（註冊商標）HP-4032、EPICLON（註冊商標）HP-7200、EPICLON（註冊商標）HP-820、EPICLON（註冊商標）HP-4700、EPICLON（註冊商標）HP-4770、EPICLON（註冊商標）EXA-830LVP、EPICLON（註冊商標）EXA-8183、EPICLON（註冊商標）EXA-8169、EPICLON（註冊商標）N-660、EPICLON（註冊商標）N-665-EXP-S、EPICLON（註冊商標）N-740（以上為產品名稱，DIC CORPORATION製）、Rika Resin（註冊商標）BEO-20E、Rika Resin（註冊商標）BEO-60E、Rika Resin（註冊商標）HBE-100、Rika Resin（註冊商標）DME-100、Rika Resin（註冊商標）L-200（產品名稱，New Japan Chemical Co.,Ltd.製）、EP-4003S、EP-4000S、EP-4088S、EP-3950S（以上為產品名稱，ADEKA CORPORATION製）、CELLOXIDE（註冊商標）2021P、CELLOXIDE（註冊商標）2081、CELLOXIDE（註冊商標）2000、EHPE3150、EPOLEAD（註冊商標）GT401、EPOLEAD（註冊商標）PB4700、EPOLEAD（註冊商標）PB3600（以上為產品名稱，Daicel Corporation製）、NC-3000、NC-3000-L、NC-3000-H、NC-3000-FH-75M、NC-3100、CER-3000-L、NC-2000-L、XD-1000、NC-7000L、NC-7300L、EPPN-501H、EPPN-501HY、EPPN-502H、EOCN-1020、EOCN-102S、EOCN-103S、EOCN-104S、CER-1020、EPPN-201、BREN-S、BREN-10S（以上為產品名稱，Nippon Kayaku Co.,Ltd.製）等。又，亦可以較佳地使用以下化合物。Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol Glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl Polyalkylene glycol type epoxy resins such as glycerol ethers; epoxy epoxy silicones such as polymethyl(glycidoxypropyl)siloxane, etc., but not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP- 4700, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, manufactured by DIC CORPORATION), Rika Resin (registered trademark) BEO-20E, Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (product name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S , EP-4088S, EP-3950S (product names above, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (product names above, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100 , CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN -104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are product names, manufactured by Nippon Kayaku Co., Ltd.), etc. In addition, the following compounds can also be preferably used.

[化學式50]

Figure 02_image098
[Chemical formula 50]
Figure 02_image098

式中，n為1～5的整數、m為1～20的整數。In the formula, n is an integer of 1-5, and m is an integer of 1-20.

在上述結構之中，從兼顧耐熱性和伸長率的提高之觀點考慮，n為1～2、m為3～7為較佳。Among the above-mentioned structures, it is preferable that n is 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.

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

-苯并㗁𠯤化合物（具有苯并㗁唑基之化合物）- 由於由開環加成反應引起交聯反應，苯并㗁𠯤化合物在硬化時不產生脫氣，從而進一步減少熱收縮以抑制產生翹曲，因此為較佳。 -Benzoxazole compounds (compounds with a benzoxazolyl group)- Since the cross-linking reaction is caused by the ring-opening addition reaction, the benzodiazepine compound is preferred without degassing during curing, thereby further reducing thermal shrinkage and suppressing warpage.

作為苯并㗁𠯤化合物的較佳例，可以舉出P-d型苯并㗁𠯤、F-a型苯并㗁𠯤、（以上為產品名稱，Shikoku Chemicals Corporation製）、聚羥基苯乙烯樹脂的苯并㗁𠯤加成物、酚醛清漆型二氫苯并㗁𠯤化合物。該等可以單獨使用或者混合使用2種以上。Preferable examples of benzodiazepine compounds include P-d-type benzodiazepines, F-a-type benzodiazepines, (the above are product names, manufactured by Shikoku Chemicals Corporation), and benzodiazepines of polyhydroxystyrene resins. Adducts, novolac-type dihydrobenzos 㗁𠯤 compounds. These can be used individually or in mixture of 2 or more types.

其他交聯劑的含量相對於本發明的樹脂組成物的總固體成分為0.1～30質量%為較佳，0.1～20質量%為更佳，0.5～15質量%為進一步較佳，1.0～10質量%為特佳。其他交聯劑可以僅含有1種，亦可以含有2種以上。在含有2種以上的其他交聯劑之情況下，其合計在上述範圍內為較佳。The content of other crosslinking agents is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, more preferably 0.5 to 15 mass %, and 1.0 to 10 mass % relative to the total solid content of the resin composition of the present invention. Mass % is particularly good. The other crosslinking agent may be contained only by one type, or may contain two or more types. When two or more types of other crosslinking agents are contained, the total is preferably within the above range.

〔聚合起始劑〕 本發明的樹脂組成物包含能夠藉由光和/或熱而開始聚合之聚合起始劑為較佳。尤其，包含光聚合起始劑為較佳。 光聚合起始劑為光自由基聚合起始劑為較佳。作為光自由基聚合起始劑，並無特別限制，能夠從公知的光自由基聚合起始劑中適當選擇。例如，對紫外線區域至可見區域的光線具有感光性之光自由基聚合起始劑為較佳。又，亦可以為與光激勵之敏化劑產生某些作用而生成活性自由基之活性劑。 [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator capable of starting polymerization by light and/or heat. In particular, it is preferable to contain a photopolymerization initiator. Preferably, the photopolymerization initiator is 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 having photosensitivity to light in the ultraviolet region to the visible region is preferred. Moreover, it can also be an activator which produces|generates active radicals by some action with the sensitizer of photoexcitation.

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。關於化合物的莫耳吸光係數，能夠使用公知的方法來測定。例如，藉由紫外可見分光光度計（Varian Medical Systems, Inc.製Cary-5 spectrophotometer），並使用乙酸乙酯溶劑在0.01g/L的濃度下進行測定為較佳。 Preferably, the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 L/mol -1 /cm -1 in the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferable to measure at a concentration of 0.01 g/L by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) using an ethyl acetate solvent.

作為光自由基聚合起始劑，能夠任意使用公知的化合物。例如，可以舉出鹵化烴衍生物（例如具有三𠯤骨架之化合物、具有㗁二唑骨架之化合物、具有三鹵甲基之化合物等）、醯基氧化膦等醯基膦化合物、六芳基雙咪唑、肟衍生物等肟化合物、有機過氧化物、硫化合物、酮化合物、芳香族鎓鹽、酮肟醚、胺基苯乙酮等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。關於該等詳細內容，能夠參閱日本特開2016-027357號公報的0165～0182段、國際公開第2015/199219號的0138～0151段的記載，並將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號中所記載的光聚合起始劑、國際公開第2018/110179號中所記載的光聚合起始劑、日本特開2019-043864號公報中所記載的光聚合起始劑、日本特開2019-044030號公報中所記載的光聚合起始劑、日本特開2019-167313號公報中所記載的過酸化物系起始劑，並將該等內容亦編入本說明書中。As the photoradical polymerization initiator, any known compounds can be used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazole skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, and hexaarylbis Oxime compounds such as imidazoles and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxyl groups such as hydroxyacetophenone Ketone compounds, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron aromatic complexes, etc. For such details, reference can be made to the descriptions of paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of International Publication No. 2015/199219, and the contents are incorporated into the present specification. In addition, the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, the compounds described in JP 6301489 A, and the compounds described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019 can be mentioned. Peroxide-based photopolymerization initiator, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, Japanese Patent Laid-Open No. 2019-043864 The photopolymerization initiator described in JP 2019-044030 A, the peracid-based initiator described in JP 2019-167313 A, These contents are also incorporated into this manual.

作為酮化合物，例如可以例示日本特開2015-087611號公報的0087段中所記載的化合物，並將該內容編入本說明書中。在市售品中，亦可以較佳地使用KAYACURE DETX-S（Nippon Kayaku Co.,Ltd.製）。As the ketone compound, for example, the compound described in paragraph 0087 of JP-A No. 2015-087611 can be exemplified, and this content is incorporated in the present specification. Among the commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

在本發明的一實施態樣中，作為光自由基聚合起始劑，能夠較佳地使用羥基苯乙酮化合物、胺基苯乙酮化合物及醯基膦化合物。更具體而言，例如能夠使用日本特開平10-291969號公報中所記載的胺基苯乙酮系起始劑、日本專利第4225898號中所記載的醯基氧化膦系起始劑，並將該內容編入本說明書中。In one embodiment of the present invention, as the photo-radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969, the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and the This content is 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.公司製）、IRGACURE 184（IRGACURE為註冊商標）、DAROCUR 1173、IRGACURE 500、IRGACURE-2959、IRGACURE 127（產品名稱：均為BASF公司製）。As the α-hydroxyketone-based initiator, 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, IRGACURE- 2959, IRGACURE 127 (product name: all made 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.公司製）、IRGACURE 907、IRGACURE 369及IRGACURE 379（產品名稱：均為BASF公司製）。As the α-amino ketone-based starter, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (the above are manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (product names: all are BASF Corporation) can be used system).

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號公報中所記載的化合物，並將該內容編入本說明書中。As the aminoacetophenone-based initiator, the compounds described in Japanese Patent Laid-Open No. 2009-191179 whose absorption maximum wavelength matches a light source with a wavelength of 365 nm or 405 nm can also be used, and the contents are incorporated in the present 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.公司製）、IRGACURE-819或IRGACURE-TPO（產品名稱：均為BASF公司製）。As an acylphosphine oxide-based initiator, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, etc. are mentioned. In addition, Omnirad 819, Omnirad TPO (the above are manufactured by IGM Resins B.V.), IRGACURE-819 or IRGACURE-TPO (product name: both manufactured by BASF Corporation) can be used.

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

作為光自由基聚合起始劑，可以更佳地舉出肟化合物。藉由使用肟化合物，能夠更有效地提高曝光寬容度。肟化合物的曝光寬容度（曝光餘量）較廣，並且亦作為光硬化促進劑而起作用，因此為特佳。As a photoradical polymerization initiator, an oxime compound can be mentioned more preferably. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound has a wide exposure latitude (exposure margin) and also functions as a photohardening accelerator, so it is particularly preferable.

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

作為較佳的肟化合物，例如可以舉出下述結構的化合物、3-（苯甲醯氧基（亞胺基））丁烷-2-酮、3-（乙醯氧基（亞胺基））丁烷-2-酮、3-（丙醯氧基（亞胺基））丁烷-2-酮、2-（乙醯氧基（亞胺基））戊烷-3-酮、2-（乙醯氧基（亞胺基））-1-苯基丙烷-1-酮、2-（苯甲醯氧基（亞胺基））-1-苯基丙烷-1-酮、3-（（4-甲苯磺醯氧基）亞胺基）丁烷-2-酮及2-（乙氧基羰氧基（亞胺基））-1-苯基丙烷-1-酮等。在本發明的樹脂組成物中，尤其使用肟化合物（肟系的光自由基聚合起始劑）作為光自由基聚合起始劑為較佳。肟系光自由基聚合起始劑在分子內具有＞C=N-O-C（=O）-的連接基。Preferable oxime compounds include, for example, compounds having the following structures, 3-(benzyloxy(imino))butan-2-one, 3-(acetoxy(imino)) ) butan-2-one, 3-(propanoyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2- (Acetyloxy(imino))-1-phenylpropan-1-one, 2-(benzyloxy(imino))-1-phenylpropan-1-one, 3-( (4-Tosylsulfonyloxy)imino)butane-2-one and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one and the like. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. The oxime-based photo-radical polymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[化學式51]

Figure 02_image100
[Chemical formula 51]
Figure 02_image100

在市售品中，亦可以較佳地使用IRGACURE OXE 01、IRGACURE OXE 02、IRGACURE OXE 03、IRGACURE OXE 04（以上為BASF公司製）、ADEKA OPTOMER N-1919（ADEKA CORPORATION製、日本特開2012-014052號公報中所記載的光自由基聚合起始劑2）。又，亦能夠使用TR-PBG-304、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 Co.,Ltd.製）、SpeedCure PDO（SARTOMER ARKEMA製）。又，亦能夠使用下述結構的肟化合物。 [化學式52]

Figure 02_image102
Among the 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, Japanese Patent Laid-Open 2012- The photoradical polymerization initiator 2) described in Gazette 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 Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Moreover, the oxime compound of the following structure can also be used. [Chemical formula 52]
Figure 02_image102

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號公報中所記載的化合物、日本專利06636081號中所記載的化合物，並將該內容編入本說明書中。As a photoradical polymerization initiator, an oxime compound having a perylene ring can also be used. Specific examples of the oxime compound having a perylene ring include the compounds described in Japanese Patent Laid-Open No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, the contents of which are incorporated in the present specification.

作為光自由基聚合起始劑，亦能夠使用具有咔唑環中的至少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號中所記載的化合物，並將該內容編入本說明書中。As the photoradical polymerization initiator, an oxime compound having at least one benzene ring in a carbazole ring serving as a skeleton of a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound described in International Publication No. 2013/083505 is mentioned, and the content is incorporated in this specification.

又，亦能夠使用具有氟原子之肟化合物。作為該種肟化合物的具體例，可以舉出日本特開2010-262028號公報中所記載之化合物、日本特表2014-500852號公報的0345段中所記載之化合物24、36～40、日本特開2013-164471號公報的0101段中所記載之化合物（C-3）等，並將該內容編入本說明書中。Moreover, the oxime compound which has a fluorine atom can also be used. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 24-500852 A. Compound (C-3) and the like described in paragraph 0101 of Unexamined Publication No. 2013-164471, and the contents thereof are incorporated into the present 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體亦較佳。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段、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，並將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 those described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466 A. The compound is the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and the contents thereof are incorporated into the present specification. Moreover, ADEKA ARKLS NCI-831 (made by ADEKA CORPORATION) is also mentioned as an oxime compound which has a nitro group.

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 a 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，並將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. As such a photopolymerization initiator, the compound described in International Publication No. 2019/088055, etc. are mentioned, and the content is incorporated in this specification.

作為光聚合起始劑，亦能夠使用具有在芳香族環上導入有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等理由考慮，醯基為更佳，苯甲醯基為進一步較佳。苯甲醯基可以具有取代基。作為取代基，鹵素原子、氰基、硝基、羥基、烷基、烷氧基、芳基、芳氧基、雜環基、雜環氧基、烯基、烷基硫基、芳基硫基、醯基或胺基為較佳，烷基、烷氧基、芳基、芳氧基、雜環氧基、烷基硫基、芳基硫基或胺基為更佳，烷氧基、烷基硫基或胺基為進一步較佳。 As the photopolymerization initiator, an oxime compound (hereinafter, also referred to as an oxime compound OX) having an aromatic ring group Ar OX1 into which an electron withdrawing group is introduced can also be used. Examples of the electron withdrawing group possessed by the above-mentioned aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, An arylsulfonyl group, a cyano group, an acyl group, and a nitro group are preferable, and an acyl group is more preferable, and a benzyl group is still more preferable because of the ease of forming a film excellent in light resistance. The benzyl group may have a substituent. As a substituent, halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkenyl group, alkylthio group, arylthio group , amide group or amine group is preferred, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclicoxy group, alkylthio group, arylthio group or amine group are more preferred, alkoxy group, alkyl group A thio group or an amine group is further preferred.

肟化合物OX為選自式（OX1）所表示之化合物及式（OX2）所表示之化合物中的至少1種為較佳，式（OX2）所表示之化合物為更佳。 [化學式53]

Figure 02_image104
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、烷基硫基、芳基硫基、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、亞膦醯基、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、烷基硫基、芳基硫基、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。 The oxime compound OX is preferably at least one selected from the group consisting of the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). [Chemical formula 53]
Figure 02_image104
In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an aryl group sulfinyl group, alkylsulfonyl group, arylsulfonyl group, yl group, yloxy group, amino group, phosphonide group, carbamoyl group or sulfamoyl group, R X2 represents alkyl, alkene alkoxy, aryl, aryloxy, heterocyclyl, heterocyclyloxy, alkylthio, arylthio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl group, arylsulfonyl group, aryloxy group or amine group, and R X3 to R X14 each independently represent a hydrogen atom or a substituent. Among them, at least one of R X10 to R X14 is an electron withdrawing group.

在上述式中，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段中所記載的化合物，並將該內容編入本說明書中。Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, which are incorporated in the present specification.

作為最佳的肟化合物，可以舉出日本特開2007-269779號公報中所示之具有特定取代基之肟化合物或日本特開2009-191061號公報中所示之具有硫芳基之肟化合物等，並將該內容編入本說明書中。As the optimum oxime compound, the oxime compound having a specific substituent shown in JP-A No. 2007-269779 or the oxime compound having a thioaryl group shown in JP-A No. 2009-191061 can be mentioned. , and incorporate it into this manual.

從曝光靈敏度的觀點考慮，光自由基聚合起始劑為選自包括三鹵甲基三𠯤化合物、苄基二甲基縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、苯并噻唑化合物、二苯甲酮化合物、苯乙酮化合物及其衍生物、環戊二烯基-苯-鐵錯合物及其鹽、鹵甲基㗁二唑化合物、3-芳基取代香豆素化合物之群組中的化合物為較佳。From the viewpoint of exposure sensitivity, the photo-radical polymerization initiator is selected from the group consisting of trihalomethyltrisium compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, 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, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

進一步較佳的光自由基聚合起始劑為三鹵甲基三𠯤化合物、α-胺基酮化合物、醯基膦化合物、氧化膦化合物、茂金屬化合物、肟化合物、三芳基咪唑二聚體、鎓鹽化合物、二苯甲酮化合物、苯乙酮化合物，選自包括三鹵甲基三𠯤化合物、α-胺基酮化合物、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的至少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又更進一步較佳。Further preferred photo-radical polymerization initiators are trihalomethyltriazole compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, Onium salt compounds, benzophenone compounds, and acetophenone compounds, selected from the group consisting of trihalomethyltriazole compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, dibenzoyl It is still more preferable to use at least one compound in the group of ketone compounds, and it is still more preferable 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-2-二甲基胺基-1-（4-嗎啉基苯基）-丁酮-1,2-甲基-1-[4-（甲硫基）苯基]-2-嗎啉基-丙酮-1等芳香族酮、烷基蒽醌等與芳香環縮環而形成之醌類、安息香烷基醚等安息香醚化合物、安息香、烷基安息香等安息香化合物、苄基二甲基縮酮等苄基衍生物等。又，亦能夠使用下述式（I）所表示之化合物。In addition, as the photoradical polymerization initiator, N, 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-morpholinophenyl)-butanone-1 , 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 and other aromatic ketones, alkyl anthraquinones and other quinones formed by condensed with aromatic rings, Benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. Moreover, the compound represented by following formula (I) can also be used.

[化學式54]

Figure 02_image106
[Chemical formula 54]
Figure 02_image106

式（I）中，R I00為碳數1～20的烷基、藉由1個以上的氧原子而中斷之碳數2～20的烷基、碳數1～12的烷氧基或苯基或碳數1～20的烷基、碳數1～12的烷氧基、鹵素原子、環戊基、環己基、碳數2～12的烯基、經藉由1個以上的氧原子而中斷之碳數2～18的烷基及碳數1～4的烷基中的至少1個取代的苯基或聯苯基，R I01為式（II）所表示之基團或為與R I00相同的基團，R I02～R I04分別獨立地為碳數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 C1-20 alkyl, C1-12 alkoxy, halogen atom, cyclopentyl, cyclohexyl, C2-12 alkenyl, interrupted by one or more oxygen atoms A phenyl group or biphenyl group substituted with at least one of the alkyl group having 2 to 18 carbon atoms and the alkyl group having 1 to 4 carbon atoms, R I01 is a group represented by formula (II) or the same as R I00 R I02 to R I04 are each independently an alkyl group with 1 to 12 carbons, an alkoxy group with 1 to 12 carbons or a halogen atom.

[化學式55]

Figure 02_image108
[Chemical formula 55]
Figure 02_image108

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段中所記載的化合物，並將該內容編入本說明書中。In addition, the compounds described in paragraphs 0048 to 0055 of International Publication No. WO 2015/125469 can also be used as the photo-radical polymerization initiator, and the contents are incorporated in the present 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聚合起始劑。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，在使用非對稱結構的化合物之情況下，結晶性降低而在溶劑等中的溶解性提高，變得難以經時析出，從而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體、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，並將該內容編入本說明書中。As the photoradical polymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator can be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained. In addition, when a compound with an asymmetric structure is used, the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation over time becomes difficult, so that the stability over time of the resin composition can be improved. Specific examples of the bifunctional or trifunctional or more than trifunctional photo-radical polymerization initiators include JP 2010-527339 A, JP 2011-524436 A, WO 2015/004565, JP 2011-524436 Dimers of oxime compounds described in paragraphs 0407 to 0412 of Table 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017/033680, compounds (E ) and compound (G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester-based photoinitiators described in paragraph 0007 of JP 2017-523465 A, JP 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 Unexamined Patent Application Publication No. 2017-151342, and Japanese Patent No. 6469669 The oxime ester photoinitiator and the like described, and the contents are incorporated into this specification.

在包含光聚合起始劑之情況下，其含量相對於本發明的樹脂組成物的總固體成分為0.1～30質量%為較佳，更佳為0.1～20質量%，進一步較佳為0.5～15質量%，更進一步較佳為1.0～10質量%。光聚合起始劑可以僅含有1種，亦可以含有2種以上。在含有2種以上的光聚合起始劑之情況下，合計量在上述範圍內為較佳。 再者，光聚合起始劑有時亦作為熱聚合起始劑而發揮功能，因此有時藉由烘箱或加熱板等的加熱而進一步進行基於光聚合起始劑之交聯。 When a photopolymerization initiator is contained, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 0.5 to 30 mass % with respect to the total solid content of the resin composition of the present invention. 15 mass %, more preferably 1.0 to 10 mass %. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above-mentioned range. In addition, since the photopolymerization initiator may function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further performed by heating in an oven, a hot plate, or the like.

〔敏化劑〕 樹脂組成物可以包括敏化劑。敏化劑吸收特定的活性放射線而成為電子激勵狀態。成為電子激勵狀態之敏化劑與熱自由基聚合起始劑、光自由基聚合起始劑等接觸，從而產生電子轉移、能量轉移、發熱等作用。藉此，熱自由基聚合起始劑、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。 作為能夠使用的敏化劑，能夠使用二苯甲酮系、米其勒酮系、香豆素系、吡唑偶氮系、苯胺基偶氮系、三苯基甲烷系、蒽醌系、蒽系、蒽吡啶酮系、亞苄基系、氧雜菁系、吡唑并三唑偶氮系、吡啶酮偶氮系、花青系、啡噻𠯤系、吡咯并吡唑偶氮次甲基系、口山口星系、酞菁系、苯并吡喃系、靛藍系等化合物。 作為敏化劑，例如可以舉出米其勒酮、4,4’-雙（二乙胺基）二苯甲酮、2,5-雙（4’-二乙胺基亞苄基）環戊烷、2,6-雙（4’-二乙胺基亞苄基）環己酮、2,6-雙（4’-二乙胺基亞苄基）-4-甲基環己酮、4,4’-雙（二甲基胺基）查耳酮、4,4’-雙（二乙胺基）查耳酮、對二甲基胺基苯亞烯丙基二氫茚酮、對二甲基胺基亞苄基二氫茚酮、2-（對二甲基胺基苯基亞聯苯基）-苯并噻唑、2-（對二甲基胺基苯基亞乙烯基）苯并噻唑、2-（對二甲基胺基苯基亞乙烯基）異萘并噻唑、1,3-雙（4’-二甲基胺基亞苄基）丙酮、1,3-雙（4’-二乙胺基亞苄基）丙酮、3,3’-羰基-雙（7-二乙胺基香豆素）、3-乙醯基-7-二甲基胺基香豆素、3-乙氧基羰基-7-二甲基胺基香豆素、3-苄氧基羰基-7-二甲基胺基香豆素、3-甲氧基羰基-7-二乙胺基香豆素、3-乙氧基羰基-7-二乙胺基香豆素、（7-（二乙胺基）香豆素-3-羧酸乙酯）、N-苯基-N’-乙基乙醇胺、N-苯基二乙醇胺、N-對甲苯基二乙醇胺、N-苯基乙醇胺、4-嗎啉基二苯甲酮、二甲基胺基苯甲酸異戊酯、二乙胺基苯甲酸異戊酯、2-巰基苯并咪唑、1-苯基-5-巰基四唑、2-巰基苯并噻唑、2-（對二甲基胺基苯乙烯基）苯并㗁唑、2-（對二甲基胺基苯乙烯基）苯并噻唑、2-（對二甲基胺基苯乙烯基）萘并（1,2-d）噻唑、2-（對二甲基胺基苯甲醯基）苯乙烯、二苯基乙醯胺、苯甲醯苯胺、N-甲基乙醯苯胺、3’,4’-二甲基乙醯苯胺等。 又，可以使用其他敏化色素。 關於敏化色素的詳細內容，能夠參閱日本特開2016-027357號公報的0161～0163段的記載，並將該內容編入本說明書中。 [Sensitizer] The resin composition may include a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state contacts with the thermal radical polymerization initiator, the photoradical polymerization initiator, etc., thereby producing electron transfer, energy transfer, and heat generation. Thereby, the thermal radical polymerization initiator and the photoradical polymerization initiator are decomposed by chemical change, and a radical, an acid, or a base is generated. As sensitizers that can be used, benzophenone-based, micheler's ketone-based, coumarin-based, pyrazoleazo-based, anilinoazo-based, triphenylmethane-based, anthraquinone-based, and anthracene-based sensitizers can be used series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, Kouyamaguchi galaxy, phthalocyanine series, benzopyran series, indigo series and other compounds. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane Alkane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4 ,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidene indanone, p-diethylamine Methylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylidene)benzo Thiazole, 2-(p-dimethylaminophenylvinylidene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4' -diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3- Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin , 3-ethoxycarbonyl-7-diethylamino coumarin, (7-(diethylamino) coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine , N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Amyl ester, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p- Dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminostyryl)benzyl ) Styrene, diphenylacetanilide, benzalanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. In addition, other sensitizing dyes can be used. For details of the sensitizing dye, the descriptions in paragraphs 0161 to 0163 of JP 2016-027357 A can be referred to, and the contents are incorporated in the present specification.

在樹脂組成物包含敏化劑之情況下，敏化劑的含量相對於樹脂組成物的總固體成分為0.01～20質量%為較佳，0.1～15質量%為更佳，0.5～10質量%為進一步較佳。敏化劑可以單獨使用1種，亦可以同時使用2種以上。When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass relative to the total solid content of the resin composition. for further better. A sensitizer may be used individually by 1 type, and may use 2 or more types together.

〔鏈轉移劑〕 本發明的樹脂組成物可以含有鏈轉移劑。關於鏈轉移劑，例如在高分子詞典第三版（高分子學會（The Society of Polymer Science,Japan）編，2005年）683-684頁中被定義。作為鏈轉移劑，例如可以使用在分子內具有-S-S-、-SO 2-S-、-N-O-、SH、PH、SiH及GeH之化合物群組、具有用於RAFT（Reversible Addition Fragmentation chain Transfer：可逆加成鏈轉移聚合）聚合之硫羰硫基之二硫代苯甲酸酯、三硫代碳酸酯、二硫代胺基甲酸酯、黃原酸酯（Xanthate）化合物等。該等對低活性自由基供給氫而生成自由基或者在被氧化之後可以藉由去質子來生成自由基。尤其，能夠較佳地使用硫醇化合物。 [Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Regarding the chain transfer agent, it is defined, for example, in pages 683-684 of the Polymer Dictionary, 3rd edition (edited by The Society of Polymer Science, Japan, 2005). As a chain transfer agent, for example, a group of compounds having -SS-, -SO 2 -S-, -NO-, SH, PH, SiH, and GeH in the molecule, a compound having a compound for RAFT (Reversible Addition Fragmentation chain Transfer: Reversible addition chain transfer polymerization) polymerized thiocarbonylthio dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds, etc. These can generate free radicals by supplying hydrogen to the less reactive radicals or can be deprotonated to generate free radicals after being oxidized. In particular, a thiol compound can be preferably used.

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

在本發明的樹脂組成物具有鏈轉移劑之情況下，鏈轉移劑的含量相對於本發明的樹脂組成物的總固體成分100質量份為0.01～20質量份為較佳，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種以上之情況下，其合計在上述範圍內為較佳。When the resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the total solid content of the resin composition of the present invention More preferably, 0.5-5 mass parts is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more types of chain transfer agents, the total is preferably within the above range.

＜鹼產生劑＞ 本發明的樹脂組成物可以包含鹼產生劑。其中，鹼產生劑為能夠藉由物理或化學作用而產生鹼之化合物。作為對本發明的樹脂組成物來說較佳的鹼產生劑，可以舉出熱鹼產生劑及光鹼產生劑。 其中，與上述特定聚合性化合物對應之化合物不對應於本發明中所述之鹼產生劑。 尤其，在樹脂組成物包含環化樹脂的前驅物之情況下，樹脂組成物包含鹼產生劑為較佳。藉由使樹脂組成物含有熱鹼產生劑，例如藉由加熱而能夠促進前驅物的環化反應，成為硬化物的機械特性或耐藥品性良好者，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得良好。 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。 對本發明之鹼產生劑並無特別限制，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、苄胺基甲酸酯化合物、硝基苄胺基甲酸酯化合物、磺酸醯胺化合物、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、胺醯亞胺化合物、鄰苯二甲醯亞胺衍生物化合物、醯氧基亞胺基化合物等。 作為非離子型鹼產生劑的具體的化合物，可以舉出式（B1）、式（B2）或式（B3）所表示之化合物。 [化學式56]

Figure 02_image110
<Alkali Generator> The resin composition of the present invention may contain an alkali generator. Among them, the base generator is a compound capable of generating a base by physical or chemical action. As a preferable alkali generator for the resin composition of this invention, a thermal alkali generator and a photobase generator are mentioned. However, the compound corresponding to the above-mentioned specific polymerizable compound does not correspond to the base generator described in the present invention. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains an alkali generator. By including a thermal alkali generator in the resin composition, for example, the cyclization reaction of the precursor can be accelerated by heating, and the cured product has good mechanical properties or chemical resistance, for example, as a rewiring layer included in a semiconductor package The performance with the interlayer insulating film becomes good. As an alkali generator, an ionic alkali generator may be sufficient, and a nonionic alkali generator may be sufficient. Examples of the base generated from the base generator include secondary amines and tertiary amines. The alkali generator of the present invention is not particularly limited, and known alkali generators can be used. As known base generators, for example, carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, carbamoyl amine compounds, acetamide compounds, urethane compounds, and benzyl carbamic acid can be used. Ester Compounds, Nitrobenzyl Carbamate Compounds, Sulfonamide Compounds, Imidazole Derivative Compounds, Aminoimide Compounds, Pyridine Derivative Compounds, α-Aminoacetophenone Derivative Compounds, Quaternary Ammonium Salts Derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amide imide compounds, phthalimide derivative compounds, acyloxyimide-based compounds, and the like. As a specific compound of a nonionic base generator, the compound represented by a formula (B1), a formula (B2), or a formula (B3) is mentioned. [Chemical formula 56]
Figure 02_image110

式（B1）及式（B2）中，Rb 1、Rb 2及Rb 3分別獨立地為不具有三級胺結構的有機基、鹵素原子或氫原子。其中，Rb 1及Rb 2不會同時成為氫原子。又，Rb 1、Rb 2及Rb 3均不具有羧基。再者，在本說明書中，三級胺結構是指3價的氮原子的3個鍵結鍵均與烴系碳原子進行共價鍵之結構。因此，在所鍵結之碳原子為形成羰基之碳原子之情況亦即在與氮原子一同形成醯胺基之情況下，並不限於此。 In formula (B1) and formula (B2), Rb 1 , Rb 2 and Rb 3 are each independently an organic group, a halogen atom or a hydrogen atom which does not have a tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. In addition, none of Rb 1 , Rb 2 and Rb 3 has a carboxyl group. In addition, in this specification, a tertiary amine structure means the structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, when the carbon atom to be bonded is a carbon atom forming a carbonyl group, that is, when forming an amide group together with a nitrogen atom, it is not limited to this.

式（B1）、式（B2）中，Rb 1、Rb 2及Rb 3中的至少1個包含環狀結構為較佳，至少2個包含環狀結構為更佳。作為環狀結構，可以為單環及縮合環中的任一個，單環或2個單環縮合而成之縮合環為較佳。單環為5員環或6員環為較佳，6員環為更佳。單環為環己烷環及苯環為較佳，環己烷環為更佳。 In formula (B1) and formula (B2), at least one of Rb 1 , Rb 2 and Rb 3 preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a condensed ring formed by condensing a monocyclic ring or two monocyclic rings is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The single ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.

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

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

式（B1）所表示之化合物為下述式（B1-1）或下述式（B1-2）所表示之化合物為較佳。 [化學式57]

Figure 02_image112
The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical formula 57]
Figure 02_image112

式中，Rb 11及Rb 12和Rb 31及Rb 32分別與式（B1）中之Rb 1及Rb 2的含義相同。 Rb 13為烷基（碳數1～24為較佳，2～18為更佳，3～12為進一步較佳）、烯基（碳數2～24為較佳，2～18為更佳，3～12為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～12為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳），在發揮本發明的效果之範圍內可以具有取代基。其中，Rb 13為芳烷基為較佳。 In the formula, Rb 11 and Rb 12 and Rb 31 and Rb 32 have the same meanings as Rb 1 and Rb 2 in the formula (B1), respectively. Rb 13 is alkyl (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), alkenyl (preferably carbon number 2-24, more preferably 2-18, 3-12 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, and 7-12 are more preferable), and may have a substituent within the range which exhibits the effect of this invention. Among them, Rb 13 is preferably an aralkyl group.

Rb 33及Rb 34分別獨立地為氫原子、烷基（碳數1～12為較佳，1～8為更佳，1～3為進一步較佳）、烯基（碳數2～12為較佳，2～8為更佳，2～3為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳），氫原子為較佳。 Rb 33 and Rb 34 are independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3), an alkenyl group (preferably having a carbon number of 2 to 12). preferably, 2-8 are more preferred, 2-3 are further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-10 is further preferred), aralkyl ( The number of carbon atoms is preferably 7 to 23, more preferably 7 to 19, and further preferably 7 to 11), and hydrogen atom is more preferred.

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

式（B1-1）所表示之化合物為式（B1-1a）所表示之化合物亦較佳。 [化學式58]

Figure 02_image114
It is also preferable that the compound represented by the formula (B1-1) is the compound represented by the formula (B1-1a). [Chemical formula 58]
Figure 02_image114

Rb 11及Rb 12與式（B1-1）中之Rb 11及Rb 12的含義相同。 Rb 15及Rb 16為氫原子、烷基（碳數1～12為較佳，1～6為更佳，1～3為進一步較佳）、烯基（碳數2～12為較佳，2～6為更佳，2～3為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～11為進一步較佳），氫原子或甲基為較佳。 Rb 17為烷基（碳數1～24為較佳，1～12為更佳，3～8為進一步較佳）、烯基（碳數2～12為較佳，2～10為更佳，3～8為進一步較佳）、芳基（碳數6～22為較佳，6～18為更佳，6～12為進一步較佳）、芳烷基（碳數7～23為較佳，7～19為更佳，7～12為進一步較佳），其中，芳基為較佳。 Rb 11 and Rb 12 have the same meanings as Rb 11 and Rb 12 in formula (B1-1). Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3), alkenyl (preferably having 2 to 12 carbon atoms, and 2 ～6 is better, 2-3 is further better), aryl (carbon number is 6-22 is better, 6-18 is better, 6-10 is further better), aralkyl (carbon number is 7 -23 is preferred, 7-19 is more preferred, 7-11 is further preferred), hydrogen atom or methyl group is preferred. Rb 17 is an alkyl group (preferably carbon number 1-24, more preferably 1-12, and further preferably 3-8), alkenyl (preferably carbon number 2-12, more preferably 2-10, 3-8 is further preferred), aryl (carbon number 6-22 is preferred, 6-18 is more preferred, 6-12 is further preferred), aralkyl (carbon number 7-23 is preferred, 7-19 are more preferable, 7-12 are further preferable), among them, aryl group is preferable.

[化學式59]

Figure 02_image116
[Chemical formula 59]
Figure 02_image116

在式（B3）中，L表示烴基，該烴基為在連接相鄰之氧原子和碳原子之連接鏈的路徑上具有飽和烴基之2價的烴基，並且連接鏈的路徑上的原子數為3個以上。又，R N1及R N2分別獨立地表示1價的有機基。 In the formula (B3), L represents a hydrocarbon group, which is a hydrocarbon group having a divalent valence of a saturated hydrocarbon group on the path of the connecting chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the connecting chain is 3 more than one. In addition, R N1 and R N2 each independently represent a monovalent organic group.

在本說明書中，“連接鏈”是指在連接連接對象的2個原子或連接原子群組之間之路徑上的原子鏈中以最短（最小原子數）的方式連接該等連接對象者。例如，在下述式所表示之化合物中，L由伸苯基伸乙基構成，並且具有伸乙基作為飽和烴基，連接鏈由4個碳原子構成，連接鏈的路徑上的原子數（亦即，為構成連接鏈之原子的數量，以下，亦稱為“連接鏈長度”或“連接鏈的長度”。）為4個。 [化學式60]

Figure 02_image118
In this specification, the "connection chain" refers to the one that connects the connection objects in the shortest (minimum number of atoms) among the atomic chains on the path connecting the two atoms of the connection object or the group of connecting atoms. For example, in the compound represented by the following formula, L is composed of phenylene ethylidene, and has ethylidene as a saturated hydrocarbon group, the connecting chain is composed of 4 carbon atoms, and the number of atoms on the path of the connecting chain (that is, is The number of atoms constituting the connecting chain, hereinafter also referred to as "connecting chain length" or "connecting chain length") is four. [Chemical formula 60]
Figure 02_image118

式（B3）之L中的碳數（亦包含除了連接鏈中的碳原子以外的碳原子）為3～24為較佳。上限為12以下為更佳，10以下為進一步較佳，8以下為特佳。下限為4以上為更佳。從快速進行上述分子內環化反應之觀點考慮，L的連接鏈長度的上限為12以下為較佳，8以下為更佳，6以下為進一步較佳，5以下為特佳。尤其，L的連接鏈長度為4或5為較佳，4為最佳。作為鹼產生劑的具體的較佳化合物，例如亦可以舉出國際公開第2020/066416號的0102～0168段中所記載的化合物、國際公開第2018/038002號的0143～0177段中所記載的化合物。The number of carbon atoms in L in the formula (B3) (including carbon atoms other than the carbon atoms in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly advancing the above-mentioned intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 5 or less. In particular, it is preferable that the linking chain length of L is 4 or 5, and 4 is the most optimal. Specific preferred compounds of the base generator include, for example, compounds described in Paragraphs 0102 to 0168 of International Publication No. 2020/066416, and compounds described in Paragraphs 0143 to 0177 of International Publication No. 2018/038002. compound.

又，鹼產生劑包含下述式（N1）所表示之化合物亦較佳。 [化學式61]

Figure 02_image120
Moreover, it is also preferable that the base generator contains a compound represented by the following formula (N1). [Chemical formula 61]
Figure 02_image120

式（N1）中，R N1及R N2分別獨立地表示1價的有機基，R C1表示氫原子或保護基，L表示2價的連接基。 In formula (N1), R N1 and R N2 each independently represent a monovalent organic group, R C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L為2價的連接基，2價的有機基為較佳。連接基的連接鏈長度為1以上為較佳，2以上為更佳。作為上限，12以下為較佳，8以下為更佳，5以下為進一步較佳。連接鏈長度為在式中的2個羰基之間成為最短路程之原子排列中存在之原子的數量。L is a divalent linking group, and a divalent organic group is preferable. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. As an upper limit, 12 or less is preferable, 8 or less is more preferable, and 5 or less is more preferable. The linking chain length is the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

式（N1）中，R N1及R N2分別獨立地表示1價的有機基（碳數1～24為較佳，2～18為更佳，3～12為進一步較佳），烴基（碳數1～24為較佳，1～12為更佳，1～10為進一步較佳）為較佳，具體而言，可以舉出脂肪族烴基（碳數1～24為較佳，1～12為更佳，1～10為進一步較佳）或芳香族烴基（碳數6～22為較佳，6～18為更佳，6～10為進一步較佳），脂肪族烴基為較佳。若作為R N1及R N2使用脂肪族烴基，則所產生之鹼的鹼性高，因此為較佳。再者，脂肪族烴基及芳香族烴基可以具有取代基，並且脂肪族烴基及芳香族烴基可以在脂肪族烴鏈中或芳香環中，取代基中具有氧原子。尤其，可以例示脂肪族烴基在烴鏈中具有氧原子之態樣。 In formula (N1), R N1 and R N2 each independently represent a monovalent organic group (preferably carbon number 1-24, more preferably 2-18, further preferably 3-12), hydrocarbon group (carbon number 1 to 24 are preferred, 1 to 12 are more preferred, and 1 to 10 are further preferred), and specifically, aliphatic hydrocarbon groups (1 to 24 carbon atoms are preferred, 1 to 12 are preferred) More preferably, 1-10 is further preferred) or aromatic hydrocarbon group (preferably carbon number 6-22, 6-18 is more preferred, 6-10 is further preferred), aliphatic hydrocarbon group is preferred. When an aliphatic hydrocarbon group is used as R N1 and R N2 , since the basicity of the generated base is high, it is preferable. In addition, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the substituent in the aliphatic hydrocarbon chain or in the aromatic ring. In particular, the aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain can be exemplified.

作為構成R N1及R N2之脂肪族烴基，可以舉出直鏈或支鏈的鏈狀烷基、環狀烷基、與鏈狀烷基和環狀烷基的組合有關之基團、在鏈中具有氧原子之烷基。直鏈或支鏈的鏈狀烷基為碳數1～24者為較佳，2～18為更佳，3～12為進一步較佳。關於直鏈或支鏈的鏈狀烷基，例如可以舉出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二烷基、異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基、第三戊基、異己基等。 環狀烷基為碳數3～12者為較佳，3～6為更佳。關於環狀烷基，例如可以舉出環丙基、環丁基、環戊基、環己基、環辛基等。 與鏈狀烷基和環狀烷基的組合有關之基團為碳數4～24者為較佳，4～18為更佳，4～12為進一步較佳。關於與鏈狀烷基和環狀烷基的組合有關之基團，例如可以舉出環己基甲基、環己基乙基、環己基丙基、甲基環己基甲基、乙基環己基乙基等。 在鏈中具有氧原子之烷基為碳數2～12者為較佳，2～6為更佳，2～4為進一步較佳。在鏈中具有氧原子之烷基可以為鏈狀，亦可以為環狀，並且可以為直鏈，亦可以為支鏈。 其中，從提高後述分解生成鹼的沸點之觀點考慮，R N1及R N2為碳數5～12的烷基為較佳。其中，在重視與金屬（例如銅）的層積層時的密接性之配方中，具有環狀的烷基之基團或碳數1～8的烷基為較佳。 Examples of the aliphatic hydrocarbon groups constituting R N1 and R N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to the combination of chain alkyl groups and cyclic alkyl groups, and chain alkyl groups. An alkyl group with an oxygen atom in it. The linear or branched chain alkyl group having 1 to 24 carbon atoms is preferable, 2 to 18 are more preferable, and 3 to 12 are further preferable. Examples of linear or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, deca Dialkyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, and the like. The cyclic alkyl group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. As a cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned, for example. The group related to the combination of the chain alkyl group and the cyclic alkyl group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Groups related to the combination of a chain alkyl group and a cyclic alkyl group include, for example, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl Wait. The alkyl group having an oxygen atom in the chain is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. Among them, it is preferable that R N1 and R N2 are alkyl groups having 5 to 12 carbon atoms from the viewpoint of increasing the boiling point of the bases generated by decomposition described later. Among them, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable in a formulation that places importance on the adhesiveness at the time of lamination with a metal (for example, copper).

R N1及R N2可以相互連接而形成環狀結構。在形成環狀結構時，可以在鏈中具有氧原子等。又，R N1及R N2所形成之環狀結構可以為單環，亦可以為縮合環，但是單環為較佳。作為所形成之環狀結構，式（N1）中的含有氮原子之5員環或6員環為較佳，例如可以舉出吡咯環、咪唑環、吡唑環、吡咯啉環、吡咯啶環、咪唑啶環、吡唑啶環、哌啶環、哌𠯤環、嗎啉環等，可以較佳地舉出吡咯啉環、吡咯啶環、哌啶環、哌𠯤環、嗎啉環。 R N1 and R N2 may be connected to each other to form a ring structure. When forming a cyclic structure, an oxygen atom or the like may be included in the chain. In addition, the cyclic structure formed by R N1 and R N2 may be a single ring or a condensed ring, but a single ring is preferable. The cyclic structure to be formed is preferably a 5-membered or 6-membered ring containing a nitrogen atom in the formula (N1), and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, and a pyrrolidine ring. , an imidazoline ring, a pyrazolidine ring, a piperidine ring, a piperidine ring, a morpholine ring, and the like, preferably a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperidine ring, and a morpholine ring.

R C1表示氫原子或保護基，氫原子為較佳。 R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

作為保護基，藉由酸或鹼的作用進行分解之保護基為較佳，可以較佳地舉出用酸進行分解之保護基。As the protecting group, a protecting group that decomposes by the action of an acid or a base is preferable, and a protecting group that decomposes with an acid is preferably used.

作為保護基的具體例，可以舉出鏈狀或環狀的烷基或在鏈中具有氧原子之鏈狀或環狀的烷基。作為鏈狀或環狀的烷基，可以舉出甲基、乙基、異丙基、第三丁基、環己基等。作為在鏈中具有氧原子之鏈狀的烷基，具體而言，可以舉出烷基氧基烷基，更具體而言，可以舉出甲氧基甲（MOM）基、乙氧基乙（EE）基等。作為在鏈中具有氧原子之環狀的烷基，可以舉出環氧基、環氧丙基、氧環丁烷基、四氫呋喃基、四氫吡喃（THP）基等。Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. As a chain or cyclic alkyl group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, etc. are mentioned. Specific examples of the chain-like alkyl group having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methoxymethyl (MOM) groups, ethoxyethyl ( EE) base et al. As a cyclic alkyl group which has an oxygen atom in a chain, an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, a tetrahydropyran (THP) group, etc. are mentioned.

作為構成L之2價的連接基，並無特別規定，但是烴基為較佳，脂肪族烴基為更佳。烴基可以具有取代基，並且亦可以在烴鏈中具有除了碳原子以外的種類的原子。更具體而言，可以在鏈中具有氧原子的2價的烴連接基為較佳，可以在鏈中具有氧原子的2價的脂肪族烴基、2價的芳香族烴基或與可以在鏈中具有氧原子的2價的脂肪族烴基和2價的芳香族烴基的組合有關之基團為更佳，可以在鏈中具有氧原子的2價的脂肪族烴基為進一步較佳。該等基團不具有氧原子為較佳。 2價的烴連接基為碳數1～24者為較佳，2～12為更佳，2～6為進一步較佳。2價的脂肪族烴基為碳數1～12者為較佳，2～6為更佳，2～4為進一步較佳。2價的芳香族烴基為碳數6～22者為較佳，6～18為更佳，6～10為進一步較佳。與2價的脂肪族烴基和2價的芳香族烴基的組合有關之基團（例如，伸芳基烷基）為碳數7～22者為較佳，7～18為更佳，7～10為進一步較佳。 The divalent linking group constituting L is not particularly limited, but a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The hydrocarbon group may have a substituent, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a bivalent hydrocarbon linking group which may have an oxygen atom in the chain is preferable, and a bivalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a bivalent aromatic hydrocarbon group, or a bivalent aromatic hydrocarbon group which may have an oxygen atom in the chain. A group related to a combination of a divalent aliphatic hydrocarbon group having an oxygen atom and a divalent aromatic hydrocarbon group is more preferable, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is further preferable. Preferably, these groups do not have oxygen atoms. The divalent hydrocarbon linking group is preferably one having 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group is preferably one having 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group related to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an aryl-extended alkyl group) is preferably one having 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 for further better.

作為連接基L，具體而言，直鏈或支鏈的鏈狀伸烷基、環狀伸烷基、與鏈狀伸烷基和環狀伸烷基的組合有關之基團、在鏈中具有氧原子之伸烷基、直鏈或支鏈的鏈狀的伸烯基、環狀的伸烯基、伸芳基、伸芳基伸烷基為較佳。 直鏈或支鏈的鏈狀伸烷基為碳數1～12者為較佳，2～6為更佳，2～4為進一步較佳。 環狀伸烷基為碳數3～12者為較佳，3～6為更佳。 與鏈狀伸烷基和環狀伸烷基的組合有關之基團為碳數4～24者為較佳，4～12為更佳，4～6為進一步較佳。 在鏈中具有氧原子之伸烷基可以為鏈狀，亦可以為環狀，並且可以為直鏈，亦可以為支鏈。在鏈中具有氧原子之伸烷基為碳數1～12者為較佳，1～6為更佳，1～3為進一步較佳。 As the linking group L, specifically, a linear or branched chain-like alkylene group, a cyclic alkylene group, a group related to a combination of a chain-like alkylene group and a cyclic alkylene group, a group having in the chain An alkylene group of an oxygen atom, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylidene group, and an arylidene group are preferred. The linear or branched chain alkylene group having 1 to 12 carbon atoms is preferred, 2 to 6 are more preferred, and 2 to 4 are further preferred. The cyclic alkylene group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The group related to the combination of the chain alkylene group and the cyclic alkylene group is preferably one having 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkylene group having an oxygen atom in the chain may be chain-like or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain is preferably one having 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.

直鏈或支鏈的鏈狀的伸烯基為碳數2～12者為較佳，2～6為更佳，2～3為進一步較佳。直鏈或支鏈的鏈狀的伸烯基的C=C鍵的數量為1～10者為較佳，1～6為更佳，1～3為進一步較佳。 環狀的伸烯基為碳數3～12者為較佳，3～6為更佳。環狀的伸烯基的C=C鍵的數量為1～6為較佳，1～4為更佳，1～2為進一步較佳。 伸芳基為碳數6～22者為較佳，6～18為更佳，6～10為進一步較佳。 伸芳基伸烷基為碳數7～23者為較佳，7～19為更佳，7～11為進一步較佳。 其中，鏈狀伸烷基、環狀伸烷基、在鏈中具有氧原子之伸烷基、鏈狀的伸烯基、伸芳基、伸芳基、伸烷基為較佳，1,2-伸乙基、丙烷二基（尤其1,3-丙烷二基）、環己烷二基（尤其1,2-環己烷二基）、伸乙烯基（尤其順式伸乙烯基）、伸苯基（1,2-伸苯基）、伸苯基亞甲基（尤其1,2-伸苯基亞甲基）、氧伸乙基（尤其1,2-乙烯氧基-1,2-伸乙基）為更佳。 The linear or branched chain alkenylene group is preferably one having 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The number of C=C bonds of the linear or branched chain alkenylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group is preferably one having 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C=C bonds of the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 2. The aryl extended group is preferably one having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The arylidene alkylene group is preferably one having 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among them, chain alkylene, cyclic alkylene, alkylene having oxygen atoms in the chain, chain alkenylene, aryl, aryl, and alkylene are preferred, 1,2 -ethylidene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylidene (especially cis-vinylidene), vinylidene Phenyl (1,2-phenylene), phenylmethylene (especially 1,2-phenylene), oxyethylidene (especially 1,2-vinyloxy-1,2- ethylidene) is better.

作為鹼產生劑，可以舉出下述例，但是本發明並不僅由此做限定性解釋。As the base generator, the following examples can be given, but the present invention is not limited to these.

[化學式62]

Figure 02_image122
[Chemical formula 62]
Figure 02_image122

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

作為離子型鹼產生劑的具體的較佳化合物，例如亦可以舉出國際公開第2018/038002號的0148～0163段中所記載的化合物。Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.

作為銨鹽的具體例，可以舉出以下化合物，但是本發明並不限定於該等。 [化學式63]

Figure 02_image124
Specific examples of the ammonium salt include the following compounds, but the present invention is not limited to these. [Chemical formula 63]
Figure 02_image124

作為亞胺鹽的具體例，可以舉出以下化合物，但是本發明並不限定於該等。 [化學式64]

Figure 02_image126
Specific examples of the imide salt include the following compounds, but the present invention is not limited to these. [Chemical formula 64]
Figure 02_image126

在本發明的樹脂組成物包含鹼產生劑之情況下，鹼產生劑的含量相對於本發明的樹脂組成物中的樹脂100質量份為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。上限為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種以上之情況下，合計量在上述範圍內為較佳。 When the resin composition of the present invention contains an alkali generator, the content of the alkali 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. The lower limit is more preferably 0.3 parts by mass or more, and more preferably 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, still more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less. Alkali generators can be used 1 type or 2 or more types. When using 2 or more types, it is preferable that the total amount is in the said range.

＜溶劑＞ 本發明的樹脂組成物包含溶劑為較佳。 溶劑能夠任意使用公知的溶劑。溶劑較佳為有機溶劑。作為有機溶劑，可以舉出酯類、醚類、酮類、環狀烴類、亞碸類、醯胺類、脲類、醇類等化合物。 ＜Solvent＞ The resin composition of the present invention preferably contains a solvent. As the solvent, any known solvent can be used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfites, amides, ureas, and alcohols.

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

作為醚類，例如可以舉出乙二醇二甲醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇乙基甲基醚、二乙二醇丁基甲基醚、三乙二醇二甲醚、四乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇二甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、乙二醇單丁醚、乙二醇單丁醚乙酸酯、二乙二醇乙基甲基醚、丙二醇單丙醚乙酸酯、二丙二醇二甲醚等作為較佳者。Examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, and triethyl ether. Glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether Ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, dipropylene glycol dimethyl ether and the like are preferred.

作為酮類，例如可以舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、3-甲基環己酮、左旋葡聚糖酮、二氫葡聚糖酮等作為較佳者。Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levodextran ketone, and dihydrodextran Sugar ketones and the like are preferred.

作為環狀烴類，例如可以舉出甲苯、二甲苯、苯甲醚等芳香族烴類、檸檬烯等環式萜烯類作為較佳者。As cyclic hydrocarbons, aromatic hydrocarbons, such as toluene, xylene, and anisole, and cyclic terpenes, such as limonene, are mentioned as preferable ones, for example.

作為亞碸類，例如可以舉出二甲基亞碸作為較佳者。As the sulfites, for example, dimethyl sulfite can be mentioned as a preferable one.

作為醯胺類，可以舉出N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-環己酯-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N,N-二甲基異丁醯胺、3-甲氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、N-甲醯基嗎啉、N-乙醯基嗎啉等作為較佳者。Examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexylester-2-pyrrolidone, N,N-dimethylethyl acetate amide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N , N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine, etc. are preferred.

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

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

關於溶劑，從塗佈面性狀的改善等觀點考慮，混合2種以上之形態亦較佳。Regarding the solvent, from the viewpoint of improving the properties of the coating surface, etc., it is also preferable to mix two or more types.

在本發明中，選自3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基溶纖劑乙酸酯、乳酸乙酯、二乙二醇二甲醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、環戊酮、γ-丁內酯、二甲基亞碸、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、N-甲基-2-吡咯啶酮、丙二醇甲醚及丙二醇甲醚乙酸酯、左旋葡聚糖酮、二氫葡聚糖酮中之1種溶劑或由2種以上構成之混合溶劑為較佳。同時使用二甲基亞碸和γ-丁內酯或同時使用N-甲基-2-吡咯啶酮和乳酸乙酯為特佳。In the present invention, selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate Ester, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, gamma-butyrolactone, dimethylsulfoxide, ethyl carbitol acetate, butyl carbitol Alcohol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, levoglucan ketone, dihydroglucan ketone, one kind of solvent or two or more kinds of solvents The mixed solvent is preferred. It is particularly preferred to use dimethylsulfoxide and γ-butyrolactone together or N-methyl-2-pyrrolidone and ethyl lactate together.

從塗佈性的觀點考慮，將溶劑的含量設為本發明的樹脂組成物的總固體成分濃度成為5～80質量%之量為較佳，設為成為5～75質量%之量為更佳，設為成為10～70質量%之量為進一步較佳，設為成為20～70質量%為更進一步較佳。關於溶劑含量，只要依據塗膜的所期望厚度和塗佈方法進行調節即可。From the viewpoint of coatability, the content of the solvent is preferably set to an amount of 5 to 80% by mass, more preferably 5 to 75% by mass of the total solid concentration of the resin composition of the present invention , it is more preferable to set it as an amount of 10-70 mass %, and it is still more preferable to set it as 20-70 mass %. The solvent content may be adjusted according to the desired thickness of the coating film and the coating method.

本發明的樹脂組成物可以僅含有1種溶劑，亦可以含有2種以上。在含有2種以上的溶劑之情況下，其合計在上述範圍內為較佳。The resin composition of this invention may contain only 1 type of solvent, and may contain 2 or more types. When two or more kinds of solvents are contained, the total is preferably within the above-mentioned 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甲矽烷基之矽烷偶合劑、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之化合物、磷酸衍生物化合物、β酮酸酯化合物、胺基化合物等。 <Metal Adhesion Improver> It is preferable that the resin composition of this invention contains the metal adhesion improver for improving the adhesion with the metal material used for electrodes, wiring, etc.. Examples of the metal adhesion improver include alkoxysilyl-containing silane coupling agents, aluminum-based adhesive agents, titanium-based adhesive agents, compounds having sulfonamide structures, compounds having thiourea, and phosphoric acid derivatives. Compounds, β-ketoester compounds, amine compounds, etc.

〔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號的0167段中所記載的化合物、日本特開2014-191002號公報的0062～0073段中所記載的化合物、國際公開第2011/080992號的0063～0071段中所記載的化合物、日本特開2014-191252號公報的0060～0061段中所記載的化合物、日本特開2014-041264號公報的0045～0052段中所記載的化合物、國際公開第2014/097594號的0055段中所記載的化合物、日本特開2018-173573的0067～0078段中所記載的化合物，並將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，使用不同的2種以上的矽烷偶合劑亦較佳。又，矽烷偶合劑使用下述化合物亦較佳。以下式中，Me表示甲基，Et表示乙基。 [Silane coupling agent] Examples of the silane coupling agent include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, and International Publication No. 2011/080992 The compounds described in paragraphs 0063 to 0071 of JP 2014-191252 A, the compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, the compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, The compounds described in paragraph 0055 of International Publication No. 2014/097594 and the compounds described in paragraphs 0067 to 0078 of JP-A No. 2018-173573 are incorporated herein by reference. Moreover, as described in paragraphs 0050 to 0058 of JP 2011-128358 A, it is also preferable to use two or more different silane coupling agents. Moreover, 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65]

Figure 02_image128
[Chemical formula 65]
Figure 02_image128

作為其他矽烷偶合劑，例如可以舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-（3,4-環氧環己基）乙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、N-2-（胺基乙基）-3-胺基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基甲矽烷基-N-（1,3-二甲基-亞丁基）丙胺、N-苯基-3-胺基丙基三甲氧基矽烷、三-（三甲氧基甲矽烷基丙基）異氰脲酸酯、3-脲基丙基三烷氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-異氰酸酯丙基三乙氧基矽烷、3-三甲氧基甲矽烷基丙基琥珀酸酐。該等能夠單獨使用1種或組合使用2種以上。Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxysilane. 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl triethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 - Methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N-2- (Aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane Oxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-amine propyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used individually by 1 type or in combination of 2 or more types.

〔鋁系接著助劑〕 作為鋁系接著助劑，例如可以舉出鋁三（乙醯乙酸乙酯）鋁、三（乙醯丙酮）鋁、乙醯乙酸乙酯二異丙醇鋁等。 [Aluminum-based Adhesives] Examples of the aluminum-based adhesive adjuvant include aluminum tris(ethylacetate)aluminum, tris(acetoacetate)aluminum, aluminum ethylacetate diisopropoxide, 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段中所記載的化合物、日本特開2013-072935號公報的0032～0043段中所記載的硫化物系化合物，並將該等內容編入本說明書中。In addition, as other metal adhesion improving agents, the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A, and the vulcanized compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A can also be used compounds, and these contents are incorporated into 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，更佳為在0.1～10質量份的範圍內，進一步較佳為在0.5～5質量份的範圍內。藉由設為上述下限值以上，圖案與金屬層的接著性變得良好，藉由設為上述上限值以下，圖案的耐熱性、機械特性變得良好。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種以上之情況下，其合計在上述範圍內為較佳。The content of the metal adhesion improver 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 even more preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the specific resin . By setting it as the said lower limit or more, the adhesiveness of a pattern and a metal layer becomes favorable, and by setting it as the said upper limit or less, the heat resistance and mechanical properties of a pattern become favorable. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is in the said range.

＜遷移抑制劑＞ 本發明的樹脂組成物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）的金屬離子轉移至膜內。 <Migration inhibitor> It is preferable that the resin composition of the present invention further contains a migration inhibitor. By including the migration inhibitor, the transfer of metal ions originating from the metal layer (metal wiring) into the film can be effectively suppressed.

作為遷移抑制劑，並無特別限制，但是可以舉出具有雜環（吡咯環、呋喃環、噻吩環、咪唑環、㗁唑環、噻唑環、吡唑環、異㗁唑環、異噻唑環、四唑環、吡啶環、嗒𠯤環、嘧啶環、吡𠯤環、哌啶環、哌𠯤環、嗎啉環、2H-吡喃環及6H-吡喃環、三𠯤環）之化合物、具有硫脲類及氫硫基之化合物、受阻酚系化合物、水楊酸衍生物系化合物、醯肼衍生物系化合物。尤其，能夠較佳地使用1,2,4-三唑、苯并三唑、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, but includes a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, tri-pyran ring) compounds, with Thiourea and hydrogen thio compounds, hindered phenolic compounds, salicylic acid derivatives, and hydrazine derivatives. In particular, 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole can be preferably used Triazole-based compounds such as azoles, and tetrazole-based 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.

作為其他遷移抑制劑，能夠使用日本特開2013-015701號公報的0094段中所記載的防鏽劑、日本特開2009-283711號公報的0073～0076段中所記載的化合物、日本特開2011-059656號公報的0052段中所記載的化合物、日本特開2012-194520號公報的0114段、0116段及0118段中所記載的化合物、國際公開第2015/199219號的0166段中所記載的化合物等，並將該等內容編入本說明書中。As other migration inhibitors, the rust inhibitor described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, and JP 2011 A can be used. - Compounds described in paragraph 0052 of Japanese Patent Publication No. 059656, compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Laid-Open Publication No. 2012-194520, and compounds described in paragraph 0166 of International Publication No. 2015/199219 compounds, etc., and these contents are incorporated into this specification.

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

[化學式66]

Figure 02_image130
[Chemical formula 66]
Figure 02_image130

在本發明的樹脂組成物具有遷移抑制劑之情況下，遷移抑制劑的含量相對於本發明的樹脂組成物的總固體成分為0.01～5.0質量%為較佳，0.05～2.0質量%為更佳，0.1～1.0質量%為進一步較佳。When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass % with respect to the total solid content of the resin composition of the present invention , 0.1 to 1.0 mass % is more preferable.

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種以上之情況下，其合計在上述範圍內為較佳。Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more kinds of migration inhibitors, it is preferable that the total is within the above-mentioned 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 the polymerization inhibitor include phenol-based compounds, quinone-based compounds, amino-based compounds, N-oxyl radical compound-based compounds, nitro-based compounds, nitroso-based compounds, heteroaromatic ring-based compounds, metal compounds, and the like .

作為聚合抑制劑的具體的化合物，例如較佳地使用對氫醌、鄰氫醌、鄰甲氧基苯酚、對甲氧基苯酚、二-第三丁基-對甲酚、五倍子酚、對-第三丁基兒茶酚、1,4-苯醌、二苯基-對苯醌、4,4’-硫代雙（3-甲基-6-第三丁基酚）、2,2’-亞甲基雙（4-甲基-6-第三丁基酚）、N-亞硝基苯基羥基胺第一鈰鹽、N-亞硝基-N-苯基羥基胺鋁鹽、N-亞硝基二苯胺、N-苯基萘胺、伸乙基二胺四乙酸、1,2-環己二胺四乙酸、乙二醇醚二胺四乙酸、2,6-二-第三丁基-4-甲基酚、5-亞硝基-8-羥基喹啉、1-亞硝基-2-萘酚、2-亞硝基-1-萘酚、2-亞硝基-5-（N-乙基-N-磺基丙基胺）酚、N-亞硝基-N-（1-萘基）羥胺銨鹽、雙（4-羥基-3,5-第三丁基）苯基甲烷、1,3,5-三（4-第三丁基-3-羥基）-2,6-二甲基芐基）-1,3,5-三𠯤-2,4,6-（1H，3H，5H）-三酮、4-羥基-2,2,6,6-四甲基哌啶1-氧自由基、2,2,6,6-四甲基哌啶1-氧自由基、吩噻𠯤、啡㗁𠯤、1,1-二苯基-2-吡咯肼、二丁基二硫代碳酸銅（II）、硝基苯、N-亞硝基-N-苯基羥胺鋁鹽、N-亞硝基-N-苯基羥基胺銨鹽等。又，亦能夠使用日本特開2015-127817號公報的0060段中所記載的聚合抑制劑及國際公開第2015/125469號的0031～0046段中所記載的化合物，並將該內容編入本說明書中。As a specific compound of the polymerization inhibitor, for example, p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, p- tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2' - Methylene bis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxylamine first cerium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N - Nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tertiary Butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5 -(N-Ethyl-N-sulfopropylamine)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl) Phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tris𠯤-2,4,6- (1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical, 2,2,6,6-tetramethylpiperidine 1-oxygen Free radicals, phenothia, phenothia, 1,1-diphenyl-2-pyrrolehydrazine, copper(II) dibutyldithiocarbonate, nitrobenzene, N-nitroso-N-phenyl Hydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. In addition, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of International Publication No. WO 2015/125469 can also be used, and the contents are incorporated into the present specification. .

在本發明的樹脂組成物包含聚合抑制劑之情況下，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為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% by mass, preferably 0.02 to 15% by mass, more preferably 0.02 to 15% by mass relative to the total solid content of the resin composition of the present invention. 0.05-10 mass % is more preferable.

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種以上之情況下，其合計在上述範圍內為較佳。Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more kinds of polymerization inhibitors, it is preferable that the total is within the above-mentioned range.

＜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依據需要能夠配合各種的添加物、例如在本領域中公知的光酸產生劑、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，例如能夠參閱日本特開2012-003225號公報的0183段以後（所對應之美國專利申請公開第2013/0034812號說明書的0237段）的記載及日本特開2008-250074號公報的0101～0104段、0107～0109段等的記載，並將該等內容編入本說明書中。在配合該等添加劑之情況下，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 contain various additives, such as photoacid generators, surfactants, higher fatty acid derivatives, thermal polymerization initiators known in the art, as necessary within the range where the effects of the present invention can be obtained. Agents, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers and other additives (for example, defoaming agents, flame retardants, etc.), etc. By appropriately containing these components, properties such as film physical properties can be adjusted. For these components, for example, refer to the descriptions in paragraph 0183 and subsequent paragraphs of Japanese Patent Application Laid-Open No. 2012-003225 (paragraph 0237 of the corresponding specification of US Patent Application Publication No. 2013/0034812) and the descriptions in Japanese Patent Application Laid-Open No. 2008-250074 paragraphs 0101 to 0104, paragraphs 0107 to 0109, etc., and these contents are incorporated into this specification. When these additives are blended, the total blending amount is preferably 3 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、矽酮系界面活性劑、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，亦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。 [Surfactant] As the surfactant, various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant can be used. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

藉由在本發明的樹脂組成物中含有界面活性劑，進一步提高作為塗佈液進行製備時的液體特性（尤其，流動性），從而能夠進一步改善塗佈厚的均勻性或省液性。亦即，在使用適用了含有界面活性劑之組成物之塗佈液而形成膜之情況下，被塗佈面與塗佈液的界面張力降低而改善對被塗佈面的潤濕性，從而提高對被塗佈面的塗佈性。因此，能夠更佳地進行厚度不均勻小的均勻厚度的膜形成。By including a surfactant in the resin composition of the present invention, the liquid properties (especially, fluidity) at the time of preparation as a coating liquid can be further improved, and the uniformity of the coating thickness and the liquid saving property can be further improved. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved, thereby improving the wettability of the surface to be coated. Improves coatability to the coated surface. Therefore, it is possible to more preferably form a film with a uniform thickness with little thickness unevenness.

作為氟系界面活性劑，例如可以舉出MEGAFACE F171、MEGAFACE F172、MEGAFACE F173、MEGAFACE F176、MEGAFACE F177、MEGAFACE F141、MEGAFACE F142、MEGAFACE F143、MEGAFACE F144、MEGAFACE R30、MEGAFACE F437、MEGAFACE F475、MEGAFACE F479、MEGAFACE F482、MEGAFACE F554、MEGAFACE F780、RS-72-K（以上為DIC CORPORATION製）、Fluorad FC430、Fluorad FC431、Fluorad FC171、Novell FC4430、Novell FC4432（以上為3M Japan Limited製）、Surflon S-382、Surflon SC-101、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC-1068、Surflon SC-381、Surflon SC-383、Surflon S-393、Surflon KH-40（以上為ASAHI GLASS CO.,LTD.製）、PF636、PF656、PF6320、PF6520、PF7002（OMNOVA Solutions Inc.製）等。氟系界面活性劑亦能夠使用日本特開2015-117327號公報的0015～0158段中所記載的化合物、日本特開2011-132503號公報的0117～0132段中所記載的化合物，並將該等內容編入本說明書中。亦能夠使用嵌段聚合物作為氟系界面活性劑，作為具體例，例如可以舉出日本特開2011-89090號公報中所記載之化合物，並將該等內容編入本說明書中。 氟系界面活性劑亦能夠較佳地使用含氟高分子化合物，該含氟高分子化合物包含源自具有氟原子之（甲基）丙烯酸酯化合物之重複單元和源自具有2個以上（較佳為5個以上）的伸烷氧基（較佳為乙烯氧基、丙烯氧基）之（甲基）丙烯酸酯化合物之重複單元，亦可以例示下述化合物作為本發明中所使用之氟系界面活性劑。 [化學式67]

Figure 02_image132
Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (the above are manufactured by DIC CORPORATION), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novell FC4430, Novell FC4432 (the above are manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (ASAHI GLASS CO above ., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A and the compounds described in paragraphs 0117 to 0132 of JP 2011-132503 A can also be used, and these The contents are incorporated into this manual. A block polymer can also be used as a fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090, which are incorporated into the present specification. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, the fluorine-containing polymer compound comprising a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a compound having two or more (preferably A repeating unit of a (meth)acrylate compound of an alkaneoxy group (preferably vinyloxy group, propyleneoxy group) having 5 or more), the following compounds can also be exemplified as the fluorine-based interface used in the present invention active agent. [Chemical formula 67]
Figure 02_image132

上述化合物的重量平均分子量較佳為3,000～50,000，5,000～30,000為更佳。 氟系界面活性劑亦能夠將在側鏈上具有乙烯性不飽和基之含氟聚合物用作氟系界面活性劑。作為具體例，可以舉出日本特開2010-164965號公報的0050～0090段及0289～0295段中所記載之化合物，並將該內容編入本說明書中。又，作為市售品，例如可以舉出DIC CORPORATION製的MEGAFACE RS-101、RS-102、RS-718K等。 The weight average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000. Fluorine-based Surfactant A fluoropolymer having an ethylenically unsaturated group on a side chain can also be used as a fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, which are incorporated into the present specification. Moreover, as a commercial item, MEGAFACE RS-101 by DIC CORPORATION, RS-102, RS-718K etc. are mentioned, for example.

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

作為矽酮系界面活性劑，例如可以舉出Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH8400（以上為Dow Corning Toray Co.,Ltd.製）、TSF-4440、TSF-4300、TSF-4445、TSF-4460、TSF-4452（以上為Momentive performance Materials Inc.製）、KP-341、KF6001、KF6002（以上為Shin-Etsu Chemical Co., Ltd.製）、BYK307、BYK323、BYK330（以上為BYK Chemie GmbH製）等。Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (the above are Dow Corning Toray Co. ., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive performance Materials Inc.), KP-341, KF6001, KF6002 (the above are Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (the above are manufactured by BYK Chemie GmbH), and the like.

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

作為非離子型界面活性劑，可以例示甘油、三羥甲基丙烷、三羥甲基乙烷以及該等乙氧基化物及丙氧基化物（例如，甘油丙氧基化物、甘油乙氧基化物等）、聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、山梨糖醇酐脂肪酸酯等。作為市售品，可以舉出Pluronic（註冊商標）L10、L31、L61、L62、10R5、17R2、25R2（BASF公司製）、Tetronic 304、701、704、901、904、150R1（BASF公司製）、Solsperse 20000（Lubrizol Japan Ltd.製）、NCW-101、NCW-1001、NCW-1002（FUJIFILM Wako Pure Chemical Corporation製）、PIONIN D-6112、D-6112-W、D-6315（TAKEMOTO OIL&FAT CO.,LTD製）、OLFIN E1010、Surfynol 104、400、440（Nissin Chemical co.,ltd.製）等。As the nonionic surfactant, glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate) can be exemplified etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilauric acid ester, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (TAKEMOTO OIL&FAT CO., LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), and the like.

作為陽離子系界面活性劑，具體而言，可以舉出有機矽氧烷聚合物KP-341（Shin-Etsu Chemical Co., Ltd.製）、（甲基）丙烯酸系（共）聚合物Polyflow No.75、No.77、No.90、No.95（KYOEISHA CHEMICAL Co.,LTD.製）、W001（Yusho Co.,Ltd.製）等。Specific examples of the cationic surfactant include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No. 75, No.77, No.90, No.95 (manufactured by KYOEISHA CHEMICAL Co., LTD.), W001 (manufactured by Yusho Co., Ltd.), and the like.

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

界面活性劑可以僅使用1種，亦可以組合使用2種以上。 界面活性劑的含量相對於組成物的總固體成分為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 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

〔高級脂肪酸衍生物〕 為了防止因氧引起的聚合阻礙，可以在本發明的樹脂組成物中添加如二十二酸或二十二酸醯胺的高級脂肪酸衍生物，從而使其在塗佈後的乾燥過程中不均勻地存在於本發明的樹脂組成物的表面上。 [Higher fatty acid derivatives] In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the resin composition of the present invention to make it non-uniform in the drying process after coating exist on the surface of the resin composition of the present 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段中所記載的化合物，並將該內容編入本說明書中。In addition, the compound described in the paragraph 0155 of International Publication No. WO 2015/199219 can also be used as the higher fatty acid derivative, and the content is incorporated in the present specification.

在本發明的樹脂組成物具有高級脂肪酸衍生物之情況下，高級脂肪酸衍生物的含量相對於本發明的樹脂組成物的總固體成分為0.1～10質量%為較佳。高級脂肪酸衍生物可以為僅1種，亦可以為2種以上。在高級脂肪酸衍生物為2種以上之情況下，其合計在上述範圍內為較佳。When the resin composition of the present invention has 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. Only one type of higher fatty acid derivatives may be used, or two or more types may be used. When there are two or more kinds of higher fatty acid derivatives, it is preferable that the total is within the above-mentioned 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為藉由熱的能量而產生自由基並開始或促進具有聚合性之化合物的聚合反應之化合物。藉由添加熱自由基聚合起始劑，亦能夠進行樹脂及聚合性化合物的聚合反應，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功能，有時能夠作為熱聚合起始劑而添加。 [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 a radical by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, so that 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，並將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 JP-A No. 2008-063554, which are incorporated herein by reference.

在包含熱聚合起始劑之情況下，其含量相對於本發明的樹脂組成物的總固體成分為0.1～30質量%為較佳，更佳為0.1～20質量%，進一步較佳為0.5～15質量%。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種以上的熱聚合起始劑之情況下，合計量在上述範圍內為較佳。When a thermal polymerization initiator is contained, 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. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more 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粒子。作為無機粒子，具體而言，能夠包含碳酸鈣、磷酸鈣、二氧化矽、高嶺土、滑石、二氧化鈦、氧化鋁、硫酸鋇、氟化鈣、氟化鋰、沸石、硫化鉬、玻璃等。 [Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, as inorganic particles, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc. can be included.

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。 無機粒子的上述平均粒徑為一次粒徑，並且為體積平均粒徑。關於體積平均粒徑，能夠藉由基於Nanotrac WAVE II EX-150（Nikkiso Co., Ltd.製）之動態光散射法進行測定。 在難以進行上述測定之情況下，亦能夠藉由離心沉降透光法、X射線透射法、雷射繞射/散射法進行測定。 The average particle diameter 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 said average particle diameter of an inorganic particle is a primary particle diameter, and is a volume average particle diameter. The volume average particle diameter can be measured by a dynamic light scattering method based on Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). In the case where it is difficult to perform the above-mentioned measurement, the measurement can also be performed by the centrifugal sedimentation light transmission method, the X-ray transmission method, and the 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、三𠯤系等紫外線吸收劑。 作為水楊酸酯系紫外線吸收劑的例子，可以舉出水楊酸苯酯、水楊酸對辛基苯酯、水楊酸對第三丁基苯酯等，作為二苯甲酮系紫外線吸收劑的例子，可以舉出2,2’-二羥基-4-甲氧基二苯甲酮、2,2’-二羥基-4,4’-二甲氧基二苯甲酮、2,2’,4,4’-四羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2,4-二羥基二苯甲酮、2-羥基-4-辛氧基二苯甲酮等。又，作為苯并三唑系紫外線吸收劑的例子，可以舉出2-（2’-羥基-3’,5’-二-第三丁基苯基）-5-氯苯并三唑、2-（2’-羥基-3’-第三丁基-5’-甲基苯基）-5-氯苯并三唑、2-（2’-羥基-3’-第三戊基-5’-異丁基苯基）-5-氯苯并三唑、2-（2’-羥基-3’-異丁基-5’-甲基苯基）-5-氯苯并三唑、2-（2’-羥基-3’-異丁基-5’-丙基苯基）-5-氯苯并三唑、2-（2’-羥基-3’,5’-二-第三丁基苯基）苯并三唑、2-（2’-羥基-5’-甲基苯基）苯并三唑、2-[2’-羥基-5’-（1,1,3,3-四甲基）苯基]苯并三唑等。 [Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, ultraviolet absorbers such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and trisulfuric acid-based absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like. Examples of benzophenone-based ultraviolet absorbers include Examples of the agent include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ',4,4'-Tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxydiphenyl ketone etc. Moreover, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2- -(2'-Hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5' -isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2- (2'-Hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butyl Phenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetrakis Methyl)phenyl]benzotriazole, etc.

作為取代丙烯腈系紫外線吸收劑的例子，可以舉出2-氰基-3,3-二苯基丙烯酸乙酯、2-氰基-3,3-二苯基丙烯酸2-乙基己酯等。進而，作為三𠯤系紫外線吸收劑的例子，可以舉出2-[4-[（2-羥基-3-十二烷氧基丙基）氧基]-2-羥基苯基]-4,6-雙（2,4-二甲基苯基）-1,3,5-三𠯤、2-[4-[（2-羥基-3-十三烷氧基丙基）氧基]-2-羥基苯基]-4,6-雙（2,4-二甲基苯基）-1,3,5-三𠯤、2-（2,4-二羥基苯基）-4,6-雙（2,4-二甲基苯基）-1,3,5-三𠯤等單（羥基苯基）三𠯤化合物；2,4-雙（2-羥基-4-丙氧基苯基）-6-（2,4-二甲基苯基）-1,3,5-三𠯤、2,4-雙（2-羥基-3-甲基-4-丙氧基苯基）-6-（4-甲基苯基）-1,3,5-三𠯤、2,4-雙（2-羥基-3-甲基-4-己氧基苯基）-6-（2,4-二甲基苯基）-1,3,5-三𠯤等雙（羥基苯基）三𠯤化合物；2,4-雙（2-羥基-4-丁氧基苯基）-6-（2,4-二丁氧基苯基）-1,3,5-三𠯤、2,4,6-三（2-羥基-4-辛氧基苯基）-1,3,5-三𠯤、2,4,6-三[2-羥基-4-（3-丁氧基-2-羥基丙氧基）苯基]-1,3,5-三𠯤等三（羥基苯基）三𠯤化合物等。Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like . Furthermore, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 is mentioned as an example of a tris-based ultraviolet absorber -Bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2- Hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris𠯤, 2-(2,4-dihydroxyphenyl)-4,6-bis( 2,4-Dimethylphenyl)-1,3,5-tris(hydroxyphenyl)tris-compounds such as 2,4-bis(2-hydroxy-4-propoxyphenyl)-6 -(2,4-Dimethylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4 -Methylphenyl)-1,3,5-tris𠯤, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethyl Phenyl)-1,3,5-tris(bis(hydroxyphenyl)tris) compounds such as bis(hydroxyphenyl)tris; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis) Butoxyphenyl)-1,3,5-tris𠯤, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris𠯤, 2,4, 6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris-tris(hydroxyphenyl)tris-compounds, etc.

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，但是在包含之情況下，紫外線吸收劑的含量相對於本發明的組成物的總固體成分質量為0.001質量%以上且1質量%以下為較佳，0.01質量%以上且0.1質量%以下為更佳。 In this invention, the said various ultraviolet absorbers may be used individually by 1 type, and may be used in combination of 2 or more types. The composition of the present invention may or may not contain an ultraviolet absorber, but when included, the content of the ultraviolet absorber is 0.001% by mass or more and 1% by mass relative to the total solid mass of the composition of the present invention. Mass % or less is preferable, and 0.01 mass % or more and 0.1 mass % or less are more preferable.

〔有機鈦化合物〕 本實施形態的樹脂組成物可以含有有機鈦化合物。由於樹脂組成物含有有機鈦化合物，因此即使在低溫下進行硬化之情況下亦能夠形成耐藥品性優異之樹脂層。 [Organo-titanium compound] The resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organotitanium compound, a resin layer excellent in chemical resistance can be formed even when it is cured at a low temperature.

作為能夠使用的有機鈦化合物，可以舉出有機基經由共價鍵或離子鍵與鈦原子鍵結者。 將有機鈦化合物的具體例示於以下I）～VII）中： I）鈦螯合化合物：其中，樹脂組成物的保存穩定性優異，並且可以獲得良好的硬化圖案，從而具有2個以上的烷氧基之鈦螯合化合物為更佳。具體的例子為二異丙醇雙（三乙醇胺）鈦、二（正丁醇）雙（2,4-戊二酮）鈦、二異丙醇雙（2,4-戊二酮）鈦、二異丙醇雙（四甲基庚二酮）鈦、二異丙醇雙（乙醯乙酸乙酯）鈦等。 II）四烷氧基鈦化合物：例如為四（正丁醇）鈦、四乙醇鈦、四（2-乙基己醇）鈦、四異丁醇鈦、四異丙醇鈦、四甲醇鈦、四甲氧基丙醇鈦、四甲基苯氧化鈦、四（正壬醇）鈦、四（正丙醇）鈦、四硬脂醇鈦、四[雙｛2,2-（烯丙氧基甲基）丁醇｝]鈦等。 III）二茂鈦化合物：例如為五甲基環戊二烯基三甲醇鈦、雙（η5-2,4-環戊二烯-1-基）雙（2,6-二氟苯基）鈦、雙（η5-2,4-環戊二烯-1-基）雙（2,6-二氟-3-（1H-吡咯-1-基）苯基）鈦等。 IV）單烷氧基鈦化合物：例如為三（二辛基磷酸酯）異丙醇鈦、三（十二烷苯基磺酸酯）異丙醇鈦等。 V）氧化鈦化合物：例如為氧化鈦雙（戊二酮）、氧化鈦雙（四甲基庚二酮）、酞菁氧化鈦等。 VI）四乙醯丙酮鈦化合物：例如為四乙醯丙酮鈦等。 VII）鈦酸酯偶合劑：例如為異丙基三十二烷基苯磺醯鈦酸鹽等。 As the organotitanium compound that can be used, an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organotitanium compounds are shown in the following I) to VII): I) Titanium chelate compound: Among them, the resin composition has excellent storage stability and can obtain a good hardened pattern, so the titanium chelate compound having two or more alkoxy groups is more preferable. Specific examples are diisopropoxide bis(triethanolamine) titanium, di(n-butanol) bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, diisopropoxide bis(2,4-pentanedione) titanium, Isopropanol bis (tetramethylheptanedione) titanium, diisopropanol bis (ethyl acetate) titanium, etc. II) Titanium tetraalkoxide compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetrakis(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, Titanium Tetramethoxypropoxide, Titanium Tetramethylphenoxide, Titanium Tetra(n-nonanol), Titanium Tetra(n-propoxide), Titanium Tetrastearyloxide, Tetrakis[bis{2,2-(allyloxy) Methyl) butanol}] titanium and so on. III) Titanocene compounds: for example, titanium pentamethylcyclopentadienyltrimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium , bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) titanium, etc. IV) Monoalkoxytitanium compounds: for example, tris(dioctyl phosphate) titanium isopropoxide, tris(dodecylphenyl sulfonate) titanium isopropoxide, and the like. V) Titanium oxide compound: for example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, and the like. VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agent: for example, isopropyl tridodecylbenzenesulfonic acid titanate and the like.

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

在配合有機鈦化合物之情況下，其配合量相對於特定樹脂100質量份為0.05～10質量份為較佳，更較佳為0.1～2質量份。在配合量為0.05質量份以上之情況下，所獲得之硬化圖案更有效地顯現出良好的耐熱性及耐藥品性，另一方面，在配合量為10質量份以下之情況下，組成物的保存穩定性更優異。When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, with respect to 100 parts by mass of the specific resin. When the compounding amount is 0.05 parts by mass or more, the obtained cured pattern exhibits good heat resistance and chemical resistance more effectively. On the other hand, when the compounding amount is 10 parts by mass or less, the The storage stability is more excellent.

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

[化學式68]

Figure 02_image134
[Chemical formula 68]
Figure 02_image134

通式（3）中，R 5表示氫原子或碳數2以上（較佳為碳數2～10）的烷基，R 6表示碳數2以上（較佳為碳數2～10）的伸烷基。R 7表示碳數2以上（較佳為碳數2～10）的伸烷基、包含氧原子及氮原子中的至少任一個之1～4價的有機基。k表示1～4的整數。 In the general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably carbon number 2 to 10), and R 6 represents an extension of carbon number 2 or more (preferably carbon number 2 to 10). alkyl. R 7 represents an alkylene group having 2 or more carbon atoms (preferably, a carbon number of 2 to 10), and a 1- to 4-valent organic group containing at least any one of an oxygen atom and a nitrogen atom. k represents an integer of 1-4.

式（3）所表示之化合物抑制樹脂所具有之脂肪族基和酚性羥基的氧化劣化。又，能夠藉由對金屬材料的防鏽作用來抑制金屬氧化。The compound represented by the formula (3) suppresses the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group contained in the resin. Moreover, metal oxidation can be suppressed by the rust preventive effect on the metal material.

能夠同時作用於樹脂和金屬材料，因此k為2～4的整數為更佳。作為R 7，可以舉出烷基、環烷基、烷氧基、烷基醚基、烷基甲矽烷基、烷氧基甲矽烷基、芳基、芳基醚基、羧基、羰基、烯丙基、乙烯基、雜環基、-O-、-NH-、-NHNH-、組合了該等者等，還可以具有取代基。其中，從在顯影液中的溶解性和金屬密接性的觀點考慮，具有烷基醚基、-NH-為較佳，從與樹脂的相互作用和金屬錯合物形成時之金屬密接性的觀點考慮，-NH-為更佳。 Since it can act on a resin and a metal material at the same time, it is more preferable that k is an integer of 2 to 4. Examples of R 7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, and an allyl group. group, vinyl group, heterocyclic group, -O-, -NH-, -NHNH-, a combination of these, etc., and may have a substituent. Among them, those having an alkyl ether group and -NH- are preferred from the viewpoints of solubility in a developer and metal adhesion, and from the viewpoints of interaction with resins and metal adhesion at the time of metal complex formation Consider, -NH- is better.

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

[化學式69]

Figure 02_image136
[Chemical formula 69]
Figure 02_image136

[化學式70]

Figure 02_image138
[Chemical formula 70]
Figure 02_image138

[化學式71]

Figure 02_image140
[Chemical formula 71]
Figure 02_image140

[化學式72]

Figure 02_image142
[Chemical formula 72]
Figure 02_image142

抗氧化劑的添加量相對於樹脂為0.1～10質量份為較佳，0.5～5質量份為更佳。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，亦容易獲得提高伸長特性或對金屬材料之密接性的效果，並且藉由將添加量設為10質量份以下，例如藉由與光敏劑的相互作用來提高樹脂組成物的靈敏度。抗氧化劑可以僅使用1種，亦可以使用2種以上。在使用2種以上之情況下，該等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, more preferably 0.5 to 5 parts by mass, with respect to the resin. By setting the addition amount to 0.1 parts by mass or more, even in a high temperature and high humidity environment, it is easy to obtain the effect of improving elongation properties and adhesion to metal materials, and by setting the addition amount to 10 parts by mass or less, for example The sensitivity of the resin composition is improved by the interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When using 2 or more types, it is preferable that these total amounts are in the said range.

〔抗凝聚劑〕 本實施形態的樹脂組成物依據需要可以含有抗凝聚劑。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-agglomeration agent as needed. As an anti-agglomeration agent, sodium polyacrylate etc. are mentioned.

在本發明中，抗凝聚劑可以單獨使用1種，亦可以組合使用2種以上。 本發明的組成物可以包含抗凝聚劑，亦可以不包含抗凝聚劑，但是在包含之情況下，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為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 this invention, an anti-agglomeration agent may be used individually by 1 type, and may be used in combination of 2 or more types. The composition of the present invention may or may not contain an anti-agglomeration agent, but when included, the content of the anti-agglomeration agent is 0.01% by mass or more and 10% by mass relative to the total solid mass of the composition of the present invention. Mass % or less is preferable, and 0.02 mass % or more and 5 mass % or less are more preferable.

〔酚系化合物〕 本實施形態的樹脂組成物依據需要可以含有酚系化合物。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、亞甲基三-FR-CR、BisRS-26X（以上為產品名稱，Honshu Chemical Industry Co.,Ltd.製）、BIP-PC、BIR-PC、BIR-PTBP、BIR-BIPC-F（以上為產品名稱，ASAHI YUKIZAI CORPORATION製）等。 [Phenolic compounds] The resin composition of this embodiment may contain a phenolic compound as needed. Examples of phenolic compounds 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, Methylenetris-FR-CR, BisRS-26X (the product names above, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC , BIR-PTBP, BIR-BIPC-F (the above is the product name, 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，但是在包含之情況下，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為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, the phenolic compound may be used alone or in combination of two or more. The composition of the present invention may or may not contain the phenolic compound, but when included, the content of the phenolic compound is 0.01% by mass or more and 30% by mass relative to the total solid mass of the composition of the present invention. Mass % or less is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

〔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、將（甲基）丙烯酸進行共聚而獲得之（甲基）丙烯酸聚合物、酚醛清漆樹脂、甲酚樹脂、聚羥基苯乙烯樹脂及該等共聚物等。其他高分子化合物可以為導入有羥甲基、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 resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolak resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. things etc. The other polymer compound may be a modified product into which a cross-linking group such as a methylol group, an alkoxymethyl group, and an epoxy group is introduced.

在本發明中，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，但是在包含之情況下，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為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, other polymer compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds, but when included, the content of the other polymer compounds is 0.01% by mass relative to the total solid mass of the composition of the present invention More than 30 mass % is preferable, and 0.02 mass % or more and 20 mass % or less are more preferable.

＜樹脂組成物的特性＞ 關於本發明的樹脂組成物的黏度，能夠藉由樹脂組成物的固體成分濃度來調整。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。若為1,000mm 2/s以上，則例如容易以作為再配線用絕緣膜所需要之膜厚進行塗佈，若為12,000mm 2/s以下，則可以獲得塗佈表面形態優異之塗膜。 <Characteristics of the resin composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm 2 /s to 12,000 mm 2 /s is preferable, 2,000 mm 2 /s to 10,000 mm 2 /s is more preferable, and 2,500 mm 2 /s to 8,000 mm 2 /s for further better. As long as it is in the said range, it becomes easy to obtain the coating film with high uniformity. If it is 1,000 mm 2 /s or more, for example, 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 morphology can be obtained.

＜關於樹脂組成物的含有物質的限制＞ 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。只要小於2.0%，則提高樹脂組成物的保存穩定性。 作為維持水分的含量之方法，可以舉出調整保管條件中之濕度及降低保管時的收容容器的孔隙率等。 <Restrictions on Substances Contained in Resin Compositions> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. As long as it is less than 2.0%, the storage stability of the resin composition is improved. As a method of maintaining the moisture content, adjustment of the humidity in the storage conditions, reduction of the porosity of the storage container during storage, and the like are exemplified.

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，但是作為有機化合物與金屬的錯合物而包含之金屬除外。在包含複數個金屬之情況下，該等金屬的合計在上述範圍內為較佳。From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million (parts per million)), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm good. Examples of the metal include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, and the like, with the exception of metals included as complexes of organic compounds and metals. When a plurality of metals are contained, it is preferable that the sum of these metals is within the above-mentioned range.

又，作為減少意外包含於本發明的樹脂組成物中之金屬雜質之方法，可以舉出如下方法：選擇金屬含量少的原料作為構成本發明的樹脂組成物之原料；對構成本發明的樹脂組成物之原料進行過濾器過濾；將聚四氟乙烯等內襯於裝置內以在盡可能抑制污染之條件下進行蒸餾。Further, as a method for reducing the metal impurities accidentally contained in the resin composition of the present invention, there can be mentioned a method of selecting a raw material having a small metal content as a raw material constituting the resin composition of the present invention; The raw material of the product is filtered through a filter; the polytetrafluoroethylene and the like are lined in the device to conduct distillation under the condition that the pollution is suppressed as much as possible.

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

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，為了抑制雜質混入原材料或本發明的樹脂組成物中，使用由6種6層樹脂構成容器內壁之多層瓶、將6種樹脂形成為7層結構之瓶亦較佳。作為該種容器，例如可以舉出日本特開2015-123351號公報中所記載的容器。As a container of the resin composition of the present invention, a conventionally known container can be used. Further, as the container, in order to suppress the contamination of impurities into the raw material or the resin composition of the present invention, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

＜樹脂組成物的硬化物＞ 藉由將本發明的樹脂組成物進行硬化，能夠獲得該樹脂組成物的硬化物。 本發明的硬化物為將本發明的樹脂組成物硬化而成之硬化物。 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170℃～350℃的範圍內為特佳。樹脂組成物的硬化物的形態並無特別限定，能夠依據用途選擇薄膜狀、棒狀、球狀、顆粒狀等。在本發明中，該硬化物為薄膜狀為較佳。又，藉由樹脂組成物的圖案加工，亦能夠依據在壁面上形成保護膜，形成用於導通的穴（Beer hall）、調整阻抗或靜電容量或者內部應力、賦予放熱功能等用途選擇該硬化物的形狀。該硬化物（由硬化物形成之膜）的膜厚為0.5μm以上且150μm以下為較佳。 將本發明的樹脂組成物進行硬化時的收縮率為50%以下為較佳，45%以下為更佳，40%以下為進一步較佳。其中，收縮率是指樹脂組成物的硬化前後的體積變化的百分率，並且能夠藉由下述的式來進行計算。 收縮率[%]=100-（硬化後的體積÷硬化前的體積）×100 <The cured product of the 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. The hardening of the resin composition is preferably carried out by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and in the range of 170°C to 350°C Excellent inside. The form of the cured product of the resin composition is not particularly limited, and a film form, a rod form, a spherical form, a granular form, and the like can be selected according to the application. In the present invention, the cured product is preferably in the form of a film. Furthermore, by patterning the resin composition, the cured product can also be selected for purposes such as forming a protective film on the wall surface, forming a beer hall for conduction, adjusting impedance, capacitance or internal stress, and imparting a heat release function. shape. The film thickness of the cured product (film formed from the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage ratio when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage ratio refers to the percentage of volume change before and after curing of the resin composition, and can be calculated by 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。只要為70%以上，則有時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 cured 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 even more preferably 90% or more. As long as it is 70% or more, it may become a cured product excellent in mechanical properties. 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 even more 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 even more 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。混合方法並無特別限定，能夠藉由先前公知的方法來進行。 混合能夠採用基於攪拌葉片之混合、基於球磨機之混合、使罐自身旋轉之混合等。 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 a conventionally known method. For the mixing, mixing by a stirring blade, mixing by a ball mill, mixing by rotating a tank itself, and the like can be employed. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

又，為了去除本發明的樹脂組成物中的灰塵或微粒等異物，進行使用過濾器之過濾為較佳。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。在過濾器的材質為聚乙烯之情況下，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。在過濾器的過濾步驟中，亦可以串聯或並聯連接複數種過濾器而使用。在使用複數種過濾器之情況下，可以組合使用孔徑或材質不同之過濾器。作為連接態樣，例如可以舉出將孔徑1μm的HDPE過濾器作為第1級且將孔徑0.2μm的HDPE過濾器作為第2級進行串聯連接之態樣。又，可以將各種材料過濾複數次。在過濾複數次之情況下，可以為循環過濾。又，亦可以在加壓之後進行過濾。在加壓並進行過濾之情況下，進行加壓之壓力例如可以舉出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，還可以進行使用吸附材料之雜質去除處理。亦可以組合過濾器過濾與使用吸附材料之雜質去除處理。作為吸附材料，能夠使用公知的吸附材料。例如，可以舉出矽膠、沸石等無機系吸附材料、活性碳等有機系吸附材料。 進而，在使用過濾器之過濾之後，還可以實施在減壓狀態下放置填充於瓶中之樹脂組成物並進行脫氣之步驟。 In addition, in order to remove foreign matter, such as dust and fine particles, in the resin composition of the present invention, it is preferable to perform filtration using a filter. The filter pore diameter is, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, HDPE (High Density Polyethylene) is better. Filters can be pre-cleaned with organic solvents. In the filtering step of the filter, a plurality of filters may be connected in series or in parallel and used. In the case of using a plurality of filters, filters with different pore sizes or materials can be used in combination. As a connection aspect, for example, an HDPE filter having a pore diameter of 1 μm as the first stage and an HDPE filter having a pore diameter of 0.2 μm as the second stage are connected in series. Also, various materials can be filtered multiple times. In the case of filtering multiple times, it can be a loop filtering. Moreover, you may filter after pressurization. In the case of pressurizing and filtering, the pressurizing pressure can be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. Preferably, it is more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, impurity removal treatment using an adsorbent can also be performed. It is also possible to combine filter filtration and impurity removal treatment using adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be mentioned. Furthermore, after the filtration using a filter, the step of leaving the resin composition filled in the bottle in a reduced pressure state and deaerating may be carried out.

（硬化物之製造方法） 本發明的硬化物之製造方法包括將樹脂組成物適用於基材上而形成膜之膜形成步驟為較佳。 又，本發明的硬化物之製造方法包括上述膜形成步驟、選擇性地曝光藉由膜形成步驟而形成之膜之曝光步驟及使用顯影液對藉由曝光步驟進行曝光之膜進行顯影而形成圖案之顯影步驟為更佳。 本發明的硬化物之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而獲得之圖案進行加熱之加熱步驟及對藉由顯影步驟而獲得之圖案進行曝光之顯影後曝光步驟中的至少一者為特佳。 又，本發明之製造方法包括上述膜形成步驟及對上述膜進行加熱之步驟亦較佳。 以下，對各步驟的詳細內容進行說明。 (Manufacturing method of hardened product) It is preferable that the manufacturing method of the hardened|cured material of this invention includes the film formation process of forming a film by applying a resin composition to a base material. Moreover, the manufacturing method of the hardened|cured material of this invention comprises the said film formation process, the exposure process of selectively exposing the film formed by the film formation process, and developing the film exposed by the exposure process using a developing solution to form a pattern The development step is better. The manufacturing method of the hardened|cured material of this invention includes the said film formation process, the said exposure process, the said development process, the heating process which heats the pattern obtained by the development process, and the exposure process of the pattern obtained by the development process. At least one of the post-development exposure steps is particularly preferred. Moreover, it is also preferable that the manufacturing method of this invention includes the said film formation step and the step of heating the said film. Hereinafter, the details of each step will be described.

＜膜形成步驟＞ 本發明的樹脂組成物能夠用於適用於基材上而形成膜之膜形成步驟中。 本發明的硬化物之製造方法包括將樹脂組成物適用於基材上而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 for forming a film by applying it to a substrate. It is preferable that the manufacturing method of the hardened|cured material of this invention includes the film formation process of forming a film by applying a resin composition to a base material.

〔基材〕 基材的種類能夠依據用途適當設定，但是並無特別限制，可以舉出矽、氮化矽、多晶矽、氧化矽、非晶矽等半導體製作基材、石英、玻璃、光學膜、陶瓷材料、蒸鍍膜、磁性膜、反射膜、Ni、Cu、Cr、Fe等金屬基材（例如，可以為由金屬形成之基材及例如藉由電鍍或蒸鍍等而形成金屬層之基材中的任一個）、紙、SOG（Spin On Glass：旋塗式玻璃）、TFT（薄膜晶體管）陣列基材、模具基材、電漿顯示面板（PDP）的電極板等。在本發明中，尤其半導體製作基材為較佳，矽基材、Cu基材及模具基材為更佳。 又，在該等基材的表面上可以設置有由六甲基二矽氮烷（HMDS）等製成之密接層和氧化層等層。 又，基材的形狀並無特別限定，可以為圓形，亦可以為矩形。 作為基材的尺寸，若為圓形，則例如直徑為100～450mm，較佳為200～450mm。若為矩形，則例如短邊的長度為100～1000mm，較佳為200～700mm。 又，作為基材，例如可以使用板狀、較佳為面板狀的基材（基板）。 [Substrate] The type of the substrate can be appropriately set according to the application, but is not particularly limited, and examples thereof include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor Metal substrates such as coating films, magnetic films, reflective films, Ni, Cu, Cr, Fe, etc. ), paper, SOG (Spin On Glass: spin-on glass), TFT (Thin Film Transistor) array substrates, mold substrates, electrode plates for plasma display panels (PDP), etc. In the present invention, especially semiconductor fabrication substrates are preferred, and silicon substrates, Cu substrates and mold substrates are even 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 these substrates. In addition, the shape of the base material is not particularly limited, and may be circular or rectangular. As a size of a base material, if it is a circle, a diameter is 100-450 mm, for example, Preferably it is 200-450 mm. In the case of a rectangle, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm. Moreover, as a base material, for example, a plate-shaped, preferably panel-shaped base material (substrate) can be used.

又，在樹脂層（例如，由硬化物形成之層）的表面或金屬層的表面上適用樹脂組成物而形成膜之情況下，樹脂層或金屬層成為基材。Moreover, when a resin composition is applied to the surface of a resin layer (for example, a layer formed of a cured product) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a 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 of applying the resin composition of the present invention to a substrate, coating is preferable.

作為所適用之方法，具體而言，可以例示浸塗法、氣刀塗佈法、簾式塗佈法、線棒塗佈法、凹版塗佈法、擠壓塗佈法、噴塗法、旋塗法、狹縫塗佈法、噴墨法等。從膜的厚度的均勻性的觀點考慮，更佳為旋塗法、狹縫塗佈法、噴塗法或噴墨法，從膜的厚度的均勻性的觀點及生產率的觀點考慮，旋塗法及狹縫塗佈法為較佳。依據方法調整樹脂組成物的固體成分濃度或塗佈條件，從而能夠獲得所期望的厚度的膜。又，亦能夠依據基材的形狀適當選擇塗佈方法，若為晶圓等圓形基材，則旋塗法、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。在為旋塗法的情況下，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賦予至偽支撐體上而形成之塗膜轉印到基材上之方法。 關於轉印方法，本發明中亦能夠較佳地使用日本特開2006-023696號公報的0023段、0036～0051段或日本特開2006-047592號公報的0096～0108段中所記載的製作方法。 又，可以進行在基材的端部中去除多餘的膜的步驟。在該種步驟的例子中，可以舉出邊珠沖洗（EBR）、背面沖洗（Back rinse）等。 又，亦可以採用預濕步驟，該預濕步驟在將樹脂組成物塗佈於基材上之前，對基材塗佈各種溶劑以提高基材的潤濕性之後，塗佈樹脂組成物。 Specific examples of the applicable method include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, and spin coating. method, slit coating method, inkjet method, etc. From the viewpoint of uniformity of film thickness, spin coating method, slit coating method, spray method or inkjet method are more preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating method and The slit coating method is preferred. A film having a desired thickness can be obtained by adjusting the solid content concentration or coating conditions of the resin composition according to the method. In addition, the coating method can also be appropriately selected according to the shape of the substrate. In the case of a circular substrate such as a wafer, spin coating, spray coating, inkjet method, etc. are preferred, and in the case of a rectangular substrate, slit A coating method, a spraying method, an ink jet method, etc. are preferable. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Moreover, the method of transcribe|transferring the coating film formed by the said application method to a dummy support beforehand is also applicable to a base material. Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used in the present invention. . Also, a step of removing excess film in the end portion of the base material may be performed. Examples of such a step include edge bead rinse (EBR), back rinse (Back rinse), and the like. In addition, a pre-wetting step may be employed, in which the resin composition is applied after various solvents are applied to the substrate to improve the wettability of the substrate before the resin composition is applied to the substrate.

＜乾燥步驟＞ 上述膜在膜形成步驟（層形成步驟）之後，為了去除溶劑，可以供於乾燥所形成之膜（層）之步驟（乾燥步驟）中。 亦即，本發明的硬化物之製造方法可以包括乾燥步驟，該乾燥步驟乾燥藉由膜形成步驟而形成之膜。 又，上述乾燥步驟在膜形成步驟之後且在曝光步驟之前進行為較佳。 乾燥步驟中之膜的乾燥溫度為50～150℃為較佳，70℃～130℃為更佳，90℃～110℃為進一步較佳。又，亦可以藉由減壓來進行乾燥。作為乾燥時間，可以例示30秒鐘～20分鐘，1分鐘～10分鐘為較佳，2分鐘～7分鐘為更佳。 <Drying step> After the film forming step (layer forming step), the above-mentioned film may be used in a step (drying step) of drying the formed film (layer) in order to remove the solvent. That is, the manufacturing method of the hardened|cured material of this invention may include the drying process which dries the film formed by the film formation process. Moreover, it is preferable to perform the said drying process after a film formation process and before an exposure process. The drying temperature of the film in the drying step is preferably 50-150°C, more preferably 70-130°C, and further preferably 90-110°C. Moreover, drying can also be performed by reducing pressure. As the drying time, 30 seconds to 20 minutes can be exemplified, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

＜曝光步驟＞ 上述膜可以供於選擇性地曝光膜之曝光步驟中。 亦即，本發明的硬化物之製造方法可以包括曝光步驟，該曝光步驟選擇性地曝光藉由膜形成步驟而形成之膜。 選擇性地曝光表示對膜的一部分進行曝光。又，藉由選擇性地曝光，在膜上形成經曝光之區域（曝光部）和未經曝光的區域（非曝光部）。 關於曝光量，只要能夠將本發明的樹脂組成物硬化，則並無特別規定，例如以在波長365nm下的曝光能量換算為50～10,000mJ/cm 2為較佳，200～8,000mJ/cm 2為更佳。 <Exposure step> The said film can be used for the 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 which selectively exposes the film formed by the film formation process. Selectively exposing means exposing a portion of the film. Moreover, by selectively exposing, an exposed area (exposed part) and an unexposed area (non-exposed part) are formed on the film. The exposure amount is not particularly limited as long as the resin composition of the present invention can be cured. For example, the exposure energy at a wavelength of 365 nm is converted to 50 to 10,000 mJ/cm 2 , preferably 200 to 8,000 mJ/cm 2 . for better.

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

關於曝光波長，若以與光源的關係進行說明，則可以舉出（1）半導體雷射（波長830nm、532nm、488nm、405nm、375nm、355nm etc.）、（2）金屬鹵化物燈、（3）高壓水銀燈、g射線（波長436nm）、h射線（波長405nm）、i射線（波長365nm）、寬（g、h、i射線的3波長）、（4）準分子雷射、KrF準分子雷射（波長248nm）、ArF準分子雷射（波長193nm）、F2準分子雷射（波長157nm）、（5）極紫外線；EUV（波長13.6nm）、（6）電子束、（7）YAG雷射的第二諧波532nm且第三諧波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，可以獲得尤其高的曝光靈敏度。 又，曝光的方式並無特別限定，只要為曝光由本發明的樹脂組成物形成之膜的至少一部分之方式即可，但是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, if the relationship with the light source is explained, (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), broad (3 wavelengths of g, h, i-ray), (4) excimer laser, KrF excimer laser radiation (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser The second harmonic of the radiation is 532nm and the third harmonic is 355nm, etc. Regarding the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferable, and among them, exposure by i-ray is preferable. Thereby, a particularly high exposure sensitivity can be obtained. In addition, the method of exposure is not particularly limited, as long as it is a method of exposing at least a part of the film formed of the resin composition of the present invention, and exposure using a mask, exposure by direct laser imaging, etc. .

＜曝光後加熱步驟＞ 上述膜可以供於在曝光後進行加熱之步驟（曝光後加熱步驟）中。 亦即，本發明的硬化物之製造方法可以包括曝光後加熱步驟，該曝光後加熱步驟加熱藉由曝光步驟進行曝光之膜。 曝光後加熱步驟能夠在曝光步驟之後且在顯影步驟之前進行。 曝光後加熱步驟中之加熱溫度為50℃～140℃為較佳，60℃～120℃為更佳。 曝光後加熱步驟中之加熱時間為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之升溫速度，從加熱開始時的溫度至最高加熱溫度為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之加熱機構，並無特別限定，能夠使用公知的加熱板、烘箱、紅外線加熱器等。 又，藉由在加熱時使氮氣、氦氣、氬氣等非活性氣體流過等而在低氧濃度的環境下進行亦較佳。 <Heating step after exposure> The above-mentioned film may be used in a step of heating 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 which heats the film exposed by the exposure process. The post-exposure heating step can be performed after the exposure step and before the developing step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, 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. Regarding the heating rate in the post-exposure heating step, the temperature from the start of heating to the maximum heating temperature is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and still more preferably 3 to 10°C/min good. In addition, the temperature increase rate can be appropriately changed during the heating process. It does not specifically limit as a heating means in a post-exposure heating process, A well-known hot plate, oven, infrared heater, etc. can be used. Moreover, it is also preferable to carry out in the environment of a low oxygen concentration by flowing inert gas, such as nitrogen gas, helium gas, and argon gas, etc. at the time of heating.

＜顯影步驟＞ 曝光後的上述膜可以供於使用顯影液進行顯影而形成圖案之顯影步驟中。 亦即，本發明的硬化物之製造方法可以包括顯影步驟，該顯影步驟使用顯影液對藉由曝光步驟進行曝光之膜進行顯影而形成圖案。 藉由進行顯影來去除膜的曝光部及非曝光部中的一者，並形成圖案。 其中，將藉由顯影步驟去除膜的非曝光部之顯影稱為負型顯影，將藉由顯影步驟去除膜的曝光部之顯影稱為正型顯影。 <Development step> The above-mentioned film after exposure can be used in the developing step of forming a pattern by developing with a developing solution. That is, the manufacturing method of the hardened|cured material of this invention may include the developing process which develops the film exposed by the exposure process using a developing solution, and forms 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. Among them, the development of removing the non-exposed portion of the film by the development step is called negative development, and the development of removing the exposed portion of the film by 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，可以舉出鹼性水溶液或包含有機溶劑之顯影液。 [Developer] As the developing solution used in the developing step, an alkaline aqueous solution or a developing solution containing an organic solvent can be exemplified.

在顯影液為鹼性水溶液之情況下，作為鹼性水溶液能夠包含之鹼性化合物，可以舉出無機鹼類、一級胺類、二級胺類、三級胺類、四級銨鹽，TMAH（氫氧化四甲銨）、氫氧化鉀、碳酸鈉、氫氧化鈉、矽酸鈉、偏矽酸鈉、氨、乙胺、正丙胺、二乙胺、二正丁胺、三乙胺、甲基二乙胺、二甲基乙醇胺、三乙醇胺、氫氧化四乙基銨、氫氧化四丙銨（Tetrapropylammonium Hydroxide）、氫氧化四丁基銨、氫氧化四戊基銨、氫氧化四己基銨、氫氧化四辛基銨、氫氧化乙基三甲基銨、氫氧化丁基三甲基銨、氫氧化甲基三戊基銨、氫氧化二丁基二戊基銨、氫氧化二甲基雙（2-羥乙基）銨、氫氧化三甲基苯基銨、氫氧化三甲基苄基銨、氫氧化三乙基苄基銨、吡咯、哌啶為較佳，更佳為TMAH。例如在使用TMAH之情況下，顯影液中之鹼性化合物的含量在顯影液總質量中為0.01～10質量%為較佳，0.1～5質量%為更佳，0.3～3質量%為進一步較佳。When the developing solution is an alkaline aqueous solution, examples of the alkaline compounds that the alkaline aqueous solution can contain include inorganic bases, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, TMAH ( Tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyl Diethylamine, Dimethylethanolamine, Triethanolamine, Tetraethylammonium Hydroxide, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Tetrapentylammonium Hydroxide, Tetrahexylammonium Hydroxide, Hydrogen Tetraoctylammonium oxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethyl bis(hydroxide) 2-hydroxyethyl)ammonium, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole and piperidine are preferred, and TMAH is more preferred. For example, in the case of 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 even more preferably 0.3 to 3% by mass in the total mass of the developer. good.

在顯影液包含有機溶劑之情況下，關於有機溶劑，作為酯類，例如可以較佳地舉出乙酸乙酯、乙酸正丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、γ-丁內酯、ε-己內酯、δ-戊內酯、烷氧基乙酸烷基酯（例：烷氧基乙酸甲酯、烷氧基乙酸乙酯、烷氧基乙酸丁酯（例如，甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等））、3-烷氧基丙酸烷基酯類（例：3-烷氧基丙酸甲酯、3-烷氧基丙酸乙酯等（例如，3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯等））、2-烷氧基丙酸烷基酯類（例：2-烷氧基丙酸甲酯、2-烷氧基丙酸乙酯、2-烷氧基丙酸丙酯等（例如，2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯））、2-烷氧基-2-甲基丙酸甲酯及2-烷氧基-2-甲基丙酸乙酯（例如，2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯等）、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯等，以及作為醚類，例如可以較佳地舉出二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單乙醚、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚（PGME）、丙二醇單甲醚乙酸酯（PGMEA）、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯等，以及作為酮類，例如可以較佳地舉出甲基乙基酮、環己酮、環戊酮、2-庚酮、3-庚酮、N-甲基-2-吡咯啶酮等，以及作為環狀烴類，例如可以較佳地舉出甲苯、二甲苯、苯甲醚等芳香族烴類、檸檬烯等環式萜烯類、作為亞碸類，可以較佳地舉出二甲基亞碸以及作為醇類，可以較佳地舉出甲醇、乙醇、丙醇、異丙醇、丁醇、戊醇、辛醇、二乙二醇、丙二醇、甲基異丁基甲醇、三乙二醇等以及作為醯胺類，可以較佳地舉出N-甲基吡咯啶酮、N-乙基吡咯啶酮、二甲基甲醯胺等。When the developing solution contains an organic solvent, the organic solvent includes, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, propionic acid, etc., for example. Butyl, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkoxyacetate alkoxyacetate (e.g. methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl methoxyacetate) Methyl oxyacetate, ethyl ethoxyacetate, etc.), 3-alkoxy propionate alkyl esters (for example: 3-alkoxy propionate methyl ester, 3-alkoxy ethyl propionate, etc.) (For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkoxy Alkyl propionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., 2-methoxypropionic acid) methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkoxy -Methyl 2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (eg, methyl 2-methoxy-2-methylpropanoate, 2-ethoxy-2- ethyl methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, 2-oxobutane Ethyl acid, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethylene glycol Cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone can be preferably used ketone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene, anisole, cyclic terpenes such as limonene, Preferable examples of the sulfites include dimethylsulfoxide, and as the alcohols, preferred examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, and diethylenediol. Alcohol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., and as the amides, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide are preferably used. Wait.

在顯影液包含有機溶劑之情況下，有機溶劑能夠使用1種或混合使用2種以上。在本發明中，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的至少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的至少1種之顯影液為更佳，包含環戊酮之顯影液為最佳。When the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, development of at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone and cyclohexanone is particularly included The solution is preferred, and the developing solution containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethylsulfoxide is more preferred, and the developing solution including cyclopentanone is the most preferred.

在顯影液包含有機溶劑之情況下，有機溶劑的含量相對於顯影液的總質量為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，上述含量可以為100質量%。When the developing solution contains an organic solvent, the content of the organic solvent 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 more relative to the total mass of the developer solution. The above are 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 components. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

〔顯影液的供給方法〕 關於顯影液的供給方法，只要能夠形成所期望的圖案，則並無特別限制，存在將形成有膜之基材浸漬於顯影液中之方法、使用噴嘴向形成於基材上之膜供給顯影液以進行旋覆浸沒顯影或連續供給顯影液之方法。噴嘴的種類並無特別限制，可以舉出直式噴嘴、噴淋噴嘴、噴霧噴嘴等。 從顯影液的滲透性、非圖像部的去除性、製造上的效率的觀點考慮，使用直式噴嘴供給顯影液之方法或使用噴霧噴嘴連續供給之方法為較佳，從顯影液向圖像部的滲透性的觀點考慮，使用噴霧噴嘴進行供給之方法為更佳。 又，可以採用在使用直式噴嘴連續供給顯影液之後，旋轉基材以從基材上去除顯影液，在旋轉乾燥之後再次使用直式噴嘴連續供給之後，旋轉基材以從基材上去除顯影液之步驟，亦可以反覆進行複數次該步驟。 又，作為顯影步驟中之顯影液的供給方法，能夠採用將顯影液連續地供給至基材之步驟、在基材上使顯影液保持大致靜止狀態之步驟、在基材上利用超聲波等使顯影液振動之步驟及組合了該等之步驟等。 [How to supply developer] The method for supplying the developer is not particularly limited as long as a desired pattern can be formed, and there are methods of immersing the substrate on which the film is formed in the developer, and supplying the developer to the film formed on the substrate using a nozzle In order to carry out spin-on immersion development or continuous supply of developer. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removal of the non-image area, and the production efficiency, the method of supplying the developer using a straight nozzle or the method of continuously supplying the developer using a spray nozzle is preferable. From the viewpoint of the permeability of the part, the method of supplying using a spray nozzle is more preferable. Also, after the developer is continuously supplied using the straight nozzle, the substrate is rotated to remove the developer from the substrate, and after the continuous supply using the straight nozzle again after spin drying, the substrate is rotated to remove the developer from the substrate. The step of liquid solution can also be repeated several times. In addition, as a method of supplying the developer in the developing step, a step of continuously supplying the developer to the substrate, a step of keeping the developer in a substantially stationary state on the substrate, and developing the substrate by ultrasonic waves or the like can be employed The steps of liquid vibration and the steps combining these, etc.

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無特別規定，能夠較佳為在10～45℃下進行，更較佳為在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 developing solution at the time of development is not particularly limited, but it can be preferably carried out at 10 to 45°C, and more preferably at 18 to 30°C.

在顯影步驟中，在使用了顯影液之處理之後，可以進一步進行使用沖洗液之圖案的清洗（沖洗）。又，可以採用與圖案接觸之顯影液沒有完全乾燥之前供給沖洗液等的方法。In the developing step, after the treatment with the developing solution, cleaning (rinsing) of the pattern using the rinsing solution may be further performed. In addition, a method of supplying a rinsing liquid or the like may be employed before the developing liquid in contact with the pattern is completely dried.

〔沖洗液〕 在顯影液為鹼性水溶液之情況下，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之情況下，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）。 [Rinse fluid] When the developing solution is an alkaline aqueous solution, for example, water can be used as the rinsing solution. In the case where the developing solution is a developing solution containing an organic solvent, as the rinsing solution, for example, a solvent different from the solvent contained in the developing solution (for example, water, an organic solvent different from the organic solvent contained in the developing solution) can be used ).

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

在沖洗液包含有機溶劑之情況下，有機溶劑能夠使用1種或混合使用2種以上。在本發明中，尤其環戊酮、γ-丁內酯、二甲基亞碸、N-甲基吡咯啶酮、環己酮、PGMEA、PGME為較佳，環戊酮、γ-丁內酯、二甲基亞碸、PGMEA、PGME為更佳，環己酮、PGMEA為進一步較佳。When the rinsing liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, especially cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are preferred, cyclopentanone, γ-butyrolactone , dimethyl sulfoxide, PGMEA, PGME are more preferred, and cyclohexanone and PGMEA are further preferred.

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

沖洗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 rinse fluid may further contain other ingredients. As another component, a well-known surfactant, a well-known antifoamer, etc. are mentioned, for example.

〔沖洗液的供給方法〕 關於沖洗液的供給方法，只要能夠形成所期望的圖案，則並無特別限制，存在將基材浸漬於沖洗液中之方法、藉由旋覆浸沒（液盤）供給至基材上、以噴淋形式將沖洗液供給至基材之方法、藉由直式噴嘴等機構將沖洗連續供給至基材之方法。 從沖洗液的滲透性、非圖像部的去除性、製造上的效率的觀點考慮，存在使用噴淋噴嘴、直式噴嘴、噴霧噴嘴等供給沖洗液之方法，使用噴霧噴嘴連續供給之方法為較佳，從沖洗液向圖像部的滲透性的觀點考慮，使用噴霧噴嘴進行供給之方法為更佳。噴嘴的種類並無特別限制，可以舉出直式噴嘴、噴淋噴嘴、噴霧噴嘴等。 亦即，沖洗步驟為藉由直式噴嘴將沖洗液供給或連續供給至上述曝光後的膜中之步驟為較佳，藉由噴霧噴嘴供給沖洗液之步驟為更佳。 又，作為沖洗步驟中之沖洗液的供給方法，能夠採用將沖洗液連續地供給至基材之步驟、在基材上使沖洗液保持大致靜止狀態之步驟、在基材上利用超聲波等使沖洗液振動之步驟及組合了該等之步驟等。 [How to supply the rinse solution] The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed. There are methods of immersing the substrate in the rinsing liquid, supplying the substrate by immersion (liquid pan) by spin coating, and spraying The method of supplying the rinsing liquid to the substrate in the form of a shower, and the method of continuously supplying the rinse to the substrate through a mechanism such as a straight nozzle. From the viewpoints of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is: Preferably, from the viewpoint of the permeability of the rinse liquid to the image portion, the method of supplying it using a spray nozzle is more preferable. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the above-mentioned exposed film through a straight nozzle, and more preferably a step of supplying the rinsing liquid through a spray nozzle. In addition, as a method of supplying the rinsing liquid in the rinsing step, a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially static state on the substrate, and rinsing the substrate with ultrasonic waves or the like can be used. The steps of liquid vibration and the steps combining these, etc.

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無特別規定，能夠較佳為在10～45℃下進行，更較佳為在18℃～30℃下進行。The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid at the time of rinsing is not particularly limited, but it can be performed preferably at 10 to 45°C, and more preferably at 18 to 30°C.

＜加熱步驟＞ 藉由顯影步驟而獲得之圖案（在進行沖洗步驟之情況下為沖洗後的圖案）可以供於對藉由上述顯影而獲得之圖案進行加熱之加熱步驟中。 亦即，本發明的硬化物之製造方法可以包括加熱步驟，該加熱步驟對藉由顯影步驟而獲得之圖案進行加熱。 又，本發明的硬化物之製造方法可以包括加熱步驟，該加熱步驟對在不進行顯影步驟的狀態下藉由其他方法而獲得之圖案或藉由膜形成步驟而獲得之膜進行加熱。 在加熱步驟中，使聚醯亞胺前驅物等樹脂環化而成為聚醯亞胺等樹脂。 又，亦進行特定樹脂或除了特定樹脂以外的交聯劑中之未反應的交聯性基的交聯等。 作為加熱步驟中之加熱溫度（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 rinsed pattern in the case of the rinse step) may be used in the heating step of heating the pattern obtained by the above development. That is, the manufacturing method of the hardened|cured material of this invention may include the heating process which heats the pattern obtained by the developing process. Moreover, the manufacturing method of the hardened|cured material of this invention may include the heating process which heats the pattern obtained by another method or the film obtained by the film formation process in the state which did not carry out the developing process. In the heating step, resins such as polyimide precursors are cyclized into resins such as polyimide. Moreover, the crosslinking etc. of the unreacted crosslinkable group in a specific resin or a crosslinking agent other than a specific resin are also performed. As the heating temperature (maximum heating temperature) in the heating step, 50-450°C is preferable, 150-350°C is more preferable, 150-250°C is further preferable, 160-250°C is further preferable, 160- 230°C is particularly preferred.

加熱步驟為藉由加熱並利用從上述鹼產生劑產生之鹼等的作用而在上述圖案內促進上述聚醯亞胺前驅物的環化反應之步驟為較佳。The heating step is preferably a step of promoting the cyclization reaction of the above-mentioned polyimide precursor in the above-mentioned pattern by heating and utilizing the action of a base or the like generated from the above-mentioned alkali generator.

關於加熱步驟中之加熱，從加熱開始時的溫度至最高加熱溫度以1～12℃/分鐘的升溫速度進行為較佳。上述升溫速度為2～10℃/分鐘為更佳，3～10℃/分鐘為進一步較佳。藉由將升溫速度設為1℃/分鐘以上，能夠確保生產率的同時，防止酸或溶劑的過度揮發，藉由將升溫速度設為12℃/分鐘以下，能夠緩和硬化物的殘存應力。 另外，在為能夠急速加熱的烘箱的情況下，從加熱開始時的溫度至最高加熱溫度以1～8℃/秒鐘的升溫速度進行為較佳，2～7℃/秒鐘為更佳，3～6℃/秒鐘為進一步較佳。 The heating in the heating step is preferably performed at a temperature increase rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature. The above-mentioned temperature increase rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min. By setting the temperature increase rate to 1°C/min or more, excessive volatilization of the acid or solvent can be prevented while maintaining productivity, and by setting the temperature increase rate to 12°C/min or less, the residual stress of the cured product can be alleviated. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out a heating rate of 1 to 8°C/sec, more preferably 2 to 7°C/sec, from the temperature at the start of heating to the maximum heating temperature. 3 to 6°C/sec is more preferable.

加熱開始時的溫度為20℃～150℃為較佳，20℃～130℃為更佳，25℃～120℃為進一步較佳。加熱開始時的溫度是指開始加熱至最高加熱溫度之步驟時的溫度。例如，在將本發明的樹脂組成物適用於基材上之後使其乾燥之情況下，為該乾燥後的膜（層）的溫度，例如從比本發明的樹脂組成物中所包含之溶劑的沸點低30～200℃的溫度開始升溫為較佳。The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the film (layer) after drying is, for example, higher than the temperature of the solvent contained in the resin composition of the present invention. It is preferable to start the temperature rise at a temperature that is 30 to 200°C lower in the boiling point.

加熱時間（在最高加熱溫度下的加熱時間）為5～360分鐘為較佳，10～300分鐘為更佳，15～240分鐘為進一步較佳。The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

尤其，在形成多層積層體之情況下，從層間的密接性的觀點考慮，加熱溫度為30℃以上為較佳，80℃以上為更佳，100℃以上為進一步較佳，120℃以上為特佳。 上述加熱溫度的上限為350℃以下為較佳，250℃以下為更佳，240℃以下為進一步較佳。 In particular, when forming a multilayer laminate, from the viewpoint of the adhesion between layers, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, more preferably 100°C or higher, and particularly 120°C or higher. good. The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

加熱可以階段性地進行。作為例子，可以進行如下步驟：從25℃以3℃/分鐘升溫至120℃且在120℃下保持60分鐘，並且從120℃以2℃/分鐘升溫至180℃且在180℃下保持120分鐘。又，如美國專利第9159547號說明書中所記載，一邊照射紫外線一邊進行處理亦較佳。藉由該種預處理步驟，能夠提高膜的特性。預處理步驟在10秒鐘～2小時左右的短時間內進行即可，15秒鐘～30分鐘為更佳。預處理可以為2個階段以上的步驟，例如可以在100～150℃的範圍內進行第1階段的預處理步驟，之後在150～200℃的範圍內進行第2階段的預處理步驟。 進而，可以在加熱後進行冷卻，作為此時的冷卻速度，1～5℃/分鐘為較佳。 Heating can be performed in stages. As an example, the following steps may be performed: ramp from 25°C to 120°C at 3°C/min and hold at 120°C for 60 minutes, and ramp from 120°C to 180°C at 2°C/min and hold at 180°C for 120 minutes . Moreover, as described in the specification of US Pat. No. 9,159,547, it is also preferable to perform treatment while irradiating ultraviolet rays. By such a pretreatment step, the characteristics of the film can be improved. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be two or more steps, for example, the pretreatment step of the first step may be performed in the range of 100 to 150°C, and then the pretreatment step of the second step may be performed in the range of 150 to 200°C. Furthermore, cooling may be performed after heating, and the cooling rate at this time is preferably 1 to 5°C/min.

在防止特定樹脂分解的方面而言，藉由在加熱步驟中使氮氣、氦氣、氬氣等非活性氣體流過且在減壓狀態下進行等而在低氧濃度的環境下進行為較佳。氧濃度為50ppm（體積比）以下為較佳，20ppm（體積比）以下為更佳。 作為加熱步驟中之加熱機構，並無特別限定，例如可以舉出加熱板、紅外線爐、電烘箱、熱風式烘箱、紅外線烘箱等。 From the viewpoint of preventing the decomposition of the specific resin, it is preferable to conduct the heating step in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, and argon under a reduced pressure state. . The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less. Although it does not specifically limit as a heating means in a heating process, For example, a hot plate, an infrared furnace, an electric oven, a hot air oven, an infrared oven etc. are mentioned.

＜顯影後曝光步驟＞ 代替上述加熱步驟或除了上述加熱步驟以外，藉由顯影步驟而獲得之（在進行沖洗步驟之情況下為沖洗後的圖案）亦可以供於曝光顯影步驟之後的圖案之顯影後曝光步驟中。 亦即，本發明的硬化物之製造方法可以包括顯影後曝光步驟，該顯影後曝光步驟對藉由顯影步驟而獲得之圖案進行曝光。本發明的硬化物之製造方法可以包括加熱步驟及顯影後曝光步驟，亦可以僅包括加熱步驟及顯影後曝光步驟中的一者。 在顯影後曝光步驟中，例如能夠促進藉由光鹼產生劑的感光而進行聚醯亞胺前驅物等的環化之反應或藉由光酸產生劑的感光而進行酸分解性基的脫離之反應等。 在顯影後曝光步驟中，只要曝光在顯影步驟中所獲得之圖案的至少一部分即可，但是曝光上述圖案的全部為較佳。 顯影後曝光步驟中之曝光量以在感光性化合物具有靈敏度之波長下之曝光能量換算為50～20,000mJ/cm 2為較佳，100～15,000mJ/cm 2為更佳。 顯影後曝光步驟例如能夠使用上述曝光步驟中之光源來進行，使用寬頻帶光為較佳。 <Exposure step after development> Instead of the above heating step or in addition to the above heating step, the image obtained by the development step (in the case of performing the rinse step, the rinsed pattern) can also be used for the development of the pattern after the exposure development step. in the post-exposure step. That is, the manufacturing method of the hardened|cured material of this invention may include the post-development exposure process which exposes the pattern obtained by the development process. The manufacturing method of the cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, a reaction of cyclization of a polyimide precursor or the like by exposure to a photobase generator can be accelerated, or a reaction of detachment of an acid-decomposable group by exposure to a photoacid generator can be accelerated. reaction etc. In the post-development exposure step, it is sufficient to expose at least a part of the pattern obtained in the development step, but it is preferable to expose all of the above-mentioned patterns. The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 , when the exposure energy at the wavelength at which the photosensitive compound has sensitivity is converted. The post-development exposure step can be performed using, for example, the light source in the above-mentioned exposure step, preferably broadband light.

＜金屬層形成步驟＞ 藉由顯影步驟而獲得之圖案（供於加熱步驟及顯影後曝光步驟中的至少一者之圖案為較佳）可以供於在圖案上形成金屬層之金屬層形成步驟中。 亦即，本發明的硬化物之製造方法包括金屬層形成步驟為較佳，該金屬層形成步驟在藉由顯影步驟而獲得之圖案（供於加熱步驟及顯影後曝光步驟中的至少一者之圖案為較佳）上形成金屬層。 <Metal layer formation step> The pattern obtained by the developing step (preferably the pattern for 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, it is preferable that the manufacturing method of the cured product of the present invention includes a metal layer forming step in the pattern obtained by the developing step (for at least one of the heating step and the post-development exposure step). pattern is preferably formed on the metal layer.

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

金屬層的形成方法並無特別限定，能夠適用現有的方法。例如，能夠使用日本特開2007-157879號公報、日本特表2001-521288號公報、日本特開2004-214501號公報、日本特開2004-101850號公報、美國專利第7888181B2、美國專利第9177926B2中所記載之方法。例如，可以考慮光微影、PVD（物理蒸鍍法）、CVD（化學氣相沉積法）、剝離、電解電鍍、無電解電鍍、蝕刻、印刷及組合了該等之方法等。更具體而言，可以舉出組合了濺射、光微影及蝕刻之圖案化方法、組合了光微影和電解電鍍之圖案化方法。作為電鍍的較佳態樣，可以舉出使用了硫酸銅或氰化銅電鍍液之電解電鍍。The formation method of the metal layer is not particularly limited, and conventional methods can be applied. For example, Japanese Patent Application Laid-Open No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Laid-Open No. 2004-214501, Japanese Patent Application Laid-Open No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. the method described. For example, photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electrolytic plating, electroless plating, etching, printing, methods combining these, and the like can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned. As a preferable aspect of electroplating, electrolytic electroplating using a copper sulfate or copper cyanide electroplating solution can be mentioned.

作為金屬層的厚度，最厚的壁厚的部分為0.01～50μm為較佳，1～10μm為更佳。The thickness of the metal layer is preferably 0.01 to 50 μm, and more preferably 1 to 10 μm, in the thickest part.

＜用途＞ 作為能夠適用本發明的硬化物之製造方法或本發明的硬化物的領域，可以舉出半導體元件的絕緣膜、再配線層用層間絕緣膜、應力緩衝膜等。除此以外，亦可以舉出密封膜、基板材料（柔性印刷電路板的基底膜或覆蓋膜、層間絕緣膜）或藉由對如上述實際安裝用途的絕緣膜進行蝕刻而形成圖案之情況等。關於該等用途，例如能夠參閱Science&Technology Co.,Ltd.“聚醯亞胺的高功能化和應用技術”2008年4月、柿本雅明/監修、CMC技術圖書館“聚醯亞胺材料的基礎和開發”2011年11月發行、日本聚醯亞胺/芳香族系高分子研究會/編“最新聚醯亞胺基礎和應用”NTS,2010年8月等。 ＜Use＞ Examples of the field to which the method for producing the cured product of the present invention or the cured product of the present invention can be applied include insulating films for semiconductor elements, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, sealing films, substrate materials (base films or cover films of flexible printed wiring boards, interlayer insulating films), and patterns formed by etching insulating films for practical mounting as described above can also be used. For such uses, for example, you can refer to Science&Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaki Kakimoto/Supervisor, CMC Technical Library "Basics and Application of Polyimide Materials" "Development" published in November 2011, Japan Polyimide/Aromatic Polymer Research Association/Edited "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc.

又，本發明的硬化物之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、蝕刻成形組件的用途、電子尤其微電子中之保護漆及介電層的製造等中。In addition, the manufacturing method of the cured product of the present invention or the cured product of the present invention can also be used for the manufacture of layouts such as offset printing plates or screen plates, the use of etching forming components, and the protection of protective paint and dielectric layers in electronics, especially in microelectronics. manufacturing etc.

（積層體及積層體之製造方法） 本發明的積層體是指具有複數層由本發明的硬化物形成之層之結構體。 本發明的積層體為包括2層以上的由硬化物形成之層之積層體，並且亦可以設為積層3層以上而成之積層體。 上述積層體中所包括之2層以上的由上述硬化物形成之層中的至少1個為由本發明的硬化物形成之層，從抑制硬化物的收縮或上述收縮所伴隨之硬化物的變形等之觀點考慮，上述積層體中所包括之所有由硬化物形成之層為由本發明的硬化物形成之層亦較佳。 (Laminated body and method for manufacturing the laminated body) The layered product of the present invention refers to a structure having a plurality of layers formed of the cured product of the present invention. The layered body of the present invention is a layered body including two or more layers formed of a cured product, and may be a layered body formed by stacking three or more layers. At least one of the two or more layers formed of the above-mentioned cured product included in the above-mentioned layered body is a layer formed of the cured product of the present invention, and suppresses the shrinkage of the cured product or the deformation of the cured product accompanying the shrinkage, etc. From a viewpoint, it is also preferable that all the layers formed of the cured product included in the above-mentioned laminate are layers formed of the cured product of the present invention.

亦即，本發明的積層體之製造方法包括本發明的硬化物之製造方法為較佳，包括重複複數次本發明的硬化物之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|cured material of this invention, and it is more preferable to include the steps of repeating the manufacturing method of the hardened|cured material of this invention several times.

本發明的積層體包括2層以上的由硬化物形成之層，在由上述硬化物形成之層之間的任一個之間包括金屬層之態樣為較佳。關於上述金屬層，藉由上述金屬層形成步驟而形成為較佳。 亦即，本發明的積層體之製造方法在複數次進行之硬化物之製造方法之間，進一步包括在由硬化物形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如上所述。 作為上述積層體，例如可以舉出至少包含依次積層有第一個由硬化物形成之層、金屬層、第二個由硬化物形成之層這3個層之層結構之積層體作為較佳者。 上述第一個由硬化物形成之層及上述第二個由硬化物形成之層均為由本發明的硬化物形成之層為較佳。用於形成上述第一個由硬化物形成之層之本發明的樹脂組成物和用於形成上述第二個由硬化物形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。本發明的積層體中之金屬層可以較佳地用作再配線層等金屬配線。 The layered product of the present invention includes two or more layers formed of a cured product, and an aspect in which a metal layer is included between any of the layers formed of the cured product is preferred. 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 forming step of forming a metal layer on the layer formed of the hardened|cured material between the manufacturing methods of the hardened|cured material performed a plurality of times. The preferred aspect of the metal layer forming step is as described above. As the above-mentioned layered product, for example, a layered product having a layer structure in which at least three layers of a first layer made of a cured product, a metal layer, and a second layer of a cured product are laminated in this order can be mentioned as a preferred one. . It is preferable that the above-mentioned first layer formed from the hardened product and the above-mentioned second layer formed from the hardened product are both layers formed from the hardened product of the present invention. The resin composition of the present invention for forming the above-mentioned first layer formed of the hardened material and the resin composition of the present invention for forming the above-mentioned second layer formed of the hardened material may be compositions of the same composition, or Compositions with different compositions may be used. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a rewiring layer.

＜積層步驟＞ 本發明的積層體之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）或金屬層的表面上再次依序進行（a）膜形成步驟（層形成步驟）、（b）曝光步驟、（c）顯影步驟、（d）加熱步驟及顯影後曝光步驟中的至少一者之一系列步驟。其中，亦可以為重複（a）膜形成步驟及（d）加熱步驟及顯影後曝光步驟中的至少一者之態樣。又，在（d）加熱步驟及顯影後曝光步驟中的至少一者之後，還可以包括（e）金屬層形成步驟。在積層步驟中可以進一步適當包括上述乾燥步驟等，這是不言而喻的。 <Lamination step> It is preferable that the manufacturing method of the laminated body of this invention includes a lamination|stacking step. The lamination step includes again sequentially performing (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, (d) a heating step, on the surface of the pattern (resin layer) or metal layer. A series of steps of at least one of the post-development exposure steps. However, at least one of the (a) film formation step and (d) the heating step and the post-development exposure step may be repeated. Moreover, after at least one of the (d) heating step and the post-development exposure step, the (e) metal layer forming step may be further included. It goes without saying that the above-mentioned drying step and the like may be further appropriately included in the lamination step.

在積層步驟之後進一步進行積層步驟之情況下，可以在上述曝光步驟之後，上述加熱步驟之後或上述金屬層形成步驟之後，進一步進行表面活化處理步驟。作為表面活化處理，可以例示電漿處理。對表面活性化處理的詳細內容將進行後述。When the layering step is further performed after the layering 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 the surface activation treatment, plasma treatment can be exemplified. Details of the surface activation treatment will be described later.

上述積層步驟進行2～20次為較佳，進行2～9次為更佳。 例如，如樹脂層/金屬層/樹脂層/金屬層/樹脂層/金屬層，將樹脂層設為2層以上且20層以下之構成為較佳，並且設為2層以上且9層以下之構成為進一步較佳。 上述各層的組成、形狀及膜厚等分別可以相同，亦可以不同。 Preferably, the above-mentioned layering step is performed 2 to 20 times, more preferably 2 to 9 times. For example, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, it is preferable to set the resin layer to 2 or more and 20 or less layers, and to set it to 2 or more and 9 layers or less. The constitution is further preferable. The composition, shape, film thickness, etc. of the above-mentioned layers may be the same or different.

在本發明中，尤其以在設置金屬層之後進一步覆蓋上述金屬層之方式形成上述本發明的樹脂組成物的硬化物（樹脂層）之態樣為較佳。具體而言，可以舉出依序重複（a）膜形成步驟、（b）曝光步驟、（c）顯影步驟、（d）加熱步驟及顯影後曝光步驟中的至少一者、（e）金屬層形成步驟之態樣或依序重複（a）膜形成步驟、（d）加熱步驟及顯影後曝光步驟中的至少一者、（e）金屬層形成步驟之態樣。藉由交替進行積層本發明的樹脂組成物層（樹脂層）之積層步驟和金屬層形成步驟，能夠交替積層本發明的樹脂組成物層（樹脂層）和金屬層。In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after the metal layer is provided. Specifically, at least one of (a) film formation step, (b) exposure step, (c) development step, (d) heating step, and post-development exposure step, and (e) metal layer are repeated in this order. In the form of the formation step, at least one of (a) the film forming step, (d) the heating step, and the post-development exposure step, and (e) the metal layer forming step are sequentially repeated. The resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated by alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer forming step.

（表面活性化處理步驟） 本發明的積層體之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，但是亦可以在上述顯影步驟之後（較佳為，在加熱步驟及顯影後曝光步驟中的至少一者之後），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。 關於表面活性化處理，可以僅對金屬層的至少一部分進行，亦可以僅對曝光後的樹脂組成物層的至少一部分進行，亦可以分別對金屬層及曝光後的樹脂組成物層這兩者的至少一部分進行。對金屬層的至少一部分進行表面活性化處理為較佳，對金屬層中在表面上形成樹脂組成物層之區域的一部分或全部進行表面活性化處理為較佳。如此，藉由對金屬層的表面進行表面活性化處理，能夠提高與設置於其表面上之樹脂組成物層（膜）的密接性。 又，對曝光後的樹脂組成物層（樹脂層）的一部分或全部亦進行表面活性化處理為較佳。如此，藉由對樹脂組成物層的表面進行表面活性化處理，能夠提高與設置於經表面活性化處理之表面上之金屬層和樹脂層的密接性。尤其，在進行負型顯影之情況等使樹脂組成物層硬化之情況下，不易受到表面處理之損壞，從而容易提高密接性。 作為表面活性化處理，具體而言，選自各種原料氣體（氧氣、氫氣、氬氣、氮氣、氮氣/氫氣混合氣體、氬氣/氧氣混合氣體等）的電漿處理、電暈放電處理、基於CF 4/O 2、NF 3/O 2、SF 6、NF 3、NF 3/O 2之蝕刻處理、基於紫外線（UV）臭氧法之表面處理、浸漬於鹽酸水溶液中以去除氧化皮膜之後浸漬於包含具有至少1種胺基和硫醇基之化合物之有機表面處理劑中的浸漬處理、使用了刷子之機械粗面化處理，電漿處理為較佳，尤其使用氧氣作為原料氣體之氧氣電漿處理為較佳。在進行電暈放電處理之情況下，能量為500～200,000J/m 2為較佳，1000～100,000J/m 2為更佳，10,000～50,000J/m 2為最佳。 (Surface activation treatment step) It is preferable that the manufacturing method of the laminated body of the present invention includes a surface activation treatment step of subjecting at least a 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 after the above-mentioned development step (preferably, after at least one of the heating step and the post-development exposure step), the resin composition layer may be surface-treated. The activation treatment step is followed by a metal layer formation step. The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the exposed resin composition layer, or may be performed on both the metal layer and the exposed resin composition layer, respectively. at least in part. Surface activation treatment is preferably performed on at least a part of the metal layer, and surface activation treatment is preferably performed on a part or all of a region of the metal layer where the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesiveness with the resin composition layer (film) provided on the surface can be improved. Moreover, it is preferable to also perform surface activation treatment on a part or all of the resin composition layer (resin layer) after exposure. In this way, by subjecting the surface of the resin composition layer to the surface activation treatment, the adhesiveness with the metal layer and the resin layer provided on the surface activated by the surface activation treatment can be improved. In particular, when the resin composition layer is hardened, such as in the case of performing negative development, it is difficult to be damaged by the surface treatment, and it is easy to improve the adhesiveness. Specifically, the surface activation treatment is selected from plasma treatment, corona discharge treatment, corona discharge treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.) Etching treatment of CF 4 /O 2 , NF 3 /O 2 , SF 6 , NF 3 , NF 3 /O 2 , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film and then immersion in Immersion treatment in organic surface treatment agents containing at least one amine group and thiol group compound, mechanical roughening treatment using a brush, plasma treatment is preferred, especially oxygen plasma using oxygen as a raw material gas Handling is better. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/m 2 , more preferably 1000-100,000 J/m 2 , and most preferably 10,000-50,000 J/m 2 .

（半導體元件及其製造方法） 本發明還揭示包含本發明的硬化物或本發明的積層體之半導體元件。 又，本發明還揭示包括本發明的硬化物之製造方法或本發明的積層體之製造方法之半導體元件之製造方法。作為將本發明的樹脂組成物用於再配線層用層間絕緣膜的形成中之半導體元件的具體例，能夠參閱日本特開2016-027357號公報的0213～0218段的記載及圖1的記載，並將該等內容編入本說明書中。 (Semiconductor element and its manufacturing method) The present invention also discloses a semiconductor element comprising the cured product of the present invention or the laminate of the present invention. Moreover, this invention also discloses the manufacturing method of the semiconductor element which includes the manufacturing method of the hardened|cured material of this invention or the manufacturing method of the laminated body of this invention. As a specific example of a semiconductor element in which the resin composition of the present invention is used in the formation of the interlayer insulating film for rewiring layers, the descriptions in paragraphs 0213 to 0218 of Japanese Patent Laid-Open No. 2016-027357 and the description in FIG. 1 can be referred to. These contents are incorporated into this manual.

（化合物） 本發明的第1態樣之化合物為下述式（1-1）所表示之化合物。 [化學式73]

Figure 02_image144
式（1-1）中，R 1分別獨立地為氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，R 2分別獨立地為氫原子、鹵素原子或1價的有機基，至少2個R 2可以鍵結而形成環結構，L 1表示3價的有機基。 上述式（1-1）所表示之化合物與上述特定聚合性化合物中之式（1-1）所表示之化合物相同，較佳態樣亦相同。 (Compound) The compound of the 1st aspect of this invention is a compound represented by following formula (1-1). [Chemical formula 73]
Figure 02_image144
In formula (1-1), R 1 is independently a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, and R 2 is independently a hydrogen atom, a halogen atom or a monovalent organic group. In the organic group, at least two R 2 can be bonded to form a ring structure, and L 1 represents a trivalent organic group. The compound represented by the above formula (1-1) is the same as the compound represented by the formula (1-1) in the above-mentioned specific polymerizable compound, and the preferred embodiments are also the same.

本發明的第2態樣之化合物為下述式（1-2）所表示之化合物。 [化學式74]

Figure 02_image146
式（1-2）中，R 1分別獨立地表示氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，L 2表示單鍵或2價的連接基，Cy表示環結構，L 3表示單鍵或2價的連接基，R 2分別獨立地表示氫原子、鹵素原子或1價的有機基，至少2個R 2可以鍵結而形成環結構。 上述式（1-2）所表示之化合物與上述特定聚合性化合物中之式（1-2）所表示之化合物相同，較佳態樣亦相同。 The compound of the second aspect of the present invention is a compound represented by the following formula (1-2). [Chemical formula 74]
Figure 02_image146
In formula (1-2), R 1 independently represents a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, L 2 represents a single bond or a divalent linking group, and Cy represents a ring Structure, L 3 represents a single bond or a divalent linking group, R 2 independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and at least two R 2 can be bonded to form a ring structure. The compound represented by the above formula (1-2) is the same as the compound represented by the formula (1-2) in the above-mentioned specific polymerizable compound, and the preferred aspects are also the same.

以下，將本發明的第1態樣之化合物及本發明的第2態樣之化合物亦統稱為“本發明的化合物”。Hereinafter, the compound of the first aspect of the present invention and the compound of the second aspect of the present invention are also collectively referred to as "the compound of the present invention".

＜鹼產生能＞ 在本發明的化合物中，在使用上述化合物合成了單聚物的情況下，上述單聚物顯示藉由在250℃下進行加熱而產生從主鏈游離之鹼之性質為較佳。 具體而言，在本發明的化合物具有自由基聚合性之情況下，使用V-601（二甲基 2,2'-偶氮雙（2-甲基丙酸酯））作為聚合起始劑，在溶劑環己酮中進行聚合反應，從而合成分子量為10,000左右的單聚物。 在本發明的化合物具有陽離子聚合性之情況下，使用對甲苯磺酸作為聚合起始劑，在溶劑環己酮中進行聚合反應，從而合成分子量為10,000左右的單聚物。 之後，在將所獲得之單聚物藉由過濾而獲取並在密封容器中1氣壓、250℃、3小時的條件下進行加熱之情況下，在源自本發明的化合物之醯胺鍵中的1個數%以上產生鹼時，上述單聚物顯示藉由在250℃下進行加熱而產生從主鏈游離之鹼之性質。 上述個數%為10個數%以上為較佳，30個數%以上為更佳。上限並無特別限定，可以為100個數%。 又，與藉由上述加熱而產生鹼之後殘存酸酐基者相比，本發明的化合物為在上述樹脂中殘存內酯結構者為較佳。 又，從本發明的化合物產生之鹼的較佳態樣與從上述特定聚合性化合物產生之鹼的較佳態樣相同。 ＜Alkali generating energy＞ Among the compounds of the present invention, when a monomer is synthesized using the above-mentioned compound, it is preferable that the above-mentioned monomer exhibits a property of generating a base free from the main chain by heating at 250°C. Specifically, when the compound of the present invention has radical polymerizability, V-601 (dimethyl 2,2'-azobis(2-methylpropionate)) is used as a polymerization initiator, The polymerization reaction was carried out in the solvent cyclohexanone to synthesize a monomer having a molecular weight of about 10,000. When the compound of the present invention has cationic polymerizability, a monomer having a molecular weight of about 10,000 is synthesized by performing a polymerization reaction in a solvent cyclohexanone using p-toluenesulfonic acid as a polymerization initiator. Then, in the case where the obtained monomer was obtained by filtration and heated in a sealed container under the conditions of 1 atmosphere, 250° C., and 3 hours, in the amide bond derived from the compound of the present invention, the When 1 several% or more of the base is generated, the above-mentioned monomer exhibits the property of generating the base free from the main chain by heating at 250°C. The above number % is preferably 10 number % or more, and more preferably 30 number % or more. The upper limit is not particularly limited, and may be 100 several %. Moreover, it is more preferable that the compound of the present invention has a lactone structure remaining in the resin, as compared with the case where the acid anhydride group remains after the base is generated by the above-mentioned heating. Moreover, the preferable aspect of the base derived from the compound of this invention is the same as the preferable aspect of the base derived from the above-mentioned specific polymerizable compound.

＜分子量、具體例＞ 本發明的化合物的分子量的較佳範圍與上述特定聚合性化合物的分子量的較佳範圍相同。 作為本發明的化合物的具體例，可以分別舉出上述特定聚合性化合物的具體例中之、與式（1-1）對應之化合物、與式（1-2）對應之化合物，但是並不限定於此。 <Molecular weight, specific example> The preferable range of the molecular weight of the compound of this invention is the same as the preferable range of the molecular weight of the said specific polymerizable compound. Specific examples of the compound of the present invention include compounds corresponding to formula (1-1) and compounds corresponding to formula (1-2) among the specific examples of the above-mentioned specific polymerizable compounds, but are not limited to here.

＜合成方法＞ 本發明的化合物例如能夠藉由後述實施例中所記載的方法來合成。 [實施例] <Synthesis method> The compound of the present invention can be synthesized, for example, by the method described in the following Examples. [Example]

以下，舉出實施例對本發明進行更具體的說明。以下實施例所示之材料、使用量、比例、處理內容、處理步驟等只要不脫離本發明的宗旨，則能夠適當地進行變更。從而，本發明的範圍並不限定於以下所示之具體例。除非另有說明，則“份”、“%”為質量基準。Hereinafter, the present invention will be described in more detail with reference to Examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

＜環化樹脂的前驅物之製造方法＞ 〔合成例1：環化樹脂的前驅物（樹脂1）的合成〕 將4,4’-氧二鄰苯二甲酸二酐（ODPA）23.48g和雙鄰苯二甲酸二酐（BPDA）22.27g加入可分離式燒瓶中，並加入甲基丙烯酸2-羥乙酯（HEMA）39.69g和四氫呋喃136.83g，在室溫（25℃）下進行攪拌，一邊攪拌一邊加入吡啶24.66g，從而獲得了反應混合物。基於反應之發熱結束之後，冷卻至室溫，並放置了16小時。 接著，在冰冷卻下，一邊攪拌將二環己基碳二醯亞胺（DCC）62.46g溶解於四氫呋喃61.57g中而獲得之溶液一邊經40分鐘加入反應混合物中，接著一邊攪拌將4,4’-二胺基二苯醚（DADPE）27.42g懸浮於四氫呋喃119.73g中者一邊經60分鐘加入。進而，在室溫下攪拌2小時之後，加入乙醇7.17g，並攪拌1小時，接著加入了四氫呋喃136.83g。藉由過濾而去除在反應混合物中產生之沉澱物，從而獲得了反應液。 將所獲得之反應液加入716.21g的乙醇中，從而生成了由粗聚合物形成之沉澱物。過濾出所生成之粗聚合物並將其溶解於四氫呋喃403.49g中，從而獲得了粗聚合物溶液。將所獲得之粗聚合物溶液滴加到8470.26g的水中以使聚合物沉澱，並過濾出所獲得之沉澱物之後進行真空乾燥，從而獲得了80.3g的粉末狀的樹脂1。藉由凝膠滲透層析法（標準聚苯乙烯換算）測定樹脂1的分子量，其結果，重量平均分子量（Mw）為20,000。推測樹脂1的結構為下述式（P-1）所表示之結構。 <Manufacturing method of precursor of cyclized resin> [Synthesis Example 1: Synthesis of Precursor of Cyclized Resin (Resin 1)] 23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of diphthalic dianhydride (BPDA) were added to the separable flask, and 2-hydroxyethyl methacrylate ( HEMA) 39.69g and tetrahydrofuran 136.83g, stirring at room temperature (25 degreeC), pyridine 24.66g was added, stirring, and the reaction mixture was obtained. After the heat generation based on the reaction was completed, it was cooled to room temperature and allowed to stand for 16 hours. Next, under ice-cooling, a solution obtained by dissolving 62.46 g of dicyclohexylcarbodiimide (DCC) in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes with stirring. -Diaminodiphenyl ether (DADPE) 27.42g was added over 60 minutes while suspending in 119.73g of tetrahydrofuran. Furthermore, after stirring at room temperature for 2 hours, 7.17 g of ethanol was added, followed by stirring for 1 hour, and then 136.83 g of tetrahydrofuran was added. A reaction liquid was obtained by removing the precipitate generated in the reaction mixture by filtration. The obtained reaction liquid was added to 716.21 g of ethanol, whereby a precipitate formed of a crude polymer was generated. The resulting crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate a polymer, and the obtained precipitate was filtered out and then vacuum-dried, whereby 80.3 g of powdery resin 1 was obtained. The molecular weight of the resin 1 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 20,000. The structure of resin 1 is estimated to be a structure represented by the following formula (P-1).

〔合成例2：環化樹脂的前驅物（樹脂2）的合成〕 混合21.2g的4,4’-氧二鄰苯二甲酸酐、18.0g的甲基丙烯酸2-羥乙酯、23.9g的吡啶及250mL的二甘二甲醚（二甘醇二甲醚、二乙二醇二甲醚），並在60℃的溫度下攪拌4小時，從而合成了4,4’-氧二鄰苯二甲酸和甲基丙烯酸2-羥乙酯的二酯。接著，將反應混合物冷卻至-10℃，一邊將溫度保持在-10±5℃一邊經60分鐘加入了17.0g的硫醯氯。在用50mL的N-甲基吡咯啶酮進行稀釋之後，將使12.6g的4,4’-二胺基二苯醚溶解於100mL的N-甲基吡咯啶酮中而獲得之溶液在-10±5℃下經60分鐘滴加到反應混合物中，並將混合物在室溫下攪拌了2小時。 接著，加入6000g的水以使聚醯亞胺前驅物沉澱，並將沉澱物（水-聚醯亞胺前驅物混合物）攪拌了15分鐘。過濾收集攪拌後的沉澱物（聚醯亞胺前驅物的固體），並使其溶解於四氫呋喃500g中。向所獲得之溶液中加入6000g的水（不良溶劑）以使聚醯亞胺前驅物沉澱，並將沉澱物（水-聚醯亞胺前驅物混合物）攪拌了15分鐘。再次過濾攪拌後的沉澱物（聚醯亞胺前驅物的固體），並在減壓狀態下，在45℃下乾燥了3天。 使乾燥後的粉體46.6g溶解於四氫呋喃419.6g中之後，添加2.3g的三乙胺，並在室溫下攪拌了35分鐘。之後，將其添加至乙醇3000g中，並過濾收集了沉澱物。將所獲得之沉澱物溶解於四氫呋喃281.8g中。向其中添加水17.1g和離子交換樹脂UP6040（Ambertec Ltd.製）46.6g，並攪拌了4小時。之後，藉由過濾而去除離子交換樹脂，並將所獲得之聚合物溶液加入庚烷4500g和乙酸乙酯500g的混合溶液中，從而獲得了沉澱物。過濾收集沉澱物，在減壓狀態下，在45℃下乾燥24小時，從而獲得了45.1g的樹脂2。 藉由凝膠滲透層析法（標準聚苯乙烯換算）測定樹脂2的分子量，其結果，重量平均分子量（Mw）為20,000。又，藉由適當調整4,4’-二胺基二苯醚的當量，還分別合成了Mw為10,000之樹脂2、Mw為30,000之樹脂2。推測樹脂2的結構為下述式（P-2）所表示之結構。 [Synthesis Example 2: Synthesis of Precursor of Cyclized Resin (Resin 2)] Mix 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diglyme, ethylene glycol dimethyl ether) and stirred at a temperature of 60°C for 4 hours, thereby synthesizing a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 17.0 g of thionium chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After dilution with 50 mL of N-methylpyrrolidone, a solution obtained by dissolving 12.6 g of 4,4'-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was at -10 It was added dropwise to the reaction mixture at ±5°C over 60 minutes, and the mixture was stirred at room temperature for 2 hours. Next, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid of polyimide precursor) was collected by filtration, and dissolved in 500 g of tetrahydrofuran. To the obtained solution, 6000 g of water (poor solvent) was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid of polyimide precursor) was filtered again and dried at 45° C. for 3 days under reduced pressure. After dissolving 46.6 g of the dried powder in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added, and the mixture was stirred at room temperature for 35 minutes. Then, this was added to 3000 g of ethanol, and the precipitate was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. To this, 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by Ambertec Ltd.) were added, followed by stirring for 4 hours. After that, the ion exchange resin was removed by filtration, and the obtained polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain a precipitate. The precipitate was collected by filtration and dried at 45° C. for 24 hours under reduced pressure to obtain 45.1 g of resin 2 . The molecular weight of the resin 2 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 20,000. Furthermore, by appropriately adjusting the equivalent weight of 4,4'-diaminodiphenyl ether, Resin 2 having Mw of 10,000 and Resin 2 having Mw of 30,000 were also synthesized. The structure of the resin 2 is estimated to be the structure represented by the following formula (P-2).

〔合成例3～合成例7：環化樹脂的前驅物（樹脂3～樹脂7）的合成〕 適當變更所使用之化合物，除此以外，藉由與合成例2相同的方法合成了下述式（P-3）～式（P-7）中的任一個所表示之結構的樹脂3～樹脂7。 樹脂3的Mw為20,000，樹脂4的Mw為20,000，樹脂5的Mw為20,000，樹脂6的Mw為20,000，樹脂7的Mw為20,000。 [Synthesis Example 3 to Synthesis Example 7: Synthesis of Precursors of Cyclized Resin (Resin 3 to Resin 7)] Resin 3 to resin having a structure represented by any one of the following formulae (P-3) to (P-7) were synthesized by the same method as in Synthesis Example 2, except that the compounds used were appropriately changed 7. The Mw of Resin 3 was 20,000, the Mw of Resin 4 was 20,000, the Mw of Resin 5 was 20,000, the Mw of Resin 6 was 20,000, and the Mw of Resin 7 was 20,000.

[化學式75]

Figure 02_image148
[化學式76]
Figure 02_image150
[Chemical formula 75]
Figure 02_image148
[Chemical formula 76]
Figure 02_image150

〔合成例8：環化樹脂（樹脂8）的合成〕 在安裝有電容器及攪拌機之燒瓶中，一邊去除水分一邊將4,4’-（六氟亞異丙基）二鄰苯二甲酸酐（Tokyo Chemical Industry Co.,Ltd.製）18.0g（40.5毫莫耳）溶解於N-甲基吡咯啶酮（NMP）80.0g中。接著，添加4,4’-二胺基二苯醚（Tokyo Chemical Industry Co.,Ltd.製）7.95g（39.7毫莫耳），在25℃下攪拌3小時，並在45℃下進一步攪拌了3小時。接著，添加吡啶12.8g（160毫莫耳）、乙酸酐10.3g（101毫莫耳）、N-甲基吡咯啶酮（NMP）40.0g，在80℃下攪拌3小時，並添加N-甲基吡咯啶酮（NMP）50g進行了稀釋。 使該反應液在1升甲醇中沉澱，並以3000rpm的速度攪拌了15分鐘。藉由過濾而獲取樹脂，在1升的甲醇中再次攪拌30分鐘並再次進行了過濾。在減壓狀態下，將所獲得之樹脂在40℃下乾燥1天，從而獲得了樹脂8。藉由凝膠滲透層析法（標準聚苯乙烯換算）測定樹脂8的分子量，其結果，重量平均分子量（Mw）為20,000。推測樹脂8的結構為下述式（P-8）所表示之結構。 [化學式77]

Figure 02_image152
[Synthesis Example 8: Synthesis of Cyclized Resin (Resin 8)] In a flask equipped with a capacitor and a stirrer, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride ( Tokyo Chemical Industry Co., Ltd.) 18.0 g (40.5 mmol) was dissolved in 80.0 g of N-methylpyrrolidone (NMP). Next, 7.95 g (39.7 mmol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, followed by stirring at 25° C. for 3 hours, and further stirring at 45° C. 3 hours. Next, 12.8 g (160 mmol) of pyridine, 10.3 g (101 mmol) of acetic anhydride, and 40.0 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80° C. for 3 hours, and N-methyl methane was added. pyrrolidone (NMP) 50g was diluted. The reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. Resin 8 was obtained by drying the obtained resin at 40° C. for 1 day under reduced pressure. The molecular weight of the resin 8 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 20,000. The structure of the resin 8 is estimated to be the structure represented by the following formula (P-8). [Chemical formula 77]
Figure 02_image152

〔合成例9：環化樹脂（樹脂9）的合成〕 在合成例8中，將4,4’-（六氟亞異丙基）二鄰苯二甲酸酐變更為等莫耳量的4,4’-氧二鄰苯二甲酸二酐（ODPA），將4,4’-二胺基二苯醚變更為等莫耳量的2,2’-雙（三氟甲基）聯苯胺，除此以外，藉由與合成例8相同的方法獲得了樹脂9。藉由凝膠滲透層析法（標準聚苯乙烯換算）測定樹脂9的分子量，其結果，重量平均分子量（Mw）為20,000。推測樹脂9的結構為下述式（P-9）所表示之結構。 [化學式78]

Figure 02_image154
[Synthesis Example 9: Synthesis of Cyclized Resin (Resin 9)] In Synthesis Example 8, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride was changed to an equimolar amount of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride. 4'-Oxydiphthalic dianhydride (ODPA), 4,4'-diaminodiphenyl ether was changed to an equimolar amount of 2,2'-bis(trifluoromethyl)benzidine, except Otherwise, Resin 9 was obtained by the same method as in Synthesis Example 8. The molecular weight of resin 9 was measured by gel permeation chromatography (standard polystyrene conversion), and as a result, the weight average molecular weight (Mw) was 20,000. The structure of resin 9 is estimated to be a structure represented by the following formula (P-9). [Chemical formula 78]
Figure 02_image154

＜實施例及比較例＞ 在各實施例中，分別混合下述表中所記載的成分，從而獲得了各樹脂組成物。又，在各比較例中，分別混合下述表中所記載的成分，從而獲得了各比較用組成物。 具體而言，除了溶劑以外的表中所記載的各成分的含量（配合量）設為表的各欄的“質量份”一欄中所記載的量（質量份）。 溶劑的含量（配合量）設為使組成物的固體成分濃度成為表中的“固體成分濃度（質量%）”的值，各溶劑的含量相對於溶劑的總質量的比率（質量比）設為表中的“比率”一欄中所記載的比率。 將所獲得之樹脂組成物及比較用組成物使用細孔的寬度為0.8μm的聚四氟乙烯製過濾器進行了加壓過濾。 又，在表中，“-”的記載表示組成物不含有對應之成分。 <Examples and Comparative Examples> In each Example, each resin composition was obtained by mixing the components described in the following table, respectively. In addition, in each comparative example, each composition for comparison was obtained by mixing the components described in the following table, respectively. Specifically, the content (compounding amount) of each component described in the table except for the solvent was set to the amount (part by mass) described in the column of "parts by mass" in each column of the table. The content (compounding amount) of the solvent is set to a value such that the solid content concentration of the composition becomes the value of "solid content concentration (mass %)" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvent is set to The ratio described in the column of "Ratio" in the table. The obtained resin composition and the composition for comparison were subjected to pressure filtration using a filter made of polytetrafluoroethylene having a pore width of 0.8 μm. In addition, in the table|surface, the description of "-" shows that a composition does not contain the corresponding component.

[表1]    實施例 比較例 比較例 比較例 比較例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 1 1 2 3 4 2 3 4 5 6 7 8 9 10 11 組成 樹脂 種類 樹脂1 樹脂1 樹脂1 樹脂1 樹脂1 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 質量份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 質量份 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 聚合起始劑 或光酸產生劑 種類 I-2 I-2 I-2 I-2 I-2 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 質量份 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 特定聚合性化合物或熱鹼產生劑 種類 A-1 - AR-1 AR-2 AR-3 A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 質量份 2 - 2 2 2 2 2 2 2 2 2 2 2 2 2 種類 - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - 聚合抑制劑 種類 B-2 B-2 B-2 B-2 B-2 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 質量份 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 矽烷偶合劑 種類 C-2 C-2 C-2 C-2 C-2 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 質量份 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 添加劑 種類 E-1 E-1 E-1 E-1 E-1 - - - - - - - - - - 質量份 2.4 2.4 2.4 2.4 2.4 - - - - - - - - - - 種類 E-2 E-2 E-2 E-2 E-2 - - - - - - - - - - 質量份 0.9 0.9 0.9 0.9 0.9 - - - - - - - - - - 溶劑 種類 NMP NMP NMP NMP NMP GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL 比率 45 45 45 45 45 40 40 40 40 40 40 40 40 40 40 種類 EL EL EL EL EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 固體成分濃度（質量%） 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 步驟 膜厚（μm） 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB溫度（℃） 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 顯影液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 曝光方式 M M M M M M M M M M M M M M M 曝光波長 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 硬化溫度（℃） 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 顯影條件 負 負 負 負 負 負 負 負 負 負 負 負 負 負 負 硬化時間（min） 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 評價 斷裂伸長率評價 B D D D D B B B B C B C B B C 耐藥品性評價 B D D D D B B B B C B C B B C 膜收縮評價 B D D D D B B B B B B B B B B [Table 1] Example Comparative example Comparative example Comparative example Comparative example Example Example Example Example Example Example Example Example Example Example 1 1 2 3 4 2 3 4 5 6 7 8 9 10 11 composition resin type Resin 1 Resin 1 Resin 1 Resin 1 Resin 1 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-2 I-2 I-2 I-2 I-2 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Specific polymeric compounds or thermal base generators type A-1 - AR-1 AR-2 AR-3 A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 parts by mass 2 - 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - polymerization inhibitor type B-2 B-2 B-2 B-2 B-2 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-2 C-2 C-2 C-2 C-2 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type E-1 E-1 E-1 E-1 E-1 - - - - - - - - - - parts by mass 2.4 2.4 2.4 2.4 2.4 - - - - - - - - - - type E-2 E-2 E-2 E-2 E-2 - - - - - - - - - - parts by mass 0.9 0.9 0.9 0.9 0.9 - - - - - - - - - - solvent type NMP NMP NMP NMP NMP GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 45 45 45 45 45 40 40 40 40 40 40 40 40 40 40 type EL EL EL EL EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration (mass %) 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 step Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB temperature (℃) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 developer cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone Exposure method M M M M M M M M M M M M M M M Exposure wavelength 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Development conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening time (min) 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 Evaluation Elongation at break evaluation B D D D D B B B B C B C B B C Drug resistance evaluation B D D D D B B B B C B C B B C Film Shrinkage Evaluation B D D D D B B B B B B B B B B

[表2]    實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 12 13 14 15 16 17 18 19 20 21 22 23 24 25 組成 樹脂 種類 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 質量份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 質量份 6 6 6 6 6 6 6 6 6 6 6 6 6 6 聚合起始劑 或光酸產生劑 種類 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 質量份 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 特定聚合性化合物或熱鹼產生劑 種類 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-21 A-22 A-23 A-24 A-25 質量份 2 2 2 2 2 2 2 2 2 2 2 2 2 2 種類 - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - 聚合抑制劑 種類 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 質量份 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 矽烷偶合劑 種類 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 質量份 1 1 1 1 1 1 1 1 1 1 1 1 1 1 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 添加劑 種類 - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - 種類 - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - 溶劑 種類 GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL 比率 40 40 40 40 40 40 40 40 40 40 40 40 40 40 種類 DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 10 10 10 10 10 10 10 10 10 10 10 10 10 10 固體成分濃度（質量%） 42 42 42 42 42 42 42 42 42 42 42 42 42 42 步驟 膜厚（μm） 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB溫度（℃） 100 100 100 100 100 100 100 100 100 100 100 100 100 100 顯影液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 曝光方式 M M M M M M M M M M M M M M 曝光波長 365 365 365 365 365 365 365 365 365 365 365 365 365 365 硬化溫度（℃） 230 230 230 230 230 230 230 230 230 230 230 230 230 230 顯影條件 負 負 負 負 負 負 負 負 負 負 負 負 負 負 硬化時間（min） 120 120 120 120 120 120 120 120 120 120 120 120 120 120 評價 斷裂伸長率評價 C C C C B B B B B B B A A C 耐藥品性評價 C C C A A A B B B B B A A C 膜收縮評價 B B B B B B B B B B B A A C [Table 2] Example Example Example Example Example Example Example Example Example Example Example Example Example Example 12 13 14 15 16 17 18 19 20 twenty one twenty two twenty three twenty four 25 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Specific polymeric compounds or thermal base generators type A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-21 A-22 A-23 A-24 A-25 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - type - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration (mass %) 42 42 42 42 42 42 42 42 42 42 42 42 42 42 step Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB temperature (℃) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 developer cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone Exposure method M M M M M M M M M M M M M M Exposure wavelength 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Development conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening time (min) 120 120 120 120 120 120 120 120 120 120 120 120 120 120 Evaluation Elongation at break evaluation C C C C B B B B B B B A A C Drug resistance evaluation C C C A A A B B B B B A A C Film Shrinkage Evaluation B B B B B B B B B B B A A C

[表3]    實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 組成 樹脂 種類 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂7 樹脂7 樹脂7 樹脂2 樹脂2 樹脂7 樹脂2 樹脂2 樹脂2 Mw 20000 20000 20000 20000 10000 30000 20000 20000 20000 20000 20000 20000 20000 20000 20000 質量份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 M-1 M-1 M-1 - - - M-1 M-1 - M-1 M-1 M-1 質量份 6 6 6 6 6 6 - - - 6 6 - 6 6 6 聚合起始劑 或光酸產生劑 種類 I-1 I-1 I-1 I-1 I-1 I-1 I-5 I-5 I-5 I-1 I-1 I-5 I-1 I-1 I-1 質量份 1.1 1.1 1.1 1.1 1.1 1.1 2 2 2 1.1 1.1 2 1.1 1.1 1.1 特定聚合性化合物或熱鹼產生劑 種類 A-26 A-27 A-28 A-29 A-1 A-1 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 質量份 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 種類 - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - 聚合抑制劑 種類 B-1 B-1 B-1 B-1 B-1 B-1 - - - B-1 B-1 - B-1 B-1 B-1 質量份 0.1 0.1 0.1 0.1 0.1 0.1 - - - 0.1 0.1 - 0.1 0.1 0.1 矽烷偶合劑 種類 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 質量份 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 添加劑 種類 - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - 種類 - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - 溶劑 種類 GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL 比率 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 種類 DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 固體成分濃度（質量%） 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 步驟 膜厚（μm） 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB溫度（℃） 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 顯影液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 TMAH aq TMAH aq TMAH aq 環戊酮 環戊酮 TMAH aq 環戊酮 環戊酮 環戊酮 曝光方式 M M M M M M M M M M M M M M M 曝光波長 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 硬化溫度（℃） 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 顯影條件 負 負 負 負 負 負 正 正 正 負 負 正 負 負 負 硬化時間（min） 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 評價 斷裂伸長率評價 C B B B B B B C B B B C C C B 耐藥品性評價 B B B B B B B C B B B C C C B 膜收縮評價 C B B B B B C C C B B C C C B [table 3] Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 7 Resin 7 Resin 7 Resin 2 Resin 2 Resin 7 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 10000 30000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 - - - M-1 M-1 - M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 - - - 6 6 - 6 6 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-5 I-5 I-5 I-1 I-1 I-5 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 2 2 2 1.1 1.1 2 1.1 1.1 1.1 Specific polymeric compounds or thermal base generators type A-26 A-27 A-28 A-29 A-1 A-1 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 - - - B-1 B-1 - B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 - - - 0.1 0.1 - 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration (mass %) 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 step Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB temperature (℃) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 developer cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone TMAH aq TMAH aq TMAH aq cyclopentanone cyclopentanone TMAH aq cyclopentanone cyclopentanone cyclopentanone Exposure method M M M M M M M M M M M M M M M Exposure wavelength 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Development conditions burden burden burden burden burden burden just just just burden burden just burden burden burden Hardening time (min) 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 Evaluation Elongation at break evaluation C B B B B B B C B B B C C C B Drug resistance evaluation B B B B B B B C B B B C C C B Film Shrinkage Evaluation C B B B B B C C C B B C C C B

[表4]    實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 組成 樹脂 種類 樹脂2 樹脂2 樹脂1 樹脂3 樹脂4 樹脂5 樹脂6 樹脂7 樹脂8 樹脂9 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 質量份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 M-1 M-1 - M-1 - M-1 M-1 M-1 M-1 DPHA M-2 M-1/M-2 M-1 質量份 6 6 6 6 6 - 6 - 6 6 2 8 6 6 3/3 6 聚合起始劑 或光酸產生劑 種類 I-1 I-1 I-1 I-1 I-1 I-4 I-1 I-5 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 質量份 1.1 1.1 1.1 1.1 1.1 2 1.1 2 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 特定聚合性化合物或熱鹼產生劑 種類 A-39 A-40 A-1 A-1 A-1 A-30 A-1 A-30 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 質量份 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 種類 - - - - - - - - - - - - - - - AX-1 質量份 - - - - - - - - - - - - - - - 1 聚合抑制劑 種類 B-1 B-1 B-1 B-1 B-1 - B-1 - B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 質量份 0.1 0.1 0.1 0.1 0.1 - 0.1 - 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 矽烷偶合劑 種類 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 質量份 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 添加劑 種類 - - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - - 種類 - - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - - 溶劑 種類 GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL 比率 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 種類 DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 固體成分濃度（質量%） 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 步驟 膜厚（μm） 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB溫度（℃） 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 顯影液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 TMAH aq 環戊酮 TMAH aq 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 曝光方式 M M M M M M M M M M M M M M M M 曝光波長 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 硬化溫度（℃） 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 顯影條件 負 負 負 負 負 正 負 正 負 負 負 負 負 負 負 負 硬化時間（min） 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 評價 斷裂伸長率評價 A A B B B B B B A A A C B B B B 耐藥品性評價 A A B B B B B B C C C A A B B B 膜收縮評價 A A B B B B B B A A B B B B B B [Table 4] Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 composition resin type Resin 2 Resin 2 Resin 1 Resin 3 Resin 4 Resin 5 Resin 6 Resin 7 Resin 8 Resin 9 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 - M-1 - M-1 M-1 M-1 M-1 DPHA M-2 M-1/M-2 M-1 parts by mass 6 6 6 6 6 - 6 - 6 6 2 8 6 6 3/3 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 I-1 I-4 I-1 I-5 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 2 1.1 2 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Specific polymeric compounds or thermal base generators type A-39 A-40 A-1 A-1 A-1 A-30 A-1 A-30 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 type - - - - - - - - - - - - - - - AX-1 parts by mass - - - - - - - - - - - - - - - 1 polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 - B-1 - B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 - 0.1 - 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - - type - - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration (mass %) 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 step Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB temperature (℃) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 developer cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone TMAH aq cyclopentanone TMAH aq cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone Exposure method M M M M M M M M M M M M M M M M Exposure wavelength 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Development conditions burden burden burden burden burden just burden just burden burden burden burden burden burden burden burden Hardening time (min) 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 Evaluation Elongation at break evaluation A A B B B B B B A A A C B B B B Drug resistance evaluation A A B B B B B B C C C A A B B B Film Shrinkage Evaluation A A B B B B B B A A B B B B B B

[表5]    實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 組成 樹脂 種類 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 質量份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 - M-1 M-1 M-1 質量份 6 6 6 6 6 6 6 6 6 6 6 - 6 6 6 聚合起始劑 或光酸產生劑 種類 I-1 I-1 I-1 I-1 I-2 I-3 I-1 I-1 I-1 I-1 I-1 I-1 I-6 I-1 I-1 質量份 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 2.0 1.1 1.1 特定聚合性化合物或熱鹼產生劑 種類 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 質量份 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 種類 AX-2 AX-3 AX-4 AX-5 - - - - - - - - - - - 質量份 1 1 1 2 - - - - - - - - - - - 聚合抑制劑 種類 B-1 B-1 B-1 B-1 B-1 B-1 B-2 B-1 B-1 B-1 B-1 - B-1 B-1 B-1 質量份 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - 0.1 0.1 0.1 矽烷偶合劑 種類 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-2 C-1 C-1 C-1 - C-1 C-1 C-1 質量份 1 1 1 1 1 1 1 1 1 1 1 - 1 1 1 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 - D-1 D-1 D-1 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 - 0.2 0.2 0.2 添加劑 種類 - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - 種類 - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - 溶劑 種類 GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL 比率 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 種類 DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 固體成分濃度（質量%） 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 步驟 膜厚（μm） 20 20 20 20 20 20 20 20 20 20 20 20 20 10 30 PB溫度（℃） 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 顯影液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 曝光方式 M M M M M M M M M M M M L M M 曝光波長 365 365 365 365 365 365 365 365 365 365 365 365 405 365 365 硬化溫度（℃） 230 230 230 230 230 230 230 230 200 180 IR 230 230 230 230 顯影條件 負 負 負 負 負 負 負 負 負 負 負 負 負 負 負 硬化時間（min） 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 評價 斷裂伸長率評價 B B B B B B B B B B B B B A B 耐藥品性評價 B B B B B B B B B B B B A A B 膜收縮評價 B B B B B B B B B B B B B B B [table 5] Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 - M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 - 6 6 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 I-2 I-3 I-1 I-1 I-1 I-1 I-1 I-1 I-6 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 2.0 1.1 1.1 Specific polymeric compounds or thermal base generators type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 parts by mass 1 1 1 1 2 2 2 2 2 2 2 2 2 2 2 type AX-2 AX-3 AX-4 AX-5 - - - - - - - - - - - parts by mass 1 1 1 2 - - - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-2 B-1 B-1 B-1 B-1 - B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-2 C-1 C-1 C-1 - C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 - 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 - D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 - 0.2 0.2 0.2 additive type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration (mass %) 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 step Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 10 30 PB temperature (℃) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 developer cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone Exposure method M M M M M M M M M M M M L M M Exposure wavelength 365 365 365 365 365 365 365 365 365 365 365 365 405 365 365 Hardening temperature (℃) 230 230 230 230 230 230 230 230 200 180 IR 230 230 230 230 Development conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening time (min) 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 Evaluation Elongation at break evaluation B B B B B B B B B B B B B A B Drug resistance evaluation B B B B B B B B B B B B A A B Film Shrinkage Evaluation B B B B B B B B B B B B B B B

[表6]    實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 組成 樹脂 種類 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 質量份 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 質量份 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 聚合起始劑 或光酸產生劑 種類 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 質量份 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 特定聚合性化合物或熱鹼產生劑 種類 A-41 A-42 A-43 A-44 A-45 A-46 A-47 A-48 A-49 A-50 A-51 A-52 A-53 A-54 A-50 質量份 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 種類 - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - 聚合抑制劑 種類 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 質量份 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 矽烷偶合劑 種類 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 質量份 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 添加劑 種類 - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - 種類 - - - - - - - - - - - - - - - 質量份 - - - - - - - - - - - - - - - 溶劑 種類 GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL 比率 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 種類 DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 固體成分濃度（質量%） 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 步驟 膜厚（μm） 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB溫度（℃） 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 顯影液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 曝光方式 M M M M M M M M M M M M M M M 曝光波長 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 硬化溫度（℃） 230 230 230 230 230 230 230 230 230 230 230 230 230 230 200 顯影條件 負 負 負 負 負 負 負 負 負 負 負 負 負 負 負 硬化時間（min） 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 評價 斷裂伸長率評價 A A A A A A A A A A A A A A A 耐藥品性評價 A A A A A A A A A A A A A A A 膜收縮評價 A A A A A A A A A A A A A A A [Table 6] Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Specific polymeric compounds or thermal base generators type A-41 A-42 A-43 A-44 A-45 A-46 A-47 A-48 A-49 A-50 A-51 A-52 A-53 A-54 A-50 parts by mass 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration (mass %) 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 step Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 PB temperature (℃) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 developer cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone Exposure method M M M M M M M M M M M M M M M Exposure wavelength 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 200 Development conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening time (min) 120 120 120 120 120 120 120 120 120 120 120 120 120 120 120 Evaluation Elongation at break evaluation A A A A A A A A A A A A A A A Drug resistance evaluation A A A A A A A A A A A A A A A Film Shrinkage Evaluation A A A A A A A A A A A A A A A

[表7]    實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 實施例 87 88 89 90 91 92 93 94 95 組成 樹脂 種類 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 樹脂2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 質量份 35 35 35 35 35 35 35 35 35 單體 種類 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 質量份 6 6 6 6 6 6 6 6 6 聚合起始劑 或光酸產生劑 種類 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 質量份 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 特定聚合性化合物或熱鹼產生劑 種類 A-50 A-55 A-56 A-57 A-20 A-57 A-20 A-57 A-20 質量份 2 2 2 2 2 2 2 2 2 種類 - - - - - - - - - 質量份 - - - - - - - - - 聚合抑制劑 種類 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 質量份 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 矽烷偶合劑 種類 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 質量份 1 1 1 1 1 1 1 1 1 遷移抑制劑 種類 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 質量份 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 添加劑 種類 - - - - - - - - - 質量份 - - - - - - - - - 種類 - - - - - - - - - 質量份 - - - - - - - - - 溶劑 種類 GBL GBL GBL GBL GBL GBL GBL GBL GBL 比率 40 40 40 40 40 40 40 40 40 種類 DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO 比率 10 10 10 10 10 10 10 10 10 固體成分濃度（質量%） 42 42 42 42 42 42 42 42 42 步驟 膜厚（μm） 20 20 20 20 20 20 20 20 20 PB溫度（℃） 100 100 100 100 100 100 100 100 100 顯影液 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 環戊酮 曝光方式 M M M M M M M M M 曝光波長 365 365 365 365 365 365 365 365 365 硬化溫度（℃） 180 230 230 230 230 200 200 180 180 顯影條件 負 負 負 負 負 負 負 負 負 硬化時間（min） 120 120 120 120 120 120 120 120 120 評價 斷裂伸長率評價 A A A A A A A A B 耐藥品性評價 A A A A A A A B A 膜收縮評價 A A A A A A A A A [Table 7] Example Example Example Example Example Example Example Example Example 87 88 89 90 91 92 93 94 95 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 monomer type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Specific polymeric compounds or thermal base generators type A-50 A-55 A-56 A-57 A-20 A-57 A-20 A-57 A-20 parts by mass 2 2 2 2 2 2 2 2 2 type - - - - - - - - - parts by mass - - - - - - - - - polymerization inhibitor type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 migration inhibitor type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - parts by mass - - - - - - - - - type - - - - - - - - - parts by mass - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 Solid content concentration (mass %) 42 42 42 42 42 42 42 42 42 step Film thickness (μm) 20 20 20 20 20 20 20 20 20 PB temperature (℃) 100 100 100 100 100 100 100 100 100 developer cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone cyclopentanone Exposure method M M M M M M M M M Exposure wavelength 365 365 365 365 365 365 365 365 365 Hardening temperature (℃) 180 230 230 230 230 200 200 180 180 Development conditions burden burden burden burden burden burden burden burden burden Hardening time (min) 120 120 120 120 120 120 120 120 120 Evaluation Elongation at break evaluation A A A A A A A A B Drug resistance evaluation A A A A A A A B A Film Shrinkage Evaluation A A A A A A A A A

表中所記載之各成分的詳細內容如下。The details of each component described in the table are as follows.

〔樹脂〕 ·樹脂1～樹脂9：藉由上述合成例而獲得之樹脂1～樹脂9 [resin] Resin 1 to Resin 9: Resin 1 to Resin 9 obtained by the above synthesis example

〔單體（其他聚合性化合物）〕 ·M-1～M-2：下述結構的化合物，括號的下標表示重複數。 ·DPHA：二新戊四醇六丙烯酸酯 [化學式79]

Figure 02_image156
[Monomers (Other Polymerizable Compounds)] ·M-1 to M-2: Compounds of the following structures, and the subscripts in parentheses indicate the number of repetitions. DPHA: Dipivalerythritol hexaacrylate [Chemical formula 79]
Figure 02_image156

〔聚合起始劑或光酸產生劑〕 ·I-1～I-6：下述結構的化合物，I-6為與上述有機金屬錯合物（具有自由基聚合起始能之有機金屬錯合物）對應之化合物。 [化學式80]

Figure 02_image158
[Polymerization initiator or photoacid generator] I-1 to I-6: compounds of the following structures, I-6 is an organometallic complex with the above-mentioned organometallic complex (organometallic complex having radical polymerization initiation energy) substance) the corresponding compound. [Chemical formula 80]
Figure 02_image158

〔特定聚合性化合物或熱鹼產生劑〕 ·A-1～A-57：下述結構的化合物。A-1～A-57均為與上述特定聚合性化合物對應之化合物。 ·AX-1～AX-5：下述結構的化合物。AX-1～AX-5均為不對應於上述特定聚合性化合物之化合物。 ·AR-1～AR-3：下述結構的化合物。AR-1～AR-3均為不對應於上述特定聚合性化合物之化合物。 再者，與苯環等環結構的邊相交之鍵結表示可以與環結構上的任一個碳原子鍵結。 [化學式81]

Figure 02_image160
[化學式82]
Figure 02_image162
[化學式83]
Figure 02_image164
[化學式84]
Figure 02_image166
[化學式85]
Figure 02_image168
[Specific polymerizable compound or thermal base generator] ·A-1 to A-57: Compounds of the following structures. A-1 to A-57 are all compounds corresponding to the above-mentioned specific polymerizable compounds. AX-1 to AX-5: compounds of the following structures. All of AX-1 to AX-5 are compounds that do not correspond to the above-mentioned specific polymerizable compounds. · AR-1 to AR-3: compounds of the following structures. AR-1 to AR-3 are all compounds that do not correspond to the above-mentioned specific polymerizable compounds. In addition, the bond which crosses the edge of the ring structure, such as a benzene ring, shows that it may bond with any carbon atom in a ring structure. [Chemical formula 81]
Figure 02_image160
[Chemical formula 82]
Figure 02_image162
[Chemical formula 83]
Figure 02_image164
[Chemical formula 84]
Figure 02_image166
[Chemical formula 85]
Figure 02_image168

-化合物A-45、化合物A-49的合成- 在燒瓶中，使氯化偏苯三酸酐10.0g溶解於二氯甲烷125.8g中。將溶液冷卻至0～5℃之後，滴加吡啶4.1g，之後滴加了甲基丙烯酸2-羥乙酯6.2g。將反應液升溫至室溫之後，攪拌了3小時。之後，藉由對反應液進行加熱減壓濃縮，從而獲得了固體的粗產物。添加乙酸乙酯100g，在懸浮狀態下攪拌30分鐘之後，去除固體，並對濾液進行加熱減壓濃縮，從而獲得了16.0g的化合物A-45-I1。 在燒瓶中，將A-45-I1 16.0g在乙酸乙酯100.0g中在懸浮狀態下進行了攪拌。滴加二環己胺（Dicyclohexylamine）17.2g之後，將溶液在75～80℃下攪拌了4小時。冷卻至室溫之後，添加1N（1mol/L）鹽酸200mL並進行了攪拌。過濾出所析出之固體之後，用水100mL對濾液進行分液清洗，並用硫酸鈉乾燥所獲得之有機層之後，進行加熱減壓濃縮，從而獲得了粗產物。進而，使用二氧化矽凝膠管柱層析法（展開溶劑：己烷/乙酸乙酯=3/1（體積比））進行純化，從而獲得了23.3g的化合物A-45（粉體、位置異構體混合物）（產率88%）。 將 1H-NMR資料示於以下。 1H-NMR、400MHz、δ（（DMSO-d6）ppm：0.66-1.14（4H，m），1.24-1.83（14H、m）、1.82-1.90（3H、d）、2.42-2.51（2H、m）、2.91-3.15（2H、m）、4.46-4.49（2H、m）、4.56-4.59（2H、m）、5.67-5.69（1H、m）、6.03（1H、d）、7.39（0.5H、d）、7，65（0.5H、s）、8.02（1H、s）、8.14（0.5H、dd）、8.43（0.5H、d）、13.43（1H、bs）。 在燒瓶中，使化合物A-45 12.0g溶解於四氫呋喃43.8g中。將溶液冷卻至0～5℃之後，滴加了硼烷-四氫呋喃錯合物四氫呋喃溶液（0.9mol/L）40mL。之後，將反應溶液升溫至室溫，並攪拌了4小時。將反應溶液注入水500mL和甲醇200g的混合溶液中，並在室溫下攪拌了2小時。藉由加熱減壓濃縮而蒸餾去除甲醇之後，用乙酸乙酯250mL進行萃取，並以用1N鹽酸240mL1次、用水100mL1次、用飽和碳酸氫鈉水溶液1次、用水240mL1次的順序對有機層進行了分液清洗。對有機層進行加熱減壓濃縮，從而獲得了粗產物18.1g。進而，使用二氧化矽凝膠管柱層析法（展開溶劑：己烷/乙酸乙酯=3/1（體積比））進行純化，從而獲得了5.8g的化合物A-49（油狀、位置異構體混合物）（產率88%）。 將 1H-NMR資料示於以下。 1H-NMR、400MHz、δ（（DMSO-d6）ppm：0.75-1.77（18H，m）、1.85-1.87（3H、m）、2.45-2.55（2H、m）、2.96-3.14（2H、m）、4.42-4.58（6H、m）、5.39（1H、q）、5.65-5.70（1H、m）、6.00-6.05（1H、m）、7.25（0.5H、d）、7.57（0.5H、d）、7.68（0.5H、d）、7.85（0.5H、dd）、7.95（0.5H、dd）、8.13（0.5H、s）。 [化學式86]

Figure 02_image170
- Synthesis of Compound A-45 and Compound A-49 - In a flask, 10.0 g of chlorinated trimellitic anhydride was dissolved in 125.8 g of methylene chloride. After cooling the solution to 0 to 5°C, 4.1 g of pyridine was added dropwise, and then 6.2 g of 2-hydroxyethyl methacrylate was added dropwise. After warming up the reaction liquid to room temperature, it stirred for 3 hours. Then, the reaction liquid was heated and concentrated under reduced pressure to obtain a solid crude product. After adding 100 g of ethyl acetate and stirring for 30 minutes in a suspended state, the solid was removed, and the filtrate was concentrated by heating under reduced pressure to obtain 16.0 g of compound A-45-I1. In the flask, 16.0 g of A-45-I1 was stirred in a suspended state in 100.0 g of ethyl acetate. After adding 17.2 g of dicyclohexylamine dropwise, the solution was stirred at 75 to 80° C. for 4 hours. After cooling to room temperature, 200 mL of 1N (1 mol/L) hydrochloric acid was added and stirred. After the precipitated solid was filtered out, the filtrate was separated and washed with 100 mL of water, and the obtained organic layer was dried with sodium sulfate, and then concentrated under reduced pressure under heating to obtain a crude product. Further, it was purified using silica gel column chromatography (developing solvent: hexane/ethyl acetate = 3/1 (volume ratio)) to obtain 23.3 g of compound A-45 (powder, location isomer mixture) (88% yield). 1 H-NMR data are shown below. 1 H-NMR, 400MHz, δ((DMSO-d6)ppm: 0.66-1.14(4H,m), 1.24-1.83(14H,m), 1.82-1.90(3H,d), 2.42-2.51(2H,m) ), 2.91-3.15 (2H, m), 4.46-4.49 (2H, m), 4.56-4.59 (2H, m), 5.67-5.69 (1H, m), 6.03 (1H, d), 7.39 (0.5H, d), 7, 65 (0.5H, s), 8.02 (1H, s), 8.14 (0.5H, dd), 8.43 (0.5H, d), 13.43 (1H, bs). In a flask, make compound A 12.0 g of -45 was dissolved in 43.8 g of tetrahydrofuran. After cooling the solution to 0 to 5°C, 40 mL of borane-tetrahydrofuran complex tetrahydrofuran solution (0.9 mol/L) was added dropwise. After that, the reaction solution was warmed to room temperature , and stirred for 4 hours. The reaction solution was poured into a mixed solution of 500 mL of water and 200 g of methanol, and stirred at room temperature for 2 hours. After the methanol was distilled off by concentration under heating and reduced pressure, extraction was performed with 250 mL of ethyl acetate. , and the organic layer was separated and washed with 240 mL of 1N hydrochloric acid once, once with 100 mL of water, once with saturated aqueous sodium bicarbonate solution, and once with 240 mL of water. The organic layer was concentrated under heating and reduced pressure to obtain a crude product 18.1 g. Further, it was purified using silica gel column chromatography (developing solvent: hexane/ethyl acetate = 3/1 (volume ratio)) to obtain 5.8 g of compound A-49 (oil 1 H-NMR data are shown below. 1 H-NMR, 400MHz, δ((DMSO-d6)ppm: 0.75-1.77(18H,m), 1.85-1.87 (3H, m), 2.45-2.55 (2H, m), 2.96-3.14 (2H, m), 4.42-4.58 (6H, m), 5.39 (1H, q), 5.65-5.70 (1H, m) ), 6.00-6.05 (1H, m), 7.25 (0.5H, d), 7.57 (0.5H, d), 7.68 (0.5H, d), 7.85 (0.5H, dd), 7.95 (0.5H, dd) , 8.13 (0.5H, s).[Chem. 86]
Figure 02_image170

-化合物A-53的合成- 在燒瓶中，將二環己胺143.7g和二氯甲烷525.2g進行了攪拌。將溶液冷卻至0～5℃之後，滴加了溴乙醯溴80.0g。升溫至室溫之後，攪拌了3小時。將反應溶液添加至水1000mL中之後，攪拌了15分鐘。過濾出析出物之後，用水400mL分液清洗了2次。用硫酸鈉進行乾燥之後，進行加熱減壓濃縮，從而獲得了粗產物。用己烷55g再漿料化之後，過濾收集固體，從而獲得了化合物A-53-I1 73.2g（粉體）（產率61%）。 在燒瓶中，將A-53-I1 20.0g、香草醇10.2g、碳酸鉀11.0g、丙酮100g進行了攪拌。將溶液升溫至40℃之後，攪拌了4小時。過濾出固體之後，進行加熱減壓濃縮而蒸餾去除了丙酮。溶解於乙酸乙酯600mL中之後，用水350mL分液清洗了3次。用硫酸鈉乾燥有機層之後，進行加熱減壓濃縮，從而獲得了粗產物（粉體）。添加己烷45g並進行30分鐘的再漿料化之後，過濾收集固體，從而獲得了23.0g的化合物A-53-I2。 在燒瓶中，用二氯甲烷38.8g溶解A-53-I2 11.0g並進行了攪拌。將溶液冷卻至0～5℃之後，滴加了三溴化硼二氯甲烷溶液（1mol/L）117mL。升溫至室溫之後，攪拌了3小時。將反應液添加至水500mL和甲醇100g的混合溶液中，並攪拌了30分鐘。添加二氯甲烷200g並進行分液之後，取出有機層，用水200mL分液了2次。用硫酸鈉進行乾燥之後，進行加熱減壓濃縮，從而獲得了粗產物（粉體）。添加己烷50g並進行15分鐘的再漿料化之後，進行過濾收集，從而獲得了12.4g的化合物A-53-I3。 在燒瓶中，將A-53-I3 4.0g、碳酸鉀2.3g、乙腈37.0g進行了懸浮攪拌之後，滴加了甲基丙烯酸1.3g。將溶液升溫至40℃之後，攪拌了6小時。藉由加熱減壓濃縮而蒸餾去除乙腈之後，添加乙酸乙酯100g以使其溶解，並用飽和碳酸氫鈉水溶液100mL分液清洗了2次，用水200mL分液清洗了2次。用硫酸鈉乾燥有機層之後，進行加熱減壓濃縮，從而獲得了粗產物。進而，使用二氧化矽凝膠管柱層析法（展開溶劑：己烷/乙酸乙酯=5/1（體積比））進行純化，從而獲得了1.4g的化合物A-53（粉體）（產率35%）。將 1H-NMR資料示於以下。 1H-NMR，400MHz，δ（（DMSO-d6）ppm：1.00-1.73（18H、m）、1.88-1.90（3H、m）、2.31（2H、q）、2.95-3.05（1H、m）、3.38-3.47（1H、m）、4.75（2H、s）、5.03（2H、s）、5.67-5.71（1H、m）、6.03-6.06（1H、m）、6.74（1H、dd）、6.83（1H、d）、6.89（1H、d）、9.64（1H、s）。 在下述式中，Me表示甲基，Cy表示環己基。 [化學式87]

Figure 02_image172
- Synthesis of Compound A-53 - In a flask, 143.7 g of dicyclohexylamine and 525.2 g of dichloromethane were stirred. After cooling the solution to 0 to 5°C, 80.0 g of bromoacetyl bromide was added dropwise. After warming up to room temperature, it stirred for 3 hours. After adding the reaction solution to 1000 mL of water, it stirred for 15 minutes. After the precipitate was filtered out, it was washed twice with 400 mL of water for liquid separation. After drying with sodium sulfate, the mixture was concentrated under reduced pressure with heating to obtain a crude product. After reslurrying with 55 g of hexane, the solid was collected by filtration to obtain 73.2 g (powder) of compound A-53-I1 (yield: 61%). In the flask, 20.0 g of A-53-I1, 10.2 g of vanillyl alcohol, 11.0 g of potassium carbonate, and 100 g of acetone were stirred. After raising the temperature of the solution to 40°C, it was stirred for 4 hours. After the solid was filtered off, the mixture was concentrated under reduced pressure under heating, and the acetone was distilled off. After dissolving in 600 mL of ethyl acetate, the solution was separated and washed three times with 350 mL of water. The organic layer was dried with sodium sulfate, and then concentrated under reduced pressure with heating to obtain a crude product (powder). After adding 45 g of hexane and reslurrying for 30 minutes, the solid was collected by filtration to obtain 23.0 g of compound A-53-I2. In the flask, 11.0 g of A-53-I2 was dissolved in 38.8 g of methylene chloride, and the mixture was stirred. After cooling the solution to 0 to 5°C, 117 mL of a boron tribromide dichloromethane solution (1 mol/L) was added dropwise. After warming up to room temperature, it stirred for 3 hours. The reaction solution was added to a mixed solution of 500 mL of water and 100 g of methanol, followed by stirring for 30 minutes. After adding 200 g of dichloromethane and carrying out liquid separation, the organic layer was taken out and liquid-separated twice with 200 mL of water. After drying with sodium sulfate, it concentrated under reduced pressure under heating to obtain a crude product (powder). After adding 50 g of hexane and reslurrying for 15 minutes, filtration was performed to obtain 12.4 g of compound A-53-I3. In the flask, 4.0 g of A-53-I3, 2.3 g of potassium carbonate, and 37.0 g of acetonitrile were suspended and stirred, and then 1.3 g of methacrylic acid was added dropwise. After raising the temperature of the solution to 40°C, it was stirred for 6 hours. After the acetonitrile was distilled off by concentration under heating and reduced pressure, 100 g of ethyl acetate was added to dissolve it, and the mixture was washed twice with 100 mL of saturated aqueous sodium bicarbonate solution and twice with 200 mL of water. The organic layer was dried with sodium sulfate, and then concentrated under reduced pressure with heating to obtain a crude product. Further, it was purified using silica gel column chromatography (developing solvent: hexane/ethyl acetate=5/1 (volume ratio)) to obtain 1.4 g of compound A-53 (powder) ( yield 35%). 1 H-NMR data are shown below. 1 H-NMR, 400MHz, δ((DMSO-d6)ppm: 1.00-1.73(18H,m), 1.88-1.90(3H,m), 2.31(2H,q), 2.95-3.05(1H,m), 3.38-3.47 (1H, m), 4.75 (2H, s), 5.03 (2H, s), 5.67-5.71 (1H, m), 6.03-6.06 (1H, m), 6.74 (1H, dd), 6.83 ( 1H, d), 6.89 (1H, d), 9.64 (1H, s). In the following formula, Me represents a methyl group, and Cy represents a cyclohexyl group. [Chemical formula 87]
Figure 02_image172

〔聚合抑制劑〕 ·B-1～B-2：下述結構的化合物 [化學式88]

Figure 02_image174
[Polymerization inhibitor] B-1 to B-2: compounds of the following structures [Chemical formula 88]
Figure 02_image174

〔矽烷偶合劑（金屬接著性改良劑）〕 ·C-1～C-2：下述結構的化合物。在下述式中，Et表示乙基。 [化學式89]

Figure 02_image176
[Silane Coupling Agent (Metal Adhesion Improver)] ·C-1 to C-2: Compounds of the following structures. In the following formula, Et represents an ethyl group. [Chemical formula 89]
Figure 02_image176

〔遷移抑制劑〕 ·D-1：下述結構的化合物 [化學式90]

Figure 02_image178
[Migration inhibitor] D-1: Compound of the following structure [Chemical formula 90]
Figure 02_image178

〔添加劑〕 ·E-1～E-2：下述結構的化合物 [化學式91]

Figure 02_image180
[Additives] E-1 to E-2: Compounds of the following structures [Chemical Formula 91]
Figure 02_image180

〔溶劑〕 ·NMP：N-甲基-2-吡咯啶酮 ·EL：乳酸乙酯 ·DMSO：二甲基亞碸 ·GBL：γ-丁內酯 [Solvent] · NMP: N-methyl-2-pyrrolidone EL: ethyl lactate DMSO: dimethyl sulfoxide GBL: gamma-butyrolactone

＜評價＞ 〔斷裂伸長率的評價〕 將各實施例及各比較例中所製備之樹脂組成物或比較用組成物，分別藉由旋塗法適用於矽晶圓上，從而形成了樹脂層。 在加熱板上將形成有所獲得之樹脂層之矽晶圓在表中的“PB溫度（℃）”一欄中所記載的溫度下乾燥5分鐘，從而在矽晶圓上獲得了表中的“膜厚（μm）”一欄中所記載的厚度的樹脂組成物層。 在表中的顯影條件一欄中記載為“負”之例子中，以500mJ/cm 2的曝光能量對矽晶圓上的樹脂組成物層的整面進行了曝光。曝光波長記載於表中的“曝光波長”中。曝光波長的單位為nm。在表中的顯影條件一欄中記載為“正”之例子中，不進行曝光。 在曝光方式一欄中記載為“M”之例子中，使用步進機作為光源進行了曝光。 在曝光方式一欄中記載為“L”之例子中，使用直接曝光裝置（ADTEC DE-6UH III）作為光源進行了曝光。在“硬化溫度（℃）”一欄中記載有數值之例子中，使用加熱板，在氮氣環境下，以10℃/分鐘的升溫速度對上述曝光後的樹脂組成物層進行升溫，在達到表的“硬化溫度（℃）”一欄中所記載的溫度之後，將上述溫度維持了表的“硬化時間（min）”中所記載的時間（分鐘）。 在“硬化溫度（℃）”一欄中記載為“IR”之例子中，使用紅外線燈加熱裝置（ADVANCE RIKO, Inc.製、RTP-6），在氮氣環境下，以10℃/分鐘的升溫速度對樹脂組成物層進行升溫，在達到230℃之後，將上述溫度維持了120分鐘。 將硬化後的樹脂組成物層（硬化物）浸漬於4.9質量%氫氟酸水溶液中，並從矽晶圓剝離了硬化物。使用衝孔機對所剝離之硬化物進行沖壓，從而製作出試樣寬度3mm、試樣長度30mm的試驗片。關於所獲得之試驗片的長邊方向的伸長率，使用拉伸試驗機（Tensilon），以十字頭速度300mm/分鐘在25℃、65%RH（相對濕度）的環境下，依據JIS-K6251進行了測定。分別實施5次測定，將5次測定中之試驗片斷裂時的伸長率（斷裂伸長率）的算術平均值用作指標值。 按照下述評價基準進行評價，評價結果記載於表的“斷裂伸長率評價”一欄中。可以說指標值越大，硬化物的膜強度越優異。 -評價基準- A：上述指標值為65%以上。 B：上述指標值為60%以上且小於65%。 C：上述指標值為50%以上且小於60%。 D：上述指標值小於50%。 <Evaluation> [Evaluation of Elongation at Break] The resin composition or the composition for comparison prepared in each Example and each Comparative Example was applied to a silicon wafer by spin coating to form a resin layer. The silicon wafer on which the obtained resin layer was formed was dried on a hot plate at the temperature described in the column of "PB temperature (°C)" in the table for 5 minutes, thereby obtaining the silicon wafer on the silicon wafer as shown in the table. The resin composition layer of the thickness described in the column of "film thickness (micrometer)". In the example described as "negative" in the column of developing conditions in the table, the entire surface of the resin composition layer on the silicon wafer was exposed with exposure energy of 500 mJ/cm 2 . The exposure wavelength is described in "Exposure wavelength" in the table. The unit of exposure wavelength is nm. In the example described as "positive" in the column of developing conditions in the table, exposure was not performed. In the example described as "M" in the column of exposure method, exposure was performed using a stepper as a light source. In the example described as "L" in the column of exposure method, exposure was performed using a direct exposure device (ADTEC DE-6UH III) as a light source. In the example in which the numerical value is described in the column of "hardening temperature (°C)", the temperature of the resin composition layer after the exposure was heated at a heating rate of 10°C/min under a nitrogen atmosphere using a hot plate, and when the temperature reached the table After the temperature described in the column of "hardening temperature (°C)", the above temperature was maintained for the time (minute) described in the "hardening time (min)" of the table. In the example described as "IR" in the "hardening temperature (°C)" column, an infrared lamp heating device (manufactured by ADVANCE RIKO, Inc., RTP-6) was used, and the temperature was increased at a rate of 10°C/min in a nitrogen atmosphere. The temperature of the resin composition layer was increased at a rate, and after reaching 230° C., the temperature was maintained for 120 minutes. The cured resin composition layer (cured product) was immersed in a 4.9 mass % hydrofluoric acid aqueous solution, and the cured product was peeled off from the silicon wafer. The peeled hardened material was punched out using a punching machine to produce a test piece having a sample width of 3 mm and a sample length of 30 mm. The elongation in the longitudinal direction of the obtained test piece was measured in accordance with JIS-K6251 at a crosshead speed of 300 mm/min in an environment of 25° C. and 65% RH (relative humidity) using a tensile tester (Tensilon). measured. The measurement was performed five times, and the arithmetic mean value of the elongation at break (elongation at break) of the test piece in the five measurements was used as an index value. The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "elongation at break evaluation" in the table. It can be said that the larger the index value, the more excellent the film strength of the cured product. -Evaluation Criteria- A: The above-mentioned index value is 65% or more. B: The above index value is more than 60% and less than 65%. C: The above-mentioned index value is 50% or more and less than 60%. D: The above index value is less than 50%.

[耐藥品性的評價] 在各實施例及比較例中，分別使用樹脂組成物或比較用組成物，與上述斷裂伸長率的評價的方法相同地獲得了硬化後的樹脂組成物層（硬化物）。 將所獲得之硬化物在下述條件下浸漬於下述藥品中，並計算出溶解速度。 藥品：二甲基亞碸（DMSO）和25質量%的氫氧化四甲銨（TMAH）水溶液的90:10（質量比）的混合物 評價條件：將上述硬化物在75℃的上述藥品中浸漬15分鐘，比較浸漬前後的硬化物的膜厚，並計算出溶解速度（nm/分鐘），。 關於所獲得之溶解速度的值，按照下述評價基準進行評價，並記載於“耐藥品性評價”一欄中。可以說溶解速度越小，耐藥品性越優異。 -評價基準- A：溶解速度小於250nm/分鐘。 B：溶解速度為250nm/分鐘以上且小於500nm/分鐘。 C：溶解速度為500nm/分鐘以上且小於750nm/分鐘。 D：溶解速度為750nm/分鐘以上。 [Evaluation of chemical resistance] In each of Examples and Comparative Examples, a resin composition or a composition for comparison was used, respectively, and a cured resin composition layer (cured product) was obtained in the same manner as in the method for evaluating the elongation at break described above. The obtained cured product was immersed in the following chemical under the following conditions, and the dissolution rate was calculated. Drug: A 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and a 25 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) Evaluation conditions: The above-mentioned cured product was immersed in the above-mentioned chemical at 75° C. for 15 minutes, the film thickness of the cured product before and after the immersion was compared, and the dissolution rate (nm/min) was calculated. The obtained value of the dissolution rate was evaluated according to the following evaluation criteria, and described in the column of "Evaluation of chemical resistance". It can be said that the lower the dissolution rate, the better the chemical resistance. -Evaluation criteria- A: The dissolution rate is less than 250 nm/min. B: The dissolution rate is 250 nm/min or more and less than 500 nm/min. C: The dissolution rate is 500 nm/min or more and less than 750 nm/min. D: The dissolution rate is 750 nm/min or more.

〔膜收縮的評價〕 將各實施例及各比較例中所製備之樹脂組成物或比較用組成物，分別藉由旋塗法適用於矽晶圓上，從而形成了樹脂層。 在加熱板上將形成有所獲得之樹脂層之矽晶圓在表中的“PB溫度（℃）”一欄中所記載的溫度下乾燥5分鐘，從而在矽晶圓上獲得了表中的“膜厚（μm）”一欄中所記載的厚度的樹脂組成物層。將該後烘烤之後的膜厚設為膜厚A。 以500mJ/cm 2的曝光能量對矽晶圓上的樹脂組成物層進行了曝光。曝光波長記載於表中的“曝光波長”中。曝光波長的單位為nm。 在曝光方式一欄中記載為“M”之例子中，使用步進機作為光源，並經由光罩進行了曝光。 在表中的顯影條件一欄中記載為“負”之例子中，作為上述光罩，使用了形成有100μm見方的正方形的非遮罩部之光罩。 在表中的顯影條件一欄中記載為“正”之例子中，作為上述光罩，使用了形成有100μm見方的正方形的遮罩部之光罩。 在曝光方式一欄中記載為“L”之例子中，使用直接曝光裝置（ADTEC DE-6UH III）作為光源，對100μm見方的正方形的區域進行了曝光。 之後，對樹脂組成物層進行了顯影。 在表的“顯影液”一欄中記載為“環戊酮”之例子中，使用環戊酮作為顯影液進行顯影，並用PGMEA進行了沖洗。 又，在表的“顯影液”一欄中記載為“TMAHaq”之例子中，使用2.38%質量氫氧化四甲銨水溶液作為顯影液進行顯影，並用純水進行了沖洗。 在“硬化溫度（℃）”一欄中記載有數值之例子中，在上述顯影之後，使用加熱板，在氮氣環境下，以10℃/分鐘的升溫速度對上述曝光後的樹脂組成物層進行升溫，在達到表的“硬化溫度（℃）”一欄中所記載的溫度之後，將上述溫度維持了表的“硬化時間（min）”中所記載的時間（分鐘）。 在“硬化溫度（℃）”一欄中記載為“IR”之例子中，使用紅外線燈加熱裝置（ADVANCE RIKO, Inc.製、RTP-6），在氮氣環境下，以10℃/分鐘的升溫速度對樹脂組成物層進行升溫，在達到230℃之後，將上述溫度維持了120分鐘。 藉由上述加熱而獲得了形成有100μm見方的正方形的圖案之硬化物。 將所獲得之硬化物的膜厚設為膜厚B。 在本評價中，關於膜厚A及膜厚B，使用膜厚測定裝置KT-22（Foothill公司製）進行了測定。 之後，依據所獲得之膜厚A及膜厚B，按照下述式計算出殘膜率X，並按照下述評價基準進行了評價。評價結果記載於表的“膜收縮”一欄中。可以說上述殘膜率X越大，所獲得之硬化物的膜收縮越降低。 殘膜率X=膜厚B/膜厚A -評價基準- A：殘膜率X為0.8以上。 B：殘膜率X為0.7以上且小於0.8。 C：殘膜率X為0.6以上且小於0.7。 D：殘膜率X小於0.6。 [Evaluation of Film Shrinkage] The resin composition or the composition for comparison prepared in each Example and each Comparative Example was applied to a silicon wafer by spin coating to form a resin layer. The silicon wafer on which the obtained resin layer was formed was dried on a hot plate at the temperature described in the column of "PB temperature (°C)" in the table for 5 minutes, thereby obtaining the silicon wafer on the silicon wafer as shown in the table. The resin composition layer of the thickness described in the column of "film thickness (micrometer)". The film thickness after this post-baking is made into film thickness A. The resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ/cm 2 . The exposure wavelength is described in "Exposure wavelength" in the table. The unit of exposure wavelength is nm. In the example described as "M" in the column of exposure method, a stepper was used as a light source, and exposure was performed through a photomask. In the example described as "negative" in the column of developing conditions in the table, as the above-mentioned mask, a mask in which a square non-mask portion of 100 μm square was formed was used. In the example described as "positive" in the column of developing conditions in the table, as the above-mentioned mask, a mask in which a square mask portion of 100 μm square was formed was used. In the example described as "L" in the column of the exposure method, a direct exposure apparatus (ADTEC DE-6UH III) was used as a light source, and a square area of 100 μm square was exposed. After that, the resin composition layer was developed. In the example described as "cyclopentanone" in the column of "developing solution" in the table, development was performed using cyclopentanone as a developing solution, and rinsed with PGMEA. In addition, in the example described as "TMAHaq" in the column of "developing solution" in the table, development was performed using a 2.38 mass % aqueous tetramethylammonium hydroxide solution as a developing solution, and washing was performed with pure water. In the example in which the numerical value is described in the column of "hardening temperature (°C)", after the above-mentioned development, the resin composition layer after the above-mentioned exposure was subjected to a heating rate of 10°C/min under a nitrogen atmosphere using a hot plate. After raising the temperature and reaching the temperature described in the "hardening temperature (°C)" column of the table, the temperature was maintained for the time (minute) described in the "hardening time (min)" of the table. In the example described as "IR" in the "hardening temperature (°C)" column, an infrared lamp heating device (manufactured by ADVANCE RIKO, Inc., RTP-6) was used, and the temperature was increased at a rate of 10°C/min in a nitrogen atmosphere. The temperature of the resin composition layer was increased at a rate, and after reaching 230° C., the temperature was maintained for 120 minutes. By the above-mentioned heating, a cured product in which a 100-μm-square pattern was formed was obtained. The film thickness of the obtained hardened|cured material was made into film thickness B. In this evaluation, the film thickness A and the film thickness B were measured using a film thickness measuring apparatus KT-22 (manufactured by Foothill). Then, based on the obtained film thickness A and film thickness B, the residual film ratio X was calculated according to the following formula, and it evaluated according to the following evaluation criteria. The evaluation results are described in the column of "film shrinkage" in the table. It can be said that the larger the residual film ratio X, the lower the film shrinkage of the obtained cured product. Residual film ratio X=film thickness B/film thickness A -Evaluation criteria- A: The residual film ratio X is 0.8 or more. B: The residual film ratio X is 0.7 or more and less than 0.8. C: The residual film ratio X is 0.6 or more and less than 0.7. D: The residual film ratio X is less than 0.6.

依據以上結果，可知藉由使用本發明的樹脂組成物，所獲得之硬化物中之膜收縮降低。 比較例1中之比較用組成物不包含特定聚合性化合物。可知在該種態樣中，所獲得之硬化物中之膜收縮沒有降低。 比較例2～比較例4中之比較用組成物分別包含“AR-1”“AR-2”或“AR-3”作為其他鹼產生劑而不包含特定聚合性化合物。可知在該種態樣中，所獲得之硬化物中之膜收縮沒有降低。 From the above results, it was found that the film shrinkage in the obtained cured product was reduced by using the resin composition of the present invention. The composition for comparison in Comparative Example 1 did not contain the specific polymerizable compound. It turned out that in this aspect, the film shrinkage of the obtained hardened|cured material did not fall. The compositions for comparison in Comparative Examples 2 to 4 each contained "AR-1", "AR-2" or "AR-3" as other base generators and did not contain a specific polymerizable compound. It turned out that in this aspect, the film shrinkage of the obtained hardened|cured material did not fall.

＜實施例101＞ 藉由旋塗法將在實施例1中所使用之樹脂組成物以層狀適用於表面上形成有銅薄層之樹脂基材的銅薄層的表面上，並在100℃下乾燥5分鐘而形成膜厚20μm的感光膜之後，使用步進機（Nikon Co.,Ltd.製，NSR1505 i6）進行了曝光。關於曝光，經由遮罩（圖案為1:1線與空間，線寬為10μm的二元遮罩）在波長365nm下進行。曝光後，在100℃下加熱了4分鐘。上述加熱後，用環己酮顯影2分鐘，並用PGMEA沖洗30秒鐘，從而獲得了層的圖案。 接著，在氮氣環境下，以10℃/分鐘的升溫速度進行升溫，在達到230℃之後，在230℃下維持120分鐘，從而形成了再配線層用層間絕緣膜。該再配線層用層間絕緣膜的絕緣性優異。 又，使用該等再配線層用層間絕緣膜製造出半導體元件，其結果，確認到正常動作。 <Example 101> The resin composition used in Example 1 was applied to the surface of the copper thin layer of the resin substrate on which the copper thin layer was formed in a layer form by spin coating, and was dried at 100° C. for 5 minutes to obtain a solution. After forming a photosensitive film with a film thickness of 20 μm, exposure was performed using a stepper (Nikon Co., Ltd., NSR1505 i6). For exposure, via a mask (a binary mask with a pattern of 1:1 line-to-space, line width 10 μm) at a wavelength of 365 nm. After exposure, it was heated at 100°C for 4 minutes. After the above heating, development was performed with cyclohexanone for 2 minutes, and rinsed with PGMEA for 30 seconds, thereby obtaining a layer pattern. Next, the temperature was increased at a temperature increase rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 120 minutes to form an interlayer insulating film for rewiring layers. This interlayer insulating film for rewiring layers is excellent in insulating properties. Moreover, a semiconductor element was manufactured using these interlayer insulating films for rewiring layers, and as a result, normal operation was confirmed.

無。none.

Claims (16)

一種樹脂組成物，其係包含： 選自包括環化樹脂及其前驅物之群組中的至少1種樹脂；以及 具有經由連接基相互鍵結之聚合性基和醯胺鍵之聚合性化合物， 前述醯胺鍵與前述連接基在羰基側鍵結， 在使用前述聚合性化合物合成了單聚物的情況下，前述單聚物顯示藉由在250℃下進行加熱而產生從主鏈游離之鹼之性質。 A resin composition comprising: at least one resin selected from the group consisting of cyclized resins and precursors thereof; and A polymerizable compound having a polymerizable group and an amide bond bonded to each other via a linking group, The aforementioned amide bond is bonded to the aforementioned linking group at the carbonyl side, When a monomer is synthesized using the above-mentioned polymerizable compound, the above-mentioned monomer exhibits the property of generating a base free from the main chain by heating at 250°C. 如請求項1所述之樹脂組成物，其中， 前述聚合性化合物中之前述聚合性基為自由基聚合性基。 The resin composition according to claim 1, wherein, The said polymerizable group in the said polymerizable compound is a radical polymerizable group. 如請求項1或請求項2所述之樹脂組成物，其中， 前述聚合性化合物為下述式（1-1）所表示之化合物， [化學式1]
Figure 03_image144
式（1-1）中，R 1分別獨立地為氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，R 2分別獨立地為氫原子、鹵素原子或1價的有機基，至少2個R 2可以鍵結而形成環結構，L 1表示3價的有機基。 The resin composition according to claim 1 or claim 2, wherein the polymerizable compound is a compound represented by the following formula (1-1), [Chemical formula 1]
Figure 03_image144
In formula (1-1), R 1 is independently a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, and R 2 is independently a hydrogen atom, a halogen atom or a monovalent organic group. In the organic group, at least two R 2 can be bonded to form a ring structure, and L 1 represents a trivalent organic group. 如請求項1或請求項2所述之樹脂組成物，其中， 前述聚合性化合物為下述式（1-2）所表示之化合物， [化學式2]
Figure 03_image183
式（1-2）中，R 1分別獨立地表示氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，L 2表示單鍵或2價的連接基，Cy表示環結構，L 3表示單鍵或2價的連接基，R 2分別獨立地表示氫原子、鹵素原子或1價的有機基，至少2個R 2可以鍵結而形成環結構。 The resin composition according to claim 1 or claim 2, wherein the polymerizable compound is a compound represented by the following formula (1-2), [Chemical formula 2]
Figure 03_image183
In formula (1-2), R 1 independently represents a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, L 2 represents a single bond or a divalent linking group, and Cy represents a ring Structure, L 3 represents a single bond or a divalent linking group, R 2 independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and at least two R 2 can be bonded to form a ring structure. 如請求項1或請求項2所述之樹脂組成物，其中， 前述樹脂具有聚合性基。 The resin composition according to claim 1 or claim 2, wherein, The aforementioned resin has a polymerizable group. 如請求項1或請求項2所述之樹脂組成物，其係進一步包含光聚合起始劑。The resin composition according to claim 1 or claim 2, further comprising a photopolymerization initiator. 如請求項1或請求項2所述之樹脂組成物，其係進一步包含與前述聚合性化合物不同之聚合性化合物。The resin composition according to claim 1 or claim 2, further comprising a polymerizable compound different from the aforementioned polymerizable compound. 如請求項1或請求項2所述之樹脂組成物，其係用於形成再配線層用層間絕緣膜。The resin composition according to claim 1 or claim 2, which is used for forming an interlayer insulating film for a rewiring layer. 一種硬化物，其係將請求項1至請求項8之任一項所述之樹脂組成物硬化而成。A hardened product obtained by hardening the resin composition according to any one of claim 1 to claim 8. 一種積層體，其係包括2層以上的由請求項9所述之硬化物形成之層，並且在由前述硬化物形成之層之間的任一個之間包括金屬層。A layered body comprising two or more layers formed of the hardened product described in claim 9, and including a metal layer between any of the layers formed of the hardened product. 一種硬化物之製造方法，其係包括將請求項1至請求項8之任一項所述之樹脂組成物適用於基材上而形成膜之膜形成步驟。A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of Claims 1 to 8 on a substrate to form a film. 如請求項11所述之硬化物之製造方法，其係包括選擇性地曝光前述膜之曝光步驟及使用顯影液對前述膜進行顯影而形成圖案之顯影步驟。The method for producing a cured product according to claim 11, comprising an exposure step of selectively exposing the film and a development step of developing the film with a developer to form a pattern. 如請求項11所述之硬化物之製造方法，其係包括在50～450℃下對前述膜進行加熱之加熱步驟。The manufacturing method of the hardened|cured material of Claim 11 which comprises the heating process of heating the said film at 50-450 degreeC. 一種半導體元件，其係包含請求項9所述之硬化物。A semiconductor element comprising the cured product of claim 9. 一種化合物，其係由下述式（1-1）表示， [化學式3]
Figure 03_image144
式（1-1）中，R 1分別獨立地為氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，R 2分別獨立地為氫原子、鹵素原子或1價的有機基，至少2個R 2可以鍵結而形成環結構，L 1表示3價的有機基。 A compound represented by the following formula (1-1), [Chemical formula 3]
Figure 03_image144
In formula (1-1), R 1 is independently a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, and R 2 is independently a hydrogen atom, a halogen atom or a monovalent organic group. In an organic group, at least two R 2 can be bonded to form a ring structure, and L 1 represents a trivalent organic group. 一種化合物，其係由下述式（1-2）表示， [化學式4]
Figure 03_image146
式（1-2）中，R 1分別獨立地表示氫原子或1價的有機基，2個R 1可以鍵結而形成環結構，L 2表示單鍵或2價的連接基，Cy表示環結構，L 3表示單鍵或2價的連接基，R 2分別獨立地表示氫原子、鹵素原子或1價的有機基，至少2個R 2可以鍵結而形成環結構。 A compound represented by the following formula (1-2), [Chemical formula 4]
Figure 03_image146
In formula (1-2), R 1 independently represents a hydrogen atom or a monovalent organic group, two R 1 can be bonded to form a ring structure, L 2 represents a single bond or a divalent linking group, and Cy represents a ring Structure, L 3 represents a single bond or a divalent linking group, R 2 independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and at least two R 2 can be bonded to form a ring structure.
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