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WO2021112189A1 - Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et résine - Google Patents

Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et résine Download PDF

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Publication number
WO2021112189A1
WO2021112189A1 PCT/JP2020/045077 JP2020045077W WO2021112189A1 WO 2021112189 A1 WO2021112189 A1 WO 2021112189A1 JP 2020045077 W JP2020045077 W JP 2020045077W WO 2021112189 A1 WO2021112189 A1 WO 2021112189A1
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group
formula
repeating unit
preferable
unit represented
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PCT/JP2020/045077
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English (en)
Japanese (ja)
Inventor
敦靖 野崎
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2021562724A priority Critical patent/JP7425088B2/ja
Priority to KR1020227018621A priority patent/KR102741857B1/ko
Priority to CN202080084112.3A priority patent/CN114761466B/zh
Publication of WO2021112189A1 publication Critical patent/WO2021112189A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/145—Polyamides; Polyesteramides; Polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/008—Azides
    • G03F7/012—Macromolecular azides; Macromolecular additives, e.g. binders
    • G03F7/0125—Macromolecular azides; Macromolecular additives, e.g. binders characterised by the polymeric binder or the macromolecular additives other than the macromolecular azides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/094—Multilayer resist systems, e.g. planarising layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H05K3/287—Photosensitive compositions
    • H10W70/695—

Definitions

  • the present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, a semiconductor device, and a resin.
  • Polyimide has excellent heat resistance and insulation properties, so it is applied to various applications.
  • the above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film and a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.
  • the polyimide may be used in the form of a curable resin composition containing polyimide, or may be used in the form of a curable resin composition containing a polyimide precursor or the like.
  • the precursor is cyclized to become a resin such as polyimide by heating, for example.
  • these curable resin compositions can be applied to a base material or the like by a known coating method or the like, for example, there is a degree of freedom in designing the shape, size, application position, etc. of the curable resin composition to be applied. It can be said that it is highly adaptable to manufacturing.
  • the curable resin composition containing polyimide or a polyimide precursor will be applied more and more in industry. ing.
  • Patent Document 1 describes a photosensitive resin composition containing a polyamic acid having a specific structure, a photopolymerizable compound, and a photopolymerization initiator.
  • curable resin composition containing polyimide it is desired to provide a curable resin composition having excellent chemical resistance of the obtained cured film.
  • One embodiment of the present invention comprises a curable resin composition having excellent chemical resistance of the obtained cured film, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the cured film. It is an object of the present invention to provide a manufacturing method and a semiconductor device including the cured film or the laminate. Moreover, another embodiment of the present invention aims to provide a novel resin.
  • Curable resin composition containing a solvent In formula (1-1), Y 1 represents a divalent linking group, Ar 1 represents a substituent or an aromatic hydrocarbon group which may have a condensed ring structure, and Y 2 is a single bond or divalent.
  • X 1 represents a tetravalent linking group
  • a 1 and A 2 independently represent an oxygen atom or -NR N-
  • R 1 and R 2 independently represent 1 respectively.
  • -valent organic group R N represents a hydrogen atom or a hydrocarbon group
  • X 2 represents a tetravalent linking group
  • X 3 represents a trivalent linking group
  • X 4 represents a trivalent linking group
  • a 4 represents an oxygen atom or -NR N - represents, R 4 represents a monovalent organic group
  • R N represents a hydrogen atom or Represents a hydrocarbon group.
  • the resin is a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), a repeating unit represented by the following formula (3-3), and a repeating unit.
  • the curable resin composition according to ⁇ 1> which comprises at least one repeating unit selected from the group consisting of repeating units represented by the following formula (3-4).
  • X 5 represents a tetravalent linking group
  • R 3 and R 4 independently represent a monovalent organic group
  • Z 1 represents a divalent linking group
  • R 3 , R 4 and Z 1 contain at least one polymerizable group
  • X 6 represents a tetravalent linking group
  • Z 2 represents a divalent linking group having a polymerizable group
  • X 7 and X 8 each independently represent a trivalent linking group
  • Z 3 and Z 4 each independently represent a divalent linking group of Z 3 and Z 4 .
  • At least one represents a divalent linking group with a polymerizable group;
  • X 7 and X 8 each independently represent a trivalent linking group
  • Z 3 and Z 4 each independently represent a divalent linking group
  • R 5 and R 6 are.
  • at least one of Z 3 and Z 4 represents a divalent linking group having a polymerizable group
  • at least one of R 5 , R 6 , Z 3 and Z 4 Contains polymerizable groups.
  • the polymerizable group contained in the repeating unit represented by the above formula (3-1) or the polymerizable group contained in the repeating unit represented by the above formula (3-2) is ethylenically unsaturated.
  • the curable resin composition according to ⁇ 2> which is a group containing a bond, a cyclic ether group, a methylol group or an alkoxymethyl group.
  • ⁇ 5> The curable resin composition according to any one of ⁇ 1> to ⁇ 4>, which contains a polymerizable compound.
  • ⁇ 6> The curable resin composition according to any one of ⁇ 1> to ⁇ 5>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 7> A cured film obtained by curing the curable resin composition according to any one of ⁇ 1> to ⁇ 6>.
  • ⁇ 8> A laminate having two or more cured films according to ⁇ 7> and having a metal layer between any of the cured films.
  • a method for producing a cured film which comprises a film forming step of applying the curable resin composition according to any one of ⁇ 1> to ⁇ 6> to a substrate to form a film.
  • the method for producing a cured film according to ⁇ 9> which comprises a step of heating the film at 50 to 450 ° C.
  • a semiconductor device having the cured film according to ⁇ 7> or the laminate according to ⁇ 8>.
  • Y 1 represents a divalent linking group
  • Ar 1 represents a substituent or an aromatic hydrocarbon group which may have a condensed ring structure
  • Y 2 is a single bond or divalent.
  • X 5 represents a tetravalent linking group
  • R 3 and R 4 independently represent a monovalent organic group
  • Z 1 represents a divalent linking group
  • R 3 , R 4 and Z 1 contain at least one polymerizable group
  • X 6 represents a tetravalent group
  • Z 2 represents a divalent linking group having a polymerizable group
  • X 7 and X 8 each independently represent a trivalent linking group
  • Z 3 and Z 4 each independently represent a divalent linking group of Z 3 and Z 4 .
  • At least one represents a divalent linking group with a polymerizable group
  • X 7 and X 8 each independently represent a trivalent linking group
  • Z 3 and Z 4 each independently represent a divalent linking group
  • R 5 and R 6 are.
  • at least one of Z 3 and Z 4 represents a divalent linking group having a polymerizable group
  • at least one of R 5 , R 6 , Z 3 and Z 4 Contains polymerizable groups.
  • a curable resin composition having excellent chemical resistance of the obtained cured film, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the curing A method for producing a film and a semiconductor device including the cured film or the laminate are provided. Further, according to another embodiment of the present invention, a novel resin is provided.
  • the present invention is not limited to the specified embodiments.
  • the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
  • the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
  • the notation not describing substitution and non-substitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • alkyl group includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • aliphatic group aliphatic hydrocarbon group
  • saturated aliphatic hydrocarbon group saturated aliphatic hydrocarbon group
  • alkyl group alkylene group
  • the group may have at least one of a branched structure and a cyclic structure.
  • alkyl group includes a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an alkyl group represented by a combination thereof, unless otherwise specified.
  • exposure includes not only exposure using light but also exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
  • (meth) acrylate means both “acrylate” and “methacrylate”, or either
  • (meth) acrylic means both “acrylic” and “methacrylic", or
  • Either, and "(meth) acryloyl” means both “acryloyl” and “methacrylic", or either.
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the total solid content means the total mass of all the components of the composition excluding the solvent.
  • the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
  • GPC measurement gel permeation chromatography
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • the direction in which the layers are stacked on the base material is referred to as "upper", or, if there is a curable resin composition layer, the direction from the base material to the curable resin composition layer. Is called “upper”, and the opposite direction is called “lower”. It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.
  • the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
  • the temperature is 23 ° C.
  • the atmospheric pressure is 101,325 Pa (1 atm)
  • the relative humidity is 50% RH.
  • the combination of preferred embodiments is a more preferred embodiment.
  • the curable resin composition of the present invention contains a repeating unit represented by the formula (1-1) and is represented by the formula (2-1). It consists of a repeating unit represented by the following formula (2-2), a repeating unit represented by the following formula (2-3), and a repeating unit represented by the following formula (2-4). It comprises a resin containing at least one repeating unit selected from the group and a solvent.
  • the repeating unit represented by the formula (1-1), the repeating unit represented by the formula (2-1), the repeating unit represented by the formula (2-2), and the formula (2-3) are included.
  • a resin containing at least one repeating unit selected from the group consisting of the repeating unit represented by) and the repeating unit represented by the following formula (2-4) is also referred to as a “specific resin”.
  • Y 1 represents a divalent linking group
  • Ar 1 represents a substituent or an aromatic hydrocarbon group which may have a condensed ring structure
  • Y 2 is a single bond or divalent.
  • X 1 represents a tetravalent linking group
  • a 1 and A 2 independently represent an oxygen atom or -NR N-
  • R 1 and R 2 independently represent 1 respectively.
  • R N represents a hydrogen atom or a hydrocarbon group
  • X 2 represents a tetravalent linking group
  • X 3 represents a trivalent linking group
  • X 4 represents a trivalent linking group
  • a 4 represents an oxygen atom or -NR N - represents, R 4 represents a monovalent organic group
  • R N represents a hydrogen atom or Represents a hydrocarbon group.
  • the curable resin composition of the present invention is preferably a negative type curable resin composition.
  • the negative type curable resin composition refers to a composition in which an unexposed portion (non-exposed portion) is removed by a developing solution when a layer formed from the curable resin composition is exposed.
  • the curable resin composition of the present invention is excellent in chemical resistance of the obtained cured film.
  • the mechanism by which the above effect is obtained is not clear, but it is presumed as follows.
  • the curable resin composition of the present invention contains a specific resin.
  • the specific resin contains a repeating unit represented by the formula (1-1).
  • the repeating unit represented by the formula (1-1) includes a condensed ring structure in which an aromatic hydrocarbon ring and an oxazole ring are condensed. Since the condensed ring structure has low solvent solubility, it is presumed that the cured film obtained from the curable resin composition containing the specific resin containing the repeating unit represented by the formula (1-1) has excellent chemical resistance.
  • R 1 and R 2 are independently monovalent organic groups.
  • R 1 or R 2 is a hydrogen atom
  • the structure in which R 1 and R 2 are monovalent organic groups has low solubility in chemicals such as polar solvents and alkaline aqueous solutions, and has low chemical resistance. It is considered to be excellent. Therefore, it is presumed that a cured film having excellent chemical resistance can be obtained even when at least one of R 1 and R 2 remains in the obtained cured film. Since the cured film has excellent chemical resistance, for example, another curable resin composition containing a solvent is further applied and cured on the cured film obtained by curing the curable resin composition of the present invention, and the laminated body is cured.
  • a polar solvent such as dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP)
  • an alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution
  • TMAH tetramethylammonium hydroxide
  • Patent Document 1 includes a repeating unit represented by the formula (1-1), a repeating unit represented by the formula (2-1), and a repeating unit represented by the formula (2-2).
  • the description also suggests for resins containing at least one repeating unit selected from the group consisting of units, repeating units represented by the formula (2-3), and repeating units represented by the formula (2-4).
  • the curable resin composition in Patent Document 1 has a problem that the chemical resistance of the obtained cured film is low.
  • the curable resin composition of the present invention contains a specific resin.
  • the specific resin contains a repeating unit represented by the formula (1-1), a repeating unit represented by the formula (2-1), a repeating unit represented by the formula (2-2), and a repeating unit represented by the formula (2-2). It contains at least one repeating unit selected from the group consisting of the repeating unit represented by -3) and the repeating unit represented by the formula (2-4).
  • the specific resin may have a repeating unit represented by the formula (1-1) in the side chain, but it is preferable to have the repeating unit in the main chain.
  • the specific resin is a repeating unit represented by the formula (2-1), a repeating unit represented by the formula (2-2), a repeating unit represented by the formula (2-3), and a repeating unit represented by the formula (2-3).
  • the side chain may have at least one repeating unit selected from the group consisting of the repeating units represented by -4), but it is preferable to have the repeating unit in the main chain.
  • the "main chain” refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin
  • the "side chain” refers to other binding chains.
  • Ar 1 represents an aromatic hydrocarbon group which may have a substituent or a condensed ring structure.
  • the aromatic hydrocarbon group in Ar 1 is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a group obtained by removing three hydrogen atoms from a benzene ring or a naphthalene ring, and more preferably three hydrogen atoms from the benzene ring.
  • the group excluding the above is more preferable. It is preferable that both the nitrogen atom and the oxygen atom in the formula (1-1) are directly bonded to the ring member contained in the aromatic hydrocarbon group in Ar 1.
  • the binding site with the nitrogen atom and the binding site with the oxygen atom in the formula (1-1) in Ar 1 are located adjacent to each other.
  • a ring member in the ring structure in which a certain binding site is present and a ring member in the ring structure in which another binding site is present are defined. It means that it is an adjacent ring member in the ring structure.
  • the adjacent position is the ortho position.
  • a known substituent can be used without particular limitation, and an alkyl group, a cyclic alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkyl halide group, a hydroxy group, a carboxy group and a sulfo group can be used. Groups, halogen atoms and the like can be mentioned.
  • a known ring structure can be used without particular limitation, and a pyrrol ring, a furan ring, a thiophene ring, an oxazol ring, an imidazole ring, a pyrazole ring, an isooxazole ring, Aromatic heterocyclic structures such as thiazole ring and isothiazole ring, pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, imidazolidine ring, pyrazolidine ring, oxazolidine ring, isoxazolidine ring, thiazolidine ring, isothiazolidine ring, dioxolan ring, dithiolan ring and the like. Saturated heterocyclic structure and the like. Further, in the present invention, Ar 1 may be in a mode having no condensed ring, or may be in a mode
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aromatic hydrocarbon group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
  • the hydrocarbon group for Y 1 it may be an aliphatic hydrocarbon group may be an aromatic hydrocarbon group, but from the viewpoint of developability, it is preferably an aromatic hydrocarbon group ..
  • a saturated aliphatic hydrocarbon group is preferable.
  • the carbon number of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 2 to 10.
  • the aliphatic hydrocarbon group may have a known substituent. Examples of the substituent include an aromatic group, an alkoxy group, an aryloxy group, a halogen atom and the like.
  • an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, and at least two hydrogen atoms are removed from the benzene ring structure. Groups are more preferred.
  • the aromatic hydrocarbon group may have a known substituent. Examples of the substituent include an aliphatic hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom and the like.
  • the heterocyclic group may be either an aliphatic heterocyclic group or an aromatic heterocyclic group, but from the viewpoint of developability, an aromatic heterocyclic group is preferable.
  • heteroatom in the heterocyclic group examples include a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, and a silicon atom.
  • the aliphatic heterocyclic group is preferably a 5-membered or 6-membered aliphatic heterocyclic group, preferably a pyrrolidine ring, a pyrazolidine ring, an imidazolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a piperazine ring, or a tetrahydro.
  • Examples thereof include a pyran ring, a dioxane ring, a thian ring, a dithian ring, a morpholine ring, an oxazine ring, and a thiomorpholin ring.
  • Examples of the aromatic heterocyclic group include a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a furan ring, a thiophene ring, an oxazole ring, an isoxazole ring, and a thiazole. Rings, isothiazole rings, thiadiazole rings and the like can be mentioned.
  • Y 2 represents a single bond or a divalent organic group, and is preferably a single bond.
  • Examples of the divalent linking group in Y 2 include the same group as the divalent linking group in Y 1 described above, and the preferred embodiment is also the same.
  • the content of the repeating unit represented by the formula (1-1) contained in the specific resin is preferably 0.1 to 60% by mass, preferably 3 to 30% by mass, based on the total mass of the specific resin. More preferably. Further, the specific resin may contain only one type of repeating unit represented by the formula (1-1), or may contain two or more types of repeating units represented by the formula (1-1) having different structures. When two or more types of repeating units represented by the formula (1-1) are included, the total content of the repeating units represented by the formula (1-1) is preferably within the above range.
  • the molar amount of the structure represented by the following formula (1-1') with respect to 1 g of the specific resin is preferably 0.01 to 2 mmol / g, preferably 0.05 to 1.5 mmol / g. Is more preferable, and 0.1 to 1 mmol / g is further preferable.
  • Ar 1 has the same meaning as Ar 1 in the formula (1-1), preferable embodiments thereof are also the same.
  • the two *'s each independently represent a binding site with another structure.
  • X 1 represents a tetravalent linking group, which is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a single bond.
  • a group in which two or more of these are linked by a linking group is exemplified, and a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms are exemplified.
  • a group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or a single bond or a linking group has a carbon number of carbon atoms.
  • a group in which two or more aromatic groups of 6 to 20 are combined is more preferable.
  • a group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an aromatic group, or a linking group in which two or more of these are bonded is more preferable.
  • 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.
  • 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.
  • the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
  • preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
  • aromatic 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 further preferable.
  • X 1 is preferably a group represented by the following formula (5) or formula (6).
  • R 112 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, —O—, —CO ⁇ , —S—, —SO. 2- , NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO.
  • it is a group selected from-, -S- and SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2-, -O-, -CO. It is more preferably a divalent group selected from the group consisting of-, -S- and SO 2-.
  • * represents a binding site with another structure, respectively.
  • X 1 examples include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
  • the tetracarboxylic dianhydride is preferably represented by the following formula (O).
  • X 1 represents a tetravalent linking group.
  • X 1 has the same meaning as X 1 in the formula (2-1), and preferred ranges are also the same.
  • tetracarboxylic dianhydride examples include pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-.
  • PMDA pyromellitic dianhydride
  • 3,3', 4,4'-biphenyltetracarboxylic dianhydride 3,3', 4,4'-.
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.
  • a 1 and A 2 independently represent an oxygen atom or ⁇ NR N ⁇ , and an oxygen atom is preferable.
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aromatic hydrocarbon group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
  • R 1 and R 2 each independently represent a monovalent organic group.
  • the monovalent organic group in R 1 and R 2 include a group containing a polymerizable group or an organic group which may contain a hetero atom, from the viewpoints of chemical resistance, developability and solvent solubility of the specific resin. Therefore, a group containing a polyalkyleneoxy group is preferable.
  • Groups containing polymerizable groups Examples of the polymerizable group contained in the group containing a polymerizable group in R 1 and R 2 include a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group or an alkoxymethyl group (preferably, the alkoxy group has a carbon number of carbon atoms).
  • Groups containing (1 to 6 alkoxymethyl groups) are preferable, and vinyl groups, (meth) allyl groups, (meth) acrylamide groups, (meth) acryloxy groups, maleimide groups, vinylphenyl groups, epoxy groups, oxetanyl groups, and methylols.
  • a group or an alkoxymethyl group is more preferable, and a (meth) acryloxy group, a (meth) acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group is further preferable.
  • the number of polymerizable groups contained in the group containing the polymerizable group is 1 or more, preferably 1 to 15, more preferably 1 to 10, and 1 to 5. More preferably, 1 or 2 is particularly preferable, and 1 is most preferable.
  • the group containing the polymerizable group is preferably a vinyl group, an allyl group, a (meth) acryloyl group, or a group represented by the following formula (III).
  • R200 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
  • R 201 is an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a (poly) alkyleneoxy group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom).
  • ⁇ 12 is preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, 1 to 6 is more preferable, and 1 to 3 is particularly preferable).
  • the (poly) alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group.
  • R 201 examples include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH 2 CH (OH) CH 2-, and more preferably an ethylene group, a propylene group, a trimethylene group, and -CH 2 CH (OH) CH 2-.
  • R 200 is a methyl group and R 201 is an ethylene group.
  • * represents a binding site with another structure.
  • Organic groups that may contain heteroatoms are preferably an organic group that does not have a polymerizable group.
  • the hetero atom in the organic group which may contain the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom and the like, and an oxygen atom is preferable.
  • the hetero atom is preferably contained as an ether bond (—O—).
  • the organic group which may contain a heteroatom is preferably an organic group having 1 to 30 carbon atoms which may contain a heteroatom, and preferably an organic group having 2 to 20 carbon atoms which may contain a heteroatom. More preferred.
  • the organic group that may contain the heteroatom is preferably an organic group having a polyalkyleneoxy group.
  • the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
  • the carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
  • the said alkylene group may have a substituent.
  • Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
  • the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, and particularly preferably 2 to 4.
  • 2 is most preferred.
  • the polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyloxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups from the viewpoint of achieving both solvent solubility and chemical resistance.
  • a group bonded to the propyleneoxy group of the above is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable.
  • the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.
  • the organic group having a polyalkyleneoxy group is preferably a group represented by the following formula (PO-1).
  • R P1 each independently represent an alkylene group
  • R P2 represents a monovalent organic group
  • n represents an integer of 2 or more
  • L P1 is connected a single bond or a divalent A group is represented
  • * represents a bond site with an oxygen atom to which R 1 or R 2 in the formula (2-1) is bonded.
  • R P1 each independently is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, an ethylene group (-CH 2 -CH 2- ) or propylene group (-CH 2- CH (CH 3 )-or-CH (CH 3 ) -CH 2- ) is more preferable, and an ethylene group is further preferable.
  • RP2 represents a monovalent organic group, preferably an alkyl group, an aromatic hydrocarbon group, an aralkyl group, or a group containing a polymerizable group, and is preferably an alkyl group. Is more preferable.
  • alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 2 to 4 carbon atoms is more preferable, and an ethyl group is further preferable.
  • aromatic hydrocarbon group an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is further preferable.
  • an aralkyl group having 7 to 30 carbon atoms is preferable, an aralkyl group having 7 to 20 carbon atoms is more preferable, and a benzyl group is more preferable.
  • the polymerizable group contained in the above-mentioned group containing a polymerizable group include a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group, or an alkoxymethyl group (preferably, an alkoxy group having 1 to 6 carbon atoms).
  • a group containing (methyl group) is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group is preferable. More preferably, a (meth) acryloxy group, a (meth) acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group is further preferable.
  • a group represented by the formula (P-1) described later is preferable, and a group represented by the formula (P-2) described later or the formula (P-3) described later is used. Is more preferable.
  • n is preferably an integer of 2 to 20, more preferably an integer of 2 to 10, further preferably an integer of 2 to 5, particularly preferably an integer of 2 to 4, and most preferably 2.
  • LP1 represents a single bond or a divalent linking group, and a single bond is preferable.
  • a bond, a urea bond, or a group in which two or more of these are combined is more preferable.
  • the R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and has a hydrogen atom and 1 carbon number. It is more preferably an alkyl group of to 4 or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and particularly preferably a hydrogen atom.
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
  • the hydrocarbon group represented by L P1 saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or, a group represented by a combination thereof
  • the number of carbon atoms More preferably, it is a saturated aliphatic hydrocarbon group of 1 to 10, a group obtained by removing two or more hydrogen atoms from the benzene ring, or a group represented by a bond thereof.
  • the organic group which may contain a hetero atom may be a hydrocarbon group substituted with a halogen atom.
  • the halogen atom in the hydrocarbon group substituted with the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the hydrocarbon group an alkyl group or an aromatic hydrocarbon group is preferable, and an alkyl group is more preferable.
  • an alkyl group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 2 to 4 carbon atoms is further preferable.
  • an aromatic hydrocarbon group an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, and a phenyl group is further preferable. That is, the hydrocarbon group substituted with a halogen atom is preferably an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. By including a hydrocarbon group substituted with a halogen atom as R 1 or R 2 , the film strength of the obtained cured film is improved.
  • R 1 and R 2 may be other substituents.
  • substituents include hydrocarbon groups having an acid group and the like.
  • hydrocarbon group having an acid group include an alkyl group having an acid group, an aromatic hydrocarbon group having an acid group, and an aralkyl group having an acid group.
  • alkyl group in the alkyl group having an acid group an alkyl group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 20 carbon atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms is further preferable.
  • Examples of the acid group in the alkyl group having an acid group include a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group and the like, and a carboxy group is preferable.
  • an aromatic hydrocarbon group in the aromatic hydrocarbon group having an acid group an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is further preferable.
  • an aralkyl group having an acid group an aralkyl group having 7 to 30 carbon atoms is preferable, an aralkyl group having 7 to 20 carbon atoms is more preferable, and a benzyl group is more preferable.
  • the acid group in the aromatic hydrocarbon group having the acid group or the aralkyl group having the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group and the like, and phenol.
  • a sex hydroxy group or a carboxy group is preferable, and a phenolic hydroxy group is more preferable.
  • an aromatic hydrocarbon group having an acid group or an aralkyl group having an acid group is preferable, and an aromatic hydrocarbon group having a phenolic hydroxy group or an aralkyl group having a phenolic hydroxy group is more preferable.
  • a phenyl group having a phenolic hydroxy group, or a benzyl group having a phenolic hydroxy group is more preferable.
  • the ratio of the molar amounts of the substituents R 1 and R 2 is preferably 0 to 30%. From the viewpoint of film strength, the above ratio is preferably 0 to 10%, more preferably 0 to 5%, and even more preferably 0 to 3%. From the viewpoint of chemical resistance, the above ratio is preferably 10 to 30%, more preferably 15 to 30%.
  • the ratio of the molar amount of R 1 and R 2 which are organic groups having 1 to 30 carbon atoms which may contain a hetero atom, is preferably 20 to 100%.
  • the lower limit of the above ratio is preferably 30% or more, more preferably 40% or more, further preferably 50% or more, and particularly preferably 60% or more. It is preferably 70% or more, and most preferably 70% or more.
  • the upper limit of the above ratio is preferably 95% or less, more preferably 90% or less, further preferably 85% or less, and preferably 80% or less. It is particularly preferable, and most preferably 70% or less.
  • the content of the repeating unit represented by the formula (2-1) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, and more preferably 20 to 60% by mass. Further, the specific resin may contain only one type of repeating unit represented by the formula (2-1), or may contain two or more types of repeating units represented by the formula (2-1) having different structures. When two or more types of repeating units represented by the formula (2-1) are included, the total content of the repeating units represented by the formula (2-1) is preferably within the above range.
  • X 2 represents a tetravalent linking group.
  • X 2 has the same meaning as X 1 in formula (2-1), and the preferred embodiment is also the same.
  • the imidization rate (ring closure rate) of the specific resin is preferably 70% or more.
  • the imidization ratio is more preferably 80% or more, and further preferably 90% or more.
  • the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
  • the imidization rate is measured by, for example, the following method.
  • the infrared absorption spectrum of the specific resin is measured, and the peak intensity P1 near 1377 cm -1, which is the absorption peak derived from the imide structure, is obtained.
  • the specific resin is heat-treated at 350 ° C. for 1 hour, and then the infrared absorption spectrum is measured again to obtain the peak intensity P2 in the vicinity of 1377 cm -1.
  • the imidization rate of the specific resin can be determined based on the following formula.
  • Imidization rate (%) (peak intensity P1 / peak intensity P2) ⁇ 100
  • the content of the repeating unit represented by the formula (2-2) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, and more preferably 20 to 60% by mass. Further, the specific resin may contain only one type of repeating unit represented by the formula (2-2), or may contain two or more types of repeating units represented by the formula (2-2) having different structures. When two or more types of repeating units represented by the formula (2-2) are included, the total content of the repeating units represented by the formula (2-2) is preferably within the above range.
  • X 3 represents a trivalent linking group.
  • X 3 is a straight-chain or branched aliphatic group, cyclic aliphatic group, an aromatic group, heteroaromatic group, or a single bond or a group linked these two or more by linking groups and the like, carbon A linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a single bond.
  • a group in which two or more of these are combined by a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferable.
  • An aromatic group having 6 to 20 carbon atoms is more preferable, and a group obtained by removing three hydrogen atoms from the benzene ring is particularly preferable.
  • a group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an aromatic group, or a linking group in which two or more of these are bonded is more preferable.
  • 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.
  • 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.
  • the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
  • preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
  • aromatic 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 further preferable.
  • X 3 is preferably at least one carboxyl group is derived from also good tricarboxylic acid compound halogenated. Chlorination is preferable as the halogenation.
  • a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Of the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be acid anhydrideized.
  • the halogenated tricarboxylic acid compound used in the production of the polyamide-imide precursor include branched chain aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. Only one kind of these tricarboxylic acid compounds may be used, or two or more kinds may be used.
  • 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, and a carbon number of carbon atoms.
  • a tricarboxylic acid compound containing 6 to 20 aromatic groups or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or carbon by a single bond or a linking group is preferable.
  • a tricarboxylic acid compound containing a group in which two or more aromatic groups of the number 6 to 20 are combined is more preferable.
  • the tricarboxylic acid compound examples include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid.
  • Or phthalic acid anhydride and benzoic acid are single-bonded, with -O-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- or phenylene group. Examples thereof include linked compounds.
  • These compounds may be compounds in which two carboxy groups are anhydrated (eg, trimellitic acid anhydride) or compounds in which at least one carboxy group is halogenated (eg, trimellitic acid chloride). There may be.
  • the imidization rate (ring closure rate) of the above-mentioned specific resin is preferably 70% or more.
  • the imidization ratio is more preferably 80% or more, and further preferably 90% or more.
  • the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
  • the content of the repeating unit represented by the formula (2-3) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, and more preferably 20 to 60% by mass. Further, the specific resin may contain only one type of repeating unit represented by the formula (2-3), or may contain two or more types of repeating units represented by the formula (2-3) having different structures. When two or more types of repeating units represented by the formula (2-3) are included, the total content of the repeating units represented by the formula (2-3) is preferably within the above range.
  • the content of the repeating unit represented by the formula (2-4) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, and more preferably 20 to 60% by mass. Further, the specific resin may contain only one type of repeating unit represented by the formula (2-4), or may contain two or more types of repeating units represented by the formula (2-4) having different structures. When two or more types of repeating units represented by the formula (2-4) are included, the total content of the repeating units represented by the formula (2-4) is preferably within the above range.
  • the specific resin is a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), a repeating unit represented by the following formula (3-3), and the following formula. It is preferable to include at least one repeating unit selected from the group consisting of the repeating units represented by (3-4). These repeating units contain polymerizable groups in their structures. As a result, a crosslinked structure due to the polymerizable group is formed in the cured film, and it is considered that the chemical resistance of the obtained cured film is further improved.
  • the polymerizable group contained in the repeating unit and the polymerizable group contained in the repeating unit represented by the above formula (3-4) are a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group or an alkoxymethyl group.
  • a group containing (preferably an alkoxymethyl group having 1 to 6 carbon atoms in the alkoxy group) is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group, a maleimide group, and a vinyl are preferable.
  • a phenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group is more preferable, and a (meth) acryloxy group, a (meth) acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group is further preferable.
  • the specific resin when the specific resin contains a repeating unit represented by the formula (2-1), the specific resin preferably contains a repeating unit represented by the formula (3-1).
  • the repeating unit represented by the formula (3-1) is a repeating unit including the repeating unit represented by the formula (2-1) in the structure.
  • the specific resin when the specific resin contains a repeating unit represented by the formula (2-2), the specific resin preferably contains a repeating unit represented by the formula (3-2).
  • the repeating unit represented by the formula (3-2) is a repeating unit including the repeating unit represented by the formula (2-2) in the structure.
  • the specific resin contains a repeating unit represented by the formula (2-3)
  • the specific resin preferably contains a repeating unit represented by the formula (3-3).
  • the repeating unit represented by the formula (3-3) is a repeating unit including two repeating units represented by the formula (2-3) in the structure.
  • the specific resin contains a repeating unit represented by the formula (2-4)
  • the specific resin preferably contains a repeating unit represented by the formula (3-4).
  • the repeating unit represented by the formula (3-4) is a repeating unit including two repeating units represented by the formula (2-4) in the structure.
  • the repeating unit represented by any of the formulas (4-1) to (4-4) described later is the repeating unit represented by any of the formulas (3-1) to (3-4). Not applicable.
  • X 5 represents a tetravalent linking group
  • R 3 and R 4 independently represent a monovalent organic group
  • Z 1 represents a divalent linking group
  • R 3 , R 4 and Z 1 contain at least one polymerizable group
  • X 6 represents a tetravalent linking group
  • Z 2 represents a divalent linking group having a polymerizable group
  • X 7 and X 8 each independently represent a trivalent linking group
  • Z 3 and Z 4 each independently represent a divalent linking group of Z 3 and Z 4 .
  • At least one represents a divalent linking group with a polymerizable group
  • X 7 and X 8 each independently represent a trivalent linking group
  • Z 3 and Z 4 each independently represent a divalent linking group
  • R 5 and R 6 are.
  • at least one of Z 3 and Z 4 represents a divalent linking group having a polymerizable group
  • at least one of R 5 , R 6 , Z 3 and Z 4 Contains polymerizable groups.
  • R 3 and R 4 are independently synonymous with R 1 and R 2 in formula (2-1), and the preferred embodiments are also the same.
  • X 5 has the same meaning as X 1 in formula (2-1), and the preferred embodiment is also the same.
  • Z 1 is a divalent linking group.
  • Z 1 is preferably a divalent linking group having a polymerizable group.
  • Z 1 has the same meaning as Z 5 in the formula (6-1) described later, and the preferred embodiment is also the same.
  • Z 1 is a divalent linking group having no polymerizable group
  • at least one of R 3 and R 4 is a group having a polymerizable group.
  • the polymerizable group in Z 1 includes a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group or an alkoxymethyl group (preferably an alkoxy group methyl group having 1 to 6 carbon atoms in the alkoxy group).
  • Groups are preferred, vinyl groups, (meth) allyl groups, (meth) acrylamide groups, (meth) acryloxy groups, maleimide groups, vinylphenyl groups, epoxy groups, oxetanyl groups, methylol groups or alkoxymethyl groups are more preferred (meth ) Acryloxy group, (meth) acrylamide group, epoxy group, methylol group or alkoxymethyl group are more preferable.
  • the number of polymerizable groups contained in Z 1 is preferably 1 or more, more preferably 1 to 15, further preferably 1 to 10, and 1 to 5. Is more preferable, 1 or 2 is particularly preferable, and 1 is most preferable.
  • Z 1 is preferably a group containing an aromatic hydrocarbon group, more preferably a group containing an aromatic hydrocarbon group having 6 to 30 carbon atoms, and has a benzene ring structure. , Or a group containing a naphthalene ring structure is more preferable, and a group containing a benzene ring structure is particularly preferable.
  • Z 1 is preferably a group represented by the following formula (Z-1).
  • Q 1 represents an organic group having 1 to 30 carbon atoms
  • a 1 represents a group containing a polymerizable group
  • n 1 represents an integer of 1 or more
  • * represents another structure. Represents a binding site.
  • Q 1 is preferably an n2 + divalent group containing an aromatic hydrocarbon group.
  • Aromatic hydrocarbon group in Q 1 is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, 2 or more benzene rings It is more preferable that the group is obtained by removing the hydrogen atom of, and it is particularly preferable that the group is obtained by removing 3 or more hydrogen atoms from the benzene ring.
  • the Q 1, 2 single * the binding site of according to formula (Z-1) is preferably either an aromatic hydrocarbon group.
  • the two nitrogen atoms according to formula (3-1) is an aromatic hydrocarbon ring structure contained in Q 1, it is preferable to directly bond.
  • the binding site with A 1 in Q 1 is an aromatic hydrocarbon group. That is, it is preferable that A 1 is directly bonded to the aromatic hydrocarbon ring structure contained in Q 1.
  • Q 1 preferably contains at least one structure selected from the group consisting of the structures represented by the following formulas (A2-1) to (A2-5), and the above formulas (A2-1) to Q1. It is more preferable that the structure is at least one selected from the group consisting of the structures represented by the formula (A2-5).
  • R A211 ⁇ R A214, R A221 ⁇ R A224, R A231 ⁇ R A238, R A241 ⁇ R A248 and R A251 ⁇ R A258 are each independently a hydrogen atom , Alkyl group, cyclic alkyl group, alkoxy group, hydroxy group, cyano group, alkyl halide group, or halogen atom, and LA231 and LA241 are independently single-bonded, carbonyl group, sulfonyl group, and divalent, respectively.
  • R A211 ⁇ R A214 at least one of R a 221 ⁇ R A224 one, at least one of R A231 ⁇ R A238, at least one of R a 241 ⁇ R A248, and, at least one of R A251 ⁇ R A258 is between a 1 in the formula (Z-1) It may be a binding site, and each independently represents a binding site with another structure.
  • Q 1 is preferably a structure represented by any of formulas (A2-1) ⁇ formula (A2-4), is represented by the formula (A2-1) It is more preferable to include a structure such as
  • R A211 ⁇ R A214 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, hydroxy It is preferable to represent a group, a cyano group, an alkyl halide group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms.
  • An alkoxy group of 6 and an alkyl group having 1 to 3 carbon atoms are more preferable, and an alkyl group having a hydrogen atom or 1 to 6 carbon atoms is more preferable.
  • R A211 ⁇ R A214 is preferably a binding site to the A 1 in at least 1 Exemplary ethynylphenylbiadamantane derivatives (Z-1), it is more preferable R A213 is a bond site of the A 1 ..
  • each of R A221 ⁇ R A224 have the same meanings as R A211 ⁇ R A214 in formula (A2-1), preferable embodiments thereof are also the same. Further, among the R A211 ⁇ R A214, it is preferably a binding site to the A 1 in at least 1 Exemplary ethynylphenylbiadamantane derivatives (Z-1), 1 or 2 is a binding site between the A 2 More preferred.
  • each of R A231 ⁇ R A238, have the same meanings as R A211 ⁇ R A214 in formula (A2-1), preferable embodiments thereof are also the same.
  • LA231 is a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, —O—, —S. -, -NR N- , a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms is preferable, and a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or a heterocyclic group.
  • R A231 ⁇ R A2308 it is preferably a binding site to the A 1 in at least 1 Exemplary ethynylphenylbiadamantane derivatives (Z-1), 1 or 2 is a binding site between the A 2 more preferably, bract one of R A231 ⁇ R A234, it is more preferably one of R A235 ⁇ R A238 is a bond site of the a 1.
  • each of R A241 ⁇ R A248 and L A 241 has the same meaning as R A231 ⁇ R A238 and L A231 in formula (A2-3), preferable embodiments thereof are also the same. Further, it is preferable that at least one of the above RA241 to RA248 is a binding site with A 1 in the formula (Z-1), and one or two are binding sites with the above A 2. More preferably, bract one of R a 241 ⁇ R A244, it is more preferably one of R A245 ⁇ R A248 is a bond site between the a 2.
  • R A251 ⁇ R A258 have the same meanings as R A211 ⁇ R A214 in formula (A2-1), preferable embodiments thereof are also the same. Further, it is preferable that at least one of the above RA251 to RA258 is a binding site with A 1 in the formula (Z-1), and one or two are binding sites with the above A 1. more preferably, bract one of R a 251 ⁇ R A254, it is more preferably one of R A255 ⁇ R A258 is a bond site of the a 1.
  • a 1 represents a group containing a polymerizable group.
  • the polymerizable group a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group or an alkoxymethyl group (preferably an alkoxy group methyl group having 1 to 6 carbon atoms in the alkoxy group) is preferable.
  • a acrylamide group, an epoxy group, a methylol group, or an alkoxymethyl group is more preferable.
  • the number of polymerizable groups contained in A 2 is 1 or more, preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5. It is particularly preferable to have one or two, and most preferably one.
  • a 1 is preferably a group represented by the following formula (P-1).
  • L 1 represents a single bond or an m + 1 valent linking group
  • a 2 represents a polymerizable group
  • m represents an integer of 1 or more
  • * represents a binding site with Q 1. ..
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
  • the hydrocarbon group represented by L 1, saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or, a group represented by a combination thereof
  • the number of carbon atoms More preferably, it is a saturated aliphatic hydrocarbon group of 1 to 10, a group obtained by removing two or more hydrogen atoms from the benzene ring, or a group represented by a bond thereof.
  • a 2 is a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group.
  • Groups are preferred, with (meth) acryloxy groups, (meth) acrylamide groups, epoxy groups, methylol groups or alkoxymethyl groups being more preferred.
  • m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, further preferably an integer of 1 to 5, and 1 or 2. Is particularly preferable, and 1 is most preferable.
  • a 1 is preferably a group represented by the following formula (P-2) or formula (P-3).
  • a 2 represents a polymerizable group, and * represents a binding site with Q 1.
  • P-2 has the same meaning as A 2 in Formula (P-1), a preferable embodiment thereof is also the same.
  • a 2 represents a polymerizable group
  • L 2 is a hydrocarbon group or a hydrocarbon group
  • Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, a carbonate bond, or an amide bond.
  • * represents a bonding site with Y 1.
  • RN is as described above.
  • a 2 has the same meaning as A 2 in Formula (P-1), a preferable embodiment thereof is also the same.
  • L 2 is preferably a hydrocarbon group, a (poly) alkyleneoxy group, or a group represented by a combination thereof, and more preferably a hydrocarbon group.
  • the (poly) alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group.
  • the polyalkyleneoxy group means a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
  • the hydrocarbon group is preferably an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a combination thereof, and more preferably an alkylene group.
  • an alkylene group having 1 to 30 carbon atoms is preferable, an alkylene group having 1 to 20 carbon atoms is more preferable, and an alkylene group having 1 to 10 carbon atoms is further preferable.
  • alkyl group includes a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an alkyl group represented by a combination thereof, unless otherwise specified.
  • an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, a phenylene group or a naphthylene group is more preferable, and a phenylene group is preferable.
  • an alkylene group in the (poly) alkyleneoxy group an alkylene group having 2 to 10 carbon atoms is preferable, an alkylene group having 2 to 4 carbon atoms is more preferable, an ethylene group or a propylene group is more preferable, and an ethylene group is further preferable. ..
  • the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, and particularly preferably 2 to 4. preferable.
  • Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, or an amide bond, and an ester bond, a urethane bond, a urea bond, or an amide bond is more preferable.
  • * represents a binding site to Q 1.
  • the distance between the polymerizable group contained in A 1 and the main chain of the specific resin is preferably 0 to 15, and more preferably 0 to 10.
  • the distance between the polymerizable group contained in A 1 and the main chain of the specific resin is the smallest of the number of atoms contained between the atom contained in the main chain of polyimide and the polymerizable group. Say a number.
  • the distance between the methacryloxy group and the main chain is 4. That is, when the polyimide has a ring structure inside the main chain, the "atoms contained in the main chain of the above-mentioned polyimide" include the ring members of the ring structure.
  • a 1 contains a plurality of polymerizable groups, of polymerizable groups contained in A 1, and a polymerizable group closest to the main chain, that the distance between the main chain of the polyimide is 0-15 It is preferably 0 to 10, and more preferably 0 to 10. Furthermore, it if A 1 contains a plurality of polymerizable groups, and all of the polymerizable groups contained in A 1, still more preferably the distance between the main chain of the polyimide is 0-15, 0-10 Is particularly preferable.
  • n1 represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and further preferably an integer of 1 to 4. It is preferably 1 or 2, and most preferably 1. Further, when n1 is an integer of 2 or more, it may be respectively the same n1 pieces of A 1, may be different.
  • the content of the repeating unit represented by the formula (3-1) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, and more preferably 20 to 60% by mass. Further, the specific resin may contain only one type of repeating unit represented by the formula (3-1), or may contain two or more types of repeating units represented by the formula (3-1) having different structures. When two or more types of repeating units represented by the formula (3-1) are included, the total content of the repeating units represented by the formula (3-1) is preferably within the above range.
  • Z 2 has the same meaning as Z 1 in formula (3-1), and the preferred embodiment is also the same.
  • the content of the repeating unit represented by the formula (3-2) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, and more preferably 20 to 60% by mass. Further, the specific resin may contain only one type of repeating unit represented by the formula (3-2), or may contain two or more types of repeating units represented by the formula (3-2) having different structures. When two or more types of repeating units represented by the formula (3-2) are included, the total content of the repeating units represented by the formula (3-2) is preferably within the above range.
  • each X 7 and X 8 independently has the same meaning as X 3 in the formula (2-3), preferable embodiments thereof are also the same.
  • at least one of Z 3 and Z 4 represents a divalent linking group having a polymerizable group, a divalent linking group having any of the Z 3 and Z 4 are polymerizable groups It is preferable to have.
  • Z 3 is a divalent linking group having a polymerizable group
  • Z 3 is synonymous with Z 1 in the formula (3-1), and the preferred embodiment is also the same.
  • Z 4 is a divalent linking group having a polymerizable group
  • Z 4 is synonymous with Z 1 in the formula (3-1), and the preferred embodiment is also the same.
  • Z 3 is a divalent linking group having no polymerizable group
  • Z 3 has the same meaning as Z 5 in the formula (6-1) described later, and the preferred embodiment is also the same.
  • Z 4 is a divalent linking group having no polymerizable group
  • Z 4 has the same meaning as Z 5 in the formula (6-1) described later, and the preferred embodiment is also the same.
  • the content of the repeating unit represented by the formula (3-3) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, and more preferably 20 to 60% by mass. Further, the specific resin may contain only one type of repeating unit represented by the formula (3-3), or may contain two or more types of repeating units represented by the formula (3-3) having different structures. When two or more types of repeating units represented by the formula (3-3) are included, the total content of the repeating units represented by the formula (3-3) is preferably within the above range.
  • each X 7 and X 8 independently has the same meaning as X 4 in the formula (2-4), preferable embodiments thereof are also the same.
  • at least one of Z 3 and Z 4 preferably represents a divalent linking group having a polymerizable group, any of Z 3 and Z 4 are divalent having a polymerizable group More preferably, it is a linking group.
  • Z 3 is a divalent linking group having a polymerizable group
  • Z 3 is synonymous with Z 1 in the formula (3-1), and the preferred embodiment is also the same.
  • Z 4 is a divalent linking group having a polymerizable group
  • Z 4 is synonymous with Z 1 in the formula (3-1), and the preferred embodiment is also the same.
  • Z 3 is a divalent linking group having no polymerizable group
  • Z 3 has the same meaning as Z 5 in the formula (6-1) described later, and the preferred embodiment is also the same.
  • Z 4 is a divalent linking group having no polymerizable group
  • Z 4 has the same meaning as Z 5 in the formula (6-1) described later, and the preferred embodiment is also the same.
  • R 5 and R 6 are synonymous with R 3 and R 4 in formula (3-1), respectively, and preferred embodiments are also the same.
  • the content of the repeating unit represented by the formula (3-4) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, and more preferably 20 to 60% by mass. Further, the specific resin may contain only one type of repeating unit represented by the formula (3-4), or may contain two or more types of repeating units represented by the formula (3-4) having different structures. When two or more types of repeating units represented by the formula (3-4) are included, the total content of the repeating units represented by the formula (3-4) is preferably within the above range.
  • the specific resin is selected from a group consisting of a repeating unit represented by the formula (4-1), a repeating unit represented by the formula (4-2), and a repeating unit represented by the formula (4-3). It is preferable to include at least one repeating unit.
  • the specific resin contains a repeating unit represented by the formula (2-1)
  • the specific resin preferably contains a repeating unit represented by the formula (4-1).
  • the repeating unit represented by the formula (4-1) is a repeating unit including the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (2-1).
  • the specific resin when the specific resin contains a repeating unit represented by the formula (2-2), the specific resin preferably contains a repeating unit represented by the formula (4-2).
  • the repeating unit represented by the formula (4-2) is a repeating unit including the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (2-2).
  • the specific resin when the specific resin contains a repeating unit represented by the formula (2-3), the specific resin preferably contains a repeating unit represented by the formula (4-3).
  • the repeating unit represented by the formula (4-3) is a repeating unit including the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (2-3).
  • the specific resin contains a repeating unit represented by the formula (2-4)
  • the specific resin preferably contains a repeating unit represented by the formula (4-4).
  • the repeating unit represented by the formula (4-4) is a repeating unit including the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (2-4).
  • X 5 represents a tetravalent organic group
  • R 3 and R 4 independently represent a monovalent organic group
  • L 41 is represented by the following formula (L-1). Structure.
  • X 5 , R 3 and R 4 are synonymous with X 5 , R 3 and R 4 in formula (3-1), respectively, and the preferred embodiments are also the same.
  • X 6 represents a tetravalent group
  • L 42 has a structure represented by the following formula (L-1).
  • X 6 has the same meaning as X 6 in the formula (3-2), preferable embodiments thereof are also the same.
  • X 7 and X 8 each independently represent a trivalent linking group
  • L 44 represents a divalent linking group
  • L 43 is represented by the following formula (L-1). Structure.
  • X 7 and X 8 are synonymous with X 7 and X 8 in formula (3-3), respectively, and so are preferred embodiments.
  • L 44 represents a divalent linking group, which is a divalent linking group having a polymerizable group in Z 3 in formula (3-3) or a divalent group having no polymerizable group. It is preferably a group similar to the linking group, and more preferably a group similar to the divalent linking group having a polymerizable group in Z 3 in the formula (3-3).
  • X 7 and X 8 each independently represent a trivalent linking group
  • L 46 represents a divalent linking group
  • L 45 is represented by the following formula (L-1). Structure.
  • X 7 and X 8 are synonymous with X 7 and X 8 in formula (3-4), respectively, and so are preferred embodiments.
  • R 5 and R 6 are synonymous with R 5 and R 6 in formula (3-4), respectively, and so are preferred embodiments.
  • L 46 represents a divalent linking group, which is a divalent linking group having a polymerizable group in Z 3 in formula (3-4) or a divalent group having no polymerizable group.
  • Y 1 represents a divalent linking group
  • Ar 1 represents a substituent or an aromatic hydrocarbon group which may have a condensed ring structure
  • Y 2 is a single bond or divalent.
  • Each Y 1, Ar 1 and Y 2 in formula (L-1) has the same meaning as Y 1, Ar 1 and Y 2 in the formula (1-1), preferable embodiments thereof are also the same.
  • the content of the repeating unit represented by the formula (4-1) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, and more preferably 20 to 60% by mass. Further, the specific resin may contain only one type of repeating unit represented by the formula (4-1), or may contain two or more types of repeating units represented by the formula (4-1) having different structures. When two or more types of repeating units represented by the formula (4-1) are included, the total content of the repeating units represented by the formula (4-1) is preferably within the above range.
  • the content of the repeating unit represented by the formula (4-2) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, and more preferably 20 to 60% by mass. Further, the specific resin may contain only one type of repeating unit represented by the formula (4-2), or may contain two or more types of repeating units represented by the formula (4-2) having different structures. When two or more types of repeating units represented by the formula (4-2) are included, the total content of the repeating units represented by the formula (4-2) is preferably within the above range.
  • the content of the repeating unit represented by the formula (4-3) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, and more preferably 20 to 60% by mass. Further, the specific resin may contain only one type of repeating unit represented by the formula (4-3), or may contain two or more types of repeating units represented by the formula (4-3) having different structures. When two or more types of repeating units represented by the formula (4-3) are included, the total content of the repeating units represented by the formula (4-3) is preferably within the above range.
  • the content of the repeating unit represented by the formula (4-4) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, and more preferably 20 to 60% by mass. Further, the specific resin may contain only one type of repeating unit represented by the formula (4-4), or may contain two or more types of repeating units represented by the formula (4-4) having different structures. When two or more types of repeating units represented by the formula (4-3) are included, the total content of the repeating units represented by the formula (4-4) is preferably within the above range.
  • the specific resin also preferably contains a repeating unit represented by the formula (5-1).
  • the repeating unit represented by the formula (5-1) is a group containing the repeating unit represented by the formula (1-1).
  • the specific resin includes a repeating unit represented by the formula (5-1), a repeating unit represented by the formula (3-1), a repeating unit represented by the formula (3-2), and a repeating unit represented by the formula (3-3). It is preferable to include at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (3-4) and the repeating unit represented by the formula (3-4), and is represented by the formula (5-1).
  • the repeating unit including the repeating unit represented by the formula (3-1) or the repeating unit represented by the formula (5-1) and the repeating unit represented by the formula (3-4). It is more preferable to include and.
  • L 51 is a structure represented by the above formula (L-1), and L 52 represents a divalent organic group.
  • L 52 is synonymous with Z 1 in formula (3-1), and the preferred embodiment is also the same.
  • the content of the repeating unit represented by the formula (5-1) is 0.1 to 80 mass with respect to the total mass of the specific resin. %, More preferably 10 to 50% by mass.
  • the specific resin may contain only one type of repeating unit represented by the formula (5-1), or may contain two or more types of repeating units represented by the formula (5-1) having different structures. When two or more types of repeating units represented by the formula (5-1) are included, the total content of the repeating units represented by the formula (5-1) is preferably within the above range.
  • the specific resin may further contain other repeating units.
  • the other repeating unit include a repeating unit represented by any of the formulas (6-1) to (6-4).
  • the repeating unit corresponding to any of the above-mentioned equations (3-1) to (3-4), equations (4-1) to (4-4) and equation (5-1) is the equation (6-1). It shall not correspond to the repeating unit represented by any of 1) to the formula (6-4).
  • X 5 represents a tetravalent linking group
  • R 3 and R 4 each independently represent a monovalent organic group having no polymerizable group
  • Z 1 represents a polymerizable group.
  • X 6 represents a tetravalent linking group, Z 6 is a polymerizable group, and a divalent group having neither the structure represented by the above formula (L-1).
  • X 7 and X 8 each independently represent a trivalent linking group, and Z 7 and Z 8 independently represent a polymerizable group and the above formula (L-1).
  • X 7 and X 8 each independently represent a trivalent linking group, and R 5 and R 6 each independently represent a monovalent organic group having no polymerizable group.
  • Z 7 and Z 8 independently represent a polymerizable group and a divalent linking group having no structure represented by the above formula (L-1).
  • X 5 has the same meaning as X 5 in the formula (3-1), preferable embodiments thereof are also the same.
  • R 3 and R 4 are independent substituents having heteroatoms in R 1 and R 2 in formula (2-1), which do not have a polymerizable group. It is preferable to have.
  • the preferred embodiment of the substituent having a heteroatom is the same as the preferred embodiment of the substituent having a heteroatom in R 1 and R 2 in the formula (2-1) and not having a polymerizable group. ..
  • the group has at least one of 2- and -NR N- bonded to it.
  • RN is as described above.
  • the aliphatic hydrocarbon group an aliphatic saturated hydrocarbon group having 2 to 30 carbon atoms is preferable, and an aliphatic saturated hydrocarbon group having 2 to 10 carbon atoms is more preferable.
  • a saturated aliphatic hydrocarbon ring group having 6 to 20 ring members is preferable.
  • the aromatic hydrocarbon group an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 12 carbon atoms is preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable.
  • it Z 5 is preferably a group containing an aliphatic hydrocarbon ring group or an aromatic hydrocarbon ring group, a group containing an aromatic hydrocarbon ring group More preferred.
  • Z 5 is preferably represented by ⁇ Ar 0 ⁇ L 0 ⁇ Ar 0 ⁇ from the viewpoint of the flexibility of the obtained cured film.
  • Ar 0 is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group is preferable.
  • L 0 is the same meaning as L A231 in the above formula (A2-3), preferable embodiments thereof are also the same.
  • Z 5 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance.
  • a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.
  • R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a fluoromethyl group. It is a difluoromethyl group or a trifluoromethyl group, and * independently represents a binding site with another structure.
  • the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
  • R 58 and R 59 are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.
  • Z 5 preferably has a structure derived from diamine.
  • diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1,3-diamino.
  • diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/0385898 are also preferable.
  • Diamines having two or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of WO 2017/038598 are also preferably used.
  • Examples of the diamine giving the structure of the above formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, and the like. Examples thereof include 2,2'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.
  • diamines can also be preferably used.
  • a diamine having a siloxane structure such as bis (3-aminopropyl) tetramethyldisiloxane or bis (paraaminophenyl) octamethylpentasiloxane may be used as the diamine component. Good.
  • X 6 has the same meaning as X 6 in the formula (3-2), preferable embodiments thereof are also the same.
  • Z 6 has the same meaning as Z 5 in formula (6-1), and the preferred embodiment is also the same.
  • X 7 and X 8 have the same meanings as X 7 and X 8 in the formula (3-3), preferable embodiments thereof are also the same.
  • Z 7 and Z 8 are independently synonymous with Z 5 in formula (6-1), and the preferred embodiment is also the same.
  • X 7 and X 8 have the same meanings as X 7 and X 8 in the formula (3-4), preferable embodiments thereof are also the same.
  • Z 7 and Z 8 are independently synonymous with Z 5 in formula (6-1), and the preferred embodiment is also the same.
  • R 5 and R 6 are independently synonymous with R 3 and R 4 in formula (6-1), and the preferred embodiments are also the same.
  • a repeating unit represented by the following formula (PAI-1) may be further included.
  • the repeating unit corresponding to the above formula (5-1) does not correspond to the repeating unit represented by the formula (PAI-1).
  • R 116 represents a divalent organic group and R 111 represents a divalent organic group.
  • R 116 is composed of a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a single bond or a linking group.
  • Examples of the linked groups are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
  • the aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable.
  • a group in which two or more of the above are combined is more preferable.
  • a group is preferable, and an —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
  • 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.
  • 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.
  • halogen atom in the halogenated alkylene group examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
  • preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
  • arylene 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 further preferable.
  • R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
  • a compound having two carboxy groups is referred to as a dicarboxylic acid compound
  • a compound having two halogenated carboxy groups is referred to as a dicarboxylic acid dihalide compound.
  • the carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
  • Examples of the halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include aciddihalide compounds. Only one kind or two or more kinds of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used.
  • the dicarboxylic acid compound or the dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic fat having 3 to 20 carbon atoms.
  • a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms is preferable.
  • a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferable.
  • dicarboxylic acid compound examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-.
  • R 111 has the same meaning as Z 1 in the above formula (3-1), and the preferred embodiment is also the same.
  • the content of the other repeating units is preferably 0.1 to 40% by mass, preferably 5 to 30% by mass, based on the total mass of the specific resin. More preferred.
  • the specific resin may be in a mode that does not substantially contain other repeating units.
  • the content of the other repeating unit is preferably 20% by mass or less, preferably 10% by mass or less, and preferably 5% by mass or less, based on the total mass of the specific resin. It is more preferably 1% by mass or less.
  • the lower limit of the content is not particularly limited and may be 0% by mass.
  • the specific resin may contain only one type of other repeating unit, or may contain two or more types of other repeating units having different structures. When two or more other repeating units are included, the total content of the other repeating units is preferably within the above range.
  • the specific resin is preferably in any of the following embodiments (1) to (5).
  • (1) The repeating unit represented by the formula (3-1) and the repeating unit represented by the formula (4-1) are included.
  • the repeating unit represented by the formula (3-2) and the repeating unit represented by the formula (4-2) are included.
  • (3) The repeating unit represented by the formula (3-3) and the repeating unit represented by the formula (4-3) are included.
  • (4) The repeating unit represented by the formula (3-4) and the repeating unit represented by the formula (4-4) are included.
  • the specific resin may further contain other repeating units.
  • the specific resin may further contain a repeating unit represented by the formula (5-1).
  • the total content of the repeating unit represented by the formula (3-1) and the repeating unit represented by the formula (4-1) with respect to the total mass of the specific resin is 50% by mass or more. It is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the total content is not particularly limited and may be 100% by mass.
  • the specific resin may further contain other repeating units.
  • the specific resin further includes at least one selected from the group consisting of the repeating unit represented by the formula (3-1) and the repeating unit represented by the formula (4-1). It may be included.
  • the specific resin may further contain a repeating unit represented by the formula (5-1).
  • the total content of the repeating unit represented by the formula (3-2) and the repeating unit represented by the formula (4-2) with respect to the total mass of the specific resin is 50% by mass or more. It is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the total content is not particularly limited and may be 100% by mass.
  • the specific resin may further contain other repeating units.
  • the specific resin further includes at least one selected from the group consisting of the repeating unit represented by the formula (3-4) and the repeating unit represented by the formula (4-4). It may be included.
  • the specific resin may further contain a repeating unit represented by the formula (5-1).
  • the total content of the repeating unit represented by the formula (3-3) and the repeating unit represented by the formula (4-3) with respect to the total mass of the specific resin is 50% by mass or more. It is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the total content is not particularly limited and may be 100% by mass.
  • the specific resin may further contain other repeating units.
  • the specific resin may further contain a repeating unit represented by the formula (5-1).
  • the total content of the repeating unit represented by the formula (3-4) and the repeating unit represented by the formula (4-4) with respect to the total mass of the specific resin is 50% by mass or more. It is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the total content is not particularly limited and may be 100% by mass.
  • the specific resin may further contain other repeating units.
  • the total content of the repeating unit represented by the formula (3-4) and the repeating unit represented by the formula (5-1) is preferably 50% by mass or more, preferably 60% by mass or more. More preferably, it is more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the total content is not particularly limited and may be 100% by mass.
  • the terminal of the specific resin is not particularly limited, but in order to improve the storage stability of the composition, the terminal is an end-capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. It may be sealed with.
  • end-capping agents it is preferable to use monoamines.
  • monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-.
  • the content of the specific resin in the curable resin composition of the present invention is 20% by mass or more with respect to the total solid content of the curable resin composition from the viewpoint of improving the breaking elongation of the obtained cured film. It is preferably 30% by mass or more, more preferably 40% by mass or more.
  • the upper limit of the content is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass, from the viewpoint of improving the resolution of the curable resin composition. It is more preferably less than or equal to 97% by mass or less, and even more preferably 95% by mass or less.
  • the weight average molecular weight (Mw) of the specific resin is preferably 2,000 to 500,000, more preferably 5,000 to 200,000, and further preferably 10,000 to 100,000. preferable.
  • the number average molecular weight (Mn) of the specific resin is preferably 800 to 250,000, more preferably 2,000 to 100,000, and even more preferably 4,000 to 50,000.
  • the degree of dispersion of the molecular weight of the specific resin is preferably 1.5 to 3.5, more preferably 2 to 3. In the present specification, the degree of molecular weight dispersion means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).
  • the acid value of the specific resin is preferably 0 to 2.0 mmol / g, more preferably 0 to 1.5 mmol / g, and even more preferably 0 to 1.0 mmol / g.
  • the acid value of the specific resin is preferably 1.2 to 7 mmol / g, more preferably 1.5 to 6 mmol / g, 2 It is more preferably ⁇ 5 mmol / g.
  • the acid value refers to the amount (mmol) of acid groups contained in 1 g of the specific resin.
  • the acid group refers to a group neutralized by an alkali having a pH of 12 or higher (for example, sodium hydroxide). Further, the acid group is preferably a group having a pKa of 10 or less. The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992. Examples of the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group and the like, and a carboxy group is preferable.
  • the molar amount of the polymerizable group (polymerizable base value, unit is mmol / g) contained in 1 g of the specific resin is preferably 0.05 to 10 mmol / g, and is 0.1 to 5 mmol / g. Is more preferable.
  • the molar amount of the ethylenically unsaturated bond contained in 1 g of the specific resin is preferably 0.05 to 10 mmol / g, and 0.1 to 0.1 to g. More preferably, it is 5 mmol / g.
  • the molar amount of the polymerizable group contained in 1 g of the specific resin is 0.05 to 10 mmol / g. It is preferably 0.1 to 5 mmol / g, and more preferably 0.1 to 5 mmol / g.
  • Specific examples of the specific resin include the specific resin used in the examples described later.
  • the method for producing the specific resin preferably includes a step (precursor production step) of reacting a diamine with a tetravalent carboxylic acid compound or a derivative thereof and a compound containing an oxazoline ring structure condensed on an aromatic ring. ..
  • diamines used in the precursor production step include diamines represented by the following formula (DA-1).
  • L 21 is synonymous with Z 1 in the formula (3-1), and the preferred embodiment is also the same.
  • the tetravalent carboxylic acid compound used in the precursor production step may be a carboxylic acid dianhydride, or two of the four carboxy groups are modified by esterification, halogenation or the like. It may be a compound having a different structure.
  • R 1 and R 2 in the above formula (2-1) are introduced by the above esterification. Further, it is preferable that the compound in which two of the above four carboxy groups are esterified is halogenated with a halogenating agent and then reacted with a diamine. In addition, the reaction conditions in the precursor production step can be appropriately determined with reference to known esterification conditions.
  • Examples of the compound having an oxazoline ring structure condensed on the aromatic ring used in the precursor production step include a diamine containing an oxazoline ring structure condensed on the aromatic ring or a dicarboxylic acid containing an oxazoline ring structure condensed on the aromatic ring. Acids can be mentioned.
  • the carboxy group in the dicarboxylic acid containing the oxazoline ring structure condensed on the aromatic ring may be a modified carboxylic acid such as halide.
  • Examples of the diamine containing an oxazoline ring structure condensed on an aromatic ring include a compound represented by the following formula (ODA-1).
  • Examples of the dicarboxylic acid containing an oxazoline ring structure condensed on an aromatic ring include a compound represented by the following formula (ODC-1).
  • ODC-1 a compound represented by the following formula (ODC-1) or Formula (ODC-1)
  • Y 1 , Ar 1, Y 2 are each synonymous with Y 1, Ar 1, Y 2 in the formula (1-1), preferred embodiments are also The same is true.
  • R represents -OH or a substituent, and preferably -OH or a halogen atom.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom is preferable.
  • the repeating unit represented by the formula (4-1) is introduced into the specific resin.
  • the repeating unit represented by the formula (5-1) is introduced into the specific resin.
  • the organic solvent may be one kind or two or more kinds.
  • the organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.
  • the precursor manufacturing step preferably includes a step of precipitating a solid.
  • the specific resin in the reaction solution can be precipitated in water, and a polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
  • the method for producing the specific resin is a compound A having two nitro groups, at least one reactive group, and an aromatic hydrocarbon group, a group capable of forming a bond with the reactive group, and a polymerizable group.
  • a step may be included in which the compound B having the above-mentioned compound B is reacted to obtain a compound C to which the compound A and the compound B are bonded, and then the nitro group in the compound C is reduced to obtain a diamine.
  • the diamine obtained in the diamine production process is used as the diamine in the precursor production process.
  • the reactive group in compound A is not particularly limited, and examples thereof include an amino group, a hydroxy group, and a carboxy group.
  • Compound A preferably has a structure in which two nitro groups and at least one reactive group are directly bonded to an aromatic hydrocarbon group.
  • the group capable of forming a bond with the reactive group in the compound B is not particularly limited, and examples thereof include a hydroxy group, a carboxy group, a carboxylic acid halide group, an epoxy group, and an isocyanate group.
  • Examples of the polymerizable group in compound B include the groups exemplified as the group contained in Z 1 in the above formula (3-1).
  • Compound C is a group obtained by reacting compound A with compound B, and is a compound having two nitro groups and a group containing at least one polymerizable group.
  • a diamine compound is obtained by reducing the nitro group in compound C.
  • known methods such as Beshan reduction, hydrogenation reaction using a metal catalyst such as palladium, platinum and nickel and a hydrogen source such as hydrogen gas and ammonium formate, and a reduction method using metal hydride as a reducing agent are used. be able to.
  • the synthesis of the dinitro compound (A-1) in the examples described later is compound C by reacting compound A 3,5-dinitrobenzoyl chloride with compound B 2-hydroxyethyl methacrylate. This is a reaction for obtaining a dinitro compound (A-1).
  • the synthesis of diamine (AA-1) in the examples described later is a reaction of reducing two nitro groups in the dinitro compound (A-1) which is compound C to obtain diamine (AA-1).
  • the method for producing the specific resin is a step of reacting a diamine compound with one carboxylic acid anhydride group and a compound having one carboxy group to obtain a carboxylic acid dianhydride having two or more amide bonds (carboxylic acid).
  • (Dianide production step) may be included.
  • the one carboxy group may be a carboxylic acid halide group.
  • the details of the above reaction may be determined with reference to a known amidation method.
  • the anhydride compound is a compound having AA-1 which is a diamine compound, one carboxylic acid anhydride group, and one carboxylic acid halide group.
  • the method for producing the ring-closed specific resin is a specific resin containing the repeating unit represented by the above formula (1-1) and the repeating unit represented by the formula (2-1), or the formula (1).
  • the imidization step of imidizing the specific resin containing the repeating unit represented by -1) and the repeating unit represented by the formula (2-4) may be included.
  • a specific resin containing the repeating unit represented by the formula (1-1) obtained in the precursor manufacturing step or the like and the repeating unit represented by the formula (2-1), or The specific resin containing the repeating unit represented by the formula (1-1) and the repeating unit represented by the formula (2-4) is imidized to obtain a ring-closed specific resin.
  • the imidization step may be any of thermal imidization (for example, imidization by heating), chemical imidization (for example, imidization using a catalyst), and imidization by a combination thereof, for example, an amine compound. It is carried out by heating in the presence of a catalyst such as.
  • a dehydrating agent may be used. Examples of the dehydrating agent include carboxylic acid anhydrides such as acetic anhydride.
  • the details of imidization can be carried out by a known method.
  • the method for producing the ring-closed specific resin may be a method of synthesizing the resin in one step by heating and dehydrating at a high temperature during the reaction of the carboxylic acid dianhydride and the diamine compound.
  • the carboxylic acid dianhydride include a carboxylic acid dianhydride represented by the above formula (O) and a carboxylic acid dianhydride represented by the above formula (DC-1).
  • the diamine compound a diamine compound represented by the above formula (DA-1) can be used.
  • the method for producing the resin used in the present invention may be a method of synthesizing the resin in one step by decarboxylating at a high temperature during the reaction of the carboxylic acid dianhydride and the diisocyanate compound.
  • the carboxylic acid dianhydride include the carboxylic acid dianhydride represented by the above formula (DC-1).
  • the carboxylic acid dianhydride is preferably a compound obtained in the above-mentioned tetravalent carboxylic acid production step.
  • the diisocyanate compound include compounds in which two amino groups in the compound represented by the above formula (DA-1) are changed to isocyanate groups.
  • known methods for synthesizing polyimide can be referred to.
  • the curable resin composition of the present invention contains a solvent.
  • a solvent a known solvent can be arbitrarily used.
  • the solvent is preferably an organic solvent.
  • the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
  • esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
  • alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)
  • 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
  • 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, ethyl 2-alkyl
  • ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol.
  • Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.
  • ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.
  • aromatic hydrocarbons for example, toluene, xylene, anisole, limonene and the like are preferable.
  • sulfoxides for example, dimethyl sulfoxide is preferable.
  • N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.
  • Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
  • the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
  • the mixed solvent to be mixed is preferable.
  • the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
  • combinations of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, and cyclopentanone and ⁇ -butyrolactone are also preferable.
  • the content of the solvent is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass.
  • the solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
  • the solvent may contain only one type, or may contain two or more types. When two or more kinds of solvents are contained, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a photosensitizer.
  • a photosensitizer a photopolymerization initiator is preferably mentioned.
  • the curable resin composition of the present invention preferably contains a photopolymerization initiator as the photosensitizer.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • the photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators.
  • a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
  • the photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol -1 ⁇ cm -1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). Is preferable.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a known compound can be arbitrarily used as the photoradical polymerization initiator.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like.
  • paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.
  • Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification.
  • KayaCure DETX manufactured by Nippon Kayaku Co., Ltd.
  • Nippon Kayaku Co., Ltd. is also preferably used.
  • a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.
  • IRGACURE 184 (IRGACURE is a registered trademark)
  • DAROCUR 1173 IRGACURE 500, IRGACURE-2959, IRGACURE 127, and IRGACURE 727 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
  • the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
  • acylphosphine-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
  • metallocene compound examples include IRGACURE-784 (manufactured by BASF).
  • the photoradical polymerization initiator is more preferably an oxime compound.
  • the exposure latitude can be improved more effectively.
  • the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
  • the compound described in JP-A-2001-233842 the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
  • Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
  • an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator.
  • IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052).
  • a radical polymerization initiator 2) is also preferably used.
  • TR-PBG-304 manufactured by Changshu Powerful Electronics New Materials Co., Ltd.
  • ADEKA ARCLUDS NCI-831 ADEKA ARCULDS NCI-930
  • DFI-091 manufactured by Daito Chemix Co., Ltd.
  • an oxime compound having the following structure can also be used.
  • an oxime compound having a fluorene ring can also be used.
  • Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081.
  • an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
  • Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
  • an oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
  • Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.
  • the photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl.
  • More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds.
  • At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.
  • the photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone).
  • 2-benzyl such as benzophenone
  • benzoin ether compounds such as benzoin alkyl ether
  • benzoin compounds such as benzoin and alkyl benzoin
  • benzyl derivatives such as benzyl dimethyl ketal.
  • a compound represented by the following formula (I) can also be used.
  • R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like.
  • R I01 is a group represented by formula (II), the same as R I00
  • the groups, R I02 to R I04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.
  • R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
  • the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.
  • the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range.
  • the curable resin composition of the present invention may contain a photoacid generator as a photosensitizer.
  • the photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime.
  • onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime.
  • examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate.
  • the quinone-diazide compounds include a polyhydroxy compound in which quinone-diazide sulfonic acid is ester-bonded, a polyamino compound in which quinone-diazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinone-diazide sulfonic acid is ester-bonded and a sulfonamide bond. Examples thereof include those bonded by at least one of the above. In the present invention, for example, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.
  • the quinone diazide either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used.
  • the 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • the 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
  • a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed.
  • a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.
  • the naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.
  • Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. Be done.
  • Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
  • a commercially available product may be used as the photoacid generator.
  • Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-469, WPAG-638, and WPAG-699. (Manufactured by Kojunyaku Co., Ltd.) and the like.
  • the content thereof is preferably 0.1 to 30% by mass, preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. Is more preferable, and 2 to 15% by mass is further preferable. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.
  • the curable resin composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator may be contained.
  • a thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the specific resin and the polymerizable compound can be allowed to proceed in the heating step described later, so that the chemical resistance can be further improved.
  • thermal radical polymerization initiator examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
  • thermosetting initiator When the thermosetting initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 5 to 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 kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.
  • the curable resin composition of the present invention may contain a thermosetting agent as a polymerization initiator.
  • the thermoacid generator generates an acid by heating, and is at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound, or a specific resin. It has the effect of promoting the cross-linking reaction of methylol groups and the like contained in.
  • the specific resin preferably contains a methylol group or an alkoxymethyl group as a polymerizable group.
  • the thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after applying the curable resin composition to the substrate, and final heating (cure: about 100 to 400) after patterning in subsequent exposure and development. It is preferable to select a thermosetting agent that generates an acid at (° C.)) because it can suppress a decrease in sensitivity during development.
  • the thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak, which is the lowest temperature when the thermoacid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule. Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
  • the acid generated from the thermoacid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane.
  • aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid
  • alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid
  • haloalkyl sulfonic acid such as sulfonic acid is preferable.
  • thermoacid generator include those described in paragraph 0055 of JP2013-072935A.
  • alkylsulfonic acid having 1 to 4 carbon atoms or haloalkylsulfonic acid having 1 to 4 carbon atoms are more preferable, and methanesulfonic acid is more preferable, from the viewpoint that there is little residue in the cured film and it is difficult to deteriorate the physical properties of the cured film.
  • thermoacid generator the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.
  • the content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
  • the content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
  • 0.01 part by mass or more the cross-linking reaction is promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved.
  • 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.
  • the curable resin composition of the present invention preferably contains a polymerizable compound.
  • the compound corresponding to the above-mentioned specific resin does not correspond to a polymerizable compound.
  • a polyfunctional polymerizable compound is preferable.
  • the polyfunctional polymerizable compound means a compound having two or more polymerizable groups. Further, as the polymerizable compound, a radically polymerizable compound is preferable, and a compound having two or more radically polymerizable groups is more preferable.
  • the radically polymerizable compound is a compound having a radically polymerizable group.
  • the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
  • the radically polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
  • the number of radically polymerizable groups contained in the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and preferably has three or more radically polymerizable groups. More preferred.
  • the upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the molecular weight of the radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.
  • the curable resin composition of the present invention preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups, and is preferably a trifunctional or higher functional radical polymerizable compound. It is more preferable to contain at least one kind. Further, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound.
  • the number of functional groups of a bifunctional or higher functional polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.
  • the radically polymerizable compound examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogeno group.
  • Substitution reactions of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
  • a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
  • examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
  • a compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993.
  • Urethane (meth) acrylates such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
  • a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
  • a preferable radically polymerizable compound other than the above it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. It is also possible to use a compound having two or more groups having the above, or a cardo resin.
  • the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a radically polymerizable compound.
  • radically polymerizable compounds examples include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku (commercially available).
  • SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
  • SR-209 which is a bifunctional methacrylate having four ethyleneoxy chains.
  • DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H ( 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 Nichiyu Co., Ltd.), etc. Can be mentioned.
  • Examples of the radically polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765.
  • Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
  • radically polymerizable compound compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. It can also be used.
  • the radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxy group or a phosphoric acid group.
  • the radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
  • a radically polymerizable compound having a group is more preferable.
  • the aliphatic polyhydroxy compound in a radical polymerizable compound in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, is pentaerythritol or dipenta. It is a compound that is erythritol.
  • examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the acid value of the radically polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
  • the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good.
  • the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. The acid value is measured according to the description of JIS K 0070: 1992.
  • a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film.
  • the monofunctional radical polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth).
  • Acrylate derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used.
  • the monofunctional radical polymerizable compound a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure. Further, from the viewpoint of pattern resolution and film elasticity, it is also preferable to use bifunctional metal acrylate or acrylate. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, and polytetraethylene.
  • Glycol diacrylate polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol Dimethacrylate, dimethylol-tricyclodecanediacrylate, dimethylol-tricyclodecanedimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) addition of bisphenol A Diacrylate, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylate having urethane bond, having ure
  • the curable resin composition of the present invention can further contain a polymerizable compound other than the radically polymerizable compound described above.
  • a polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group (methylol group), an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.
  • R 104 represents an organic group having a t-valence of 1 to 200 carbon atoms
  • R 105 is a group represented by -OR 106 or -OCO-R 107.
  • R 106 indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 107 indicates an organic group having 1 to 10 carbon atoms.
  • R 404 represents a divalent organic group having 1 to 200 carbon atoms
  • R 405 represents a group represented by -OR 406 or -OCO-R 407
  • R 406 is a hydrogen atom or carbon.
  • R 407 indicates an organic group having 1 to 10 carbon atoms.
  • u represents an integer of 3 to 8
  • R 504 represents a u-valent organic group having 1 to 200 carbon atoms
  • R 505 represents a group represented by -OR 506 or -OCO-R 507.
  • R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 507 represents an organic group having 1 to 10 carbon atoms.
  • Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML.
  • Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, and the like.
  • HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), NIKALAC MX-280, Examples thereof include NIKALAC MX-270 and NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.
  • the epoxy compound preferably contains a polyethylene oxide group.
  • 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.
  • epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidi).
  • Roxypropyl) Epoxy group-containing silicone such as siloxane, epoxy resin which is an isocyanuric acid derivative such as glycidyl isocyanurate, and epoxy which is a glycol uryl derivative such as N, N', N'', N'''-tetraglycidyl glycol uryl. Resin and the like can be mentioned, but the present invention is not limited to these.
  • the above-mentioned isocyanuric acid derivative or glycoluril derivative is preferable. It is presumed that this is because an aprotic and highly polar structure such as an isocyanul ring structure and a ring structure such as a glycoluryl structure is effective for chemical resistance.
  • an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
  • an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
  • Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain polyethylene oxide groups.
  • oxetane compound compound having an oxetanyl group
  • the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and the like.
  • examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like.
  • the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or Two or more kinds may be mixed.
  • benzoxazine compound are BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly.
  • examples thereof include a benzoxazine adduct of a hydroxystyrene resin and a phenol novolac type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.
  • the content of the polymerizable compound is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
  • One type of polymerizable compound may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.
  • the curable resin composition of the present invention may contain another resin (hereinafter, also simply referred to as “other resin”) different from the above-mentioned specific resin.
  • other resins include a polyimide different from the specific resin, a polyimide precursor different from the specific resin, polysiloxane, a resin containing a siloxane structure, an epoxy resin, an acrylic resin, and the like.
  • a composition having excellent coatability can be obtained, and a cured film having excellent chemical resistance can be obtained.
  • the composition is formed by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the polymerizable compound described later or in addition to the polymerizable compound described later. It is possible to improve the coatability of an object, the chemical resistance of a cured film, and the like.
  • the polyimide which is another resin, contains a repeating unit represented by the above formula (4).
  • the repeating unit represented by the formula (4) may be one kind, but may be two or more kinds. Further, the polyimide may contain other types of repeating units in addition to the repeating unit of the above formula (4).
  • a polyimide precursor in which 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units is the repeating unit represented by the formula (4) is exemplified. Will be done. As an upper limit, 100 mol% or less is practical.
  • the weight average molecular weight (Mw) of the polyimide is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
  • the degree of dispersion of the molecular weight of polyimide is preferably 1.5 to 3.5, more preferably 2 to 3.
  • Polyimide can be obtained, for example, by cyclizing a polyimide precursor, which is another resin described later, by heating or the like.
  • the polyimide precursor preferably contains a repeating unit represented by the above formula (1).
  • the repeating unit represented by the formula (1) may be one kind, but may be two or more kinds. Further, the structural isomer of the repeating unit represented by the formula (1) may be contained. Further, the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (1).
  • the polyimide precursor in the present invention 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
  • the degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the polyimide precursor is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
  • the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
  • the organic solvent may be one kind or two or more kinds.
  • the organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
  • the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
  • the content of the other resin is preferably 0.01% by mass or more with respect to the total solid content of the curable resin composition. It is more preferably 05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and 10% by mass or more. It is even more preferable to have.
  • the content of the other resin in the curable resin composition of the present invention is preferably 80% by mass or less, and preferably 75% by mass or less, based on the total solid content of the curable resin composition. It is more preferably 70% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the content of other resins may be low.
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, based on the total solid content of the curable resin composition. It is more preferably 5% by mass or less, and even more preferably 1% by mass or less.
  • the lower limit of the content is not particularly limited, and may be 0% by mass or more.
  • the curable resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains an onium salt.
  • the curable resin composition contains a resin containing a repeating unit represented by the formula (2-1) or a repeating unit represented by the formula (2-4) as a specific resin
  • the curable resin composition is thermally. It preferably contains a base generator.
  • the type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
  • an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability
  • a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.
  • the onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond. .. That is, the onium salt may be an intramolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are different molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
  • an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.
  • the onium salt used in the present invention may be a thermobase generator.
  • the thermal base generator refers to a compound that generates a base by heating, and examples thereof include an acidic compound that generates a base when heated to 40 ° C. or higher.
  • ammonium salt means a salt of an ammonium cation and an anion.
  • R 1 to R 4 each independently represent a hydrogen atom or a hydrocarbon group, and at least two of R 1 to R 4 may be bonded to each other to form a ring.
  • R 1 to R 4 are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or 6 to 6 carbon atoms. It is more preferably 12 aryl groups.
  • R 1 to R 4 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group.
  • the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.
  • the ammonium cation is preferably represented by any of the following formulas (Y1-1) and (Y1-2).
  • R 101 represents an n-valent organic group
  • R 1 has the same meaning as R 1 in the formula (101)
  • Ar 101 and Ar 102 are each independently , Represents an aryl group
  • n represents an integer of 1 or more.
  • R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
  • n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • Ar 101 and Ar 102 are preferably phenyl groups or naphthyl groups, respectively, and more preferably phenyl groups.
  • the anion in the ammonium salt one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfuric acid anion is preferable, and a carboxylic acid anion is more preferable because both salt stability and thermodegradability can be achieved.
  • the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
  • the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion.
  • the stability, curability and developability of the curable resin composition can be further improved.
  • the stability, curability and developability of the curable resin composition can be further improved.
  • the carboxylic acid anion is preferably represented by the following formula (X1).
  • EWG represents an electron-attracting group.
  • the electron-attracting group means that Hammett's substituent constant ⁇ m shows a positive value.
  • ⁇ m is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642.
  • the EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
  • R x1 to R x3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxy group, and Ar is an aromatic group. Represents.
  • the carboxylic acid anion is preferably represented by the following formula (XA).
  • L 10 represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR X - represents and divalent connecting group selected from the group consisting a combination thereof, R X is , Hydrogen atom, alkyl group, alkenyl group or aryl group.
  • carboxylic acid anion examples include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion.
  • the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt is used as an anion.
  • the lower limit of pKa is not particularly limited, but it is preferably -3 or more, and preferably -2 or more, from the viewpoint that the generated base is difficult to neutralize and the cyclization efficiency of the specific resin or the like is improved. Is more preferable.
  • the above pKa includes Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, F. See Nachod, F.C .; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 19). Can be done. For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.
  • ammonium salt examples include the following compounds, but the present invention is not limited thereto.
  • the iminium salt means a salt of an iminium cation and an anion.
  • the anion include the same as the anion in the above-mentioned ammonium salt, and the preferred embodiment is also the same.
  • a pyridinium cation is preferable.
  • a cation represented by the following formula (102) is also preferable.
  • R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group
  • R 7 represents a hydrocarbon group
  • at least two of R 5 to R 7 are bonded to each other to form a ring. It may be formed.
  • R 5 and R 6 are synonymous with R 1 to R 4 in the above formula (101), and the preferred embodiment is also the same.
  • R 7 preferably combines with at least one of R 5 and R 6 to form a ring.
  • the ring may contain a heteroatom. Examples of the hetero atom include a nitrogen atom. Further, as the ring, a pyridine ring is preferable.
  • the iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).
  • R 101 represents an n-valent organic group
  • R 5 has the same meaning as R 5 in the formula (102)
  • R 7 is R in the formula (102) Synonymous with 7
  • n represents an integer of 1 or more
  • m represents an integer of 0 or more.
  • R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms.
  • n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.
  • iminium salt examples include the following compounds, but the present invention is not limited thereto.
  • the sulfonium salt means a salt of a sulfonium cation and an anion.
  • the anion include the same as the anion in the above-mentioned ammonium salt, and the preferred embodiment is also the same.
  • sulfonium cation a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable. Further, as the sulfonium cation, a cation represented by the following formula (103) is preferable.
  • R 8 to R 10 each independently represent a hydrocarbon group.
  • R 8 to R 10 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 8 to R 10 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have 10 alkoxy groups.
  • R 8 to R 10 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • the iodonium salt means a salt of an iodonium cation and an anion.
  • the anion include the same as the anion in the above-mentioned ammonium salt, and the preferred embodiment is also the same.
  • iodonium cation a diaryl iodonium cation is preferable. Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.
  • R 11 and R 12 each independently represent a hydrocarbon group.
  • R 11 and R 12 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • R 11 and R 12 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • the phosphonium salt means a salt of a phosphonium cation and an anion.
  • the anion include the same as the anion in the above-mentioned ammonium salt, and the preferred embodiment is also the same.
  • a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation. Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.
  • R 13 to R 16 each independently represent a hydrogen atom or a hydrocarbon group.
  • Each of R 13 to R 16 is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 13 to R 16 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • R 13 to R 16 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
  • the onium salt one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention may contain a thermosetting agent.
  • the curable resin composition when the curable resin composition contains a resin containing a repeating unit represented by the formula (2-1) or a repeating unit represented by the formula (2-4) as a specific resin, the curable resin composition is thermally. It preferably contains a base generator.
  • the thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt. Examples of other thermobase generators include nonionic thermobase generators. Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).
  • Rb 1 , Rb 2 and Rb 3 are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Further, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
  • the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.
  • Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure.
  • the cyclic structure may be either a monocyclic ring or a condensed ring, and a fused ring in which two monocyclic rings or two monocyclic rings are condensed is preferable.
  • the single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring.
  • a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
  • Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have substituents as long as the effects of the present invention are exhibited. Rb 1 and Rb 2 may be coupled to each other to form a ring.
  • Rb 1 and Rb 2 are particularly linear, branched, or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
  • a cyclohexyl group which may be used is more preferable.
  • an alkyl group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6.
  • alkoxy group (2 to 24 carbon atoms are preferable, 2 to 12 is more preferable, 2 to 6 is more preferable
  • arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable).
  • an arylalkenyl group (8 to 24 carbon atoms is preferable, 8 to 20 is more preferable, 8 to 16 is more preferable), and an alkoxyl group (1 to 24 carbon atoms is preferable, 2 to 2 to 24).
  • 18 is more preferable, 3 to 12 is more preferable), an aryloxy group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), or an arylalkyloxy group (7 to 12 carbon atoms is more preferable).
  • 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
  • a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable.
  • Rb 3 may further have a substituent as long as the effect of the present invention is exhibited.
  • the compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
  • Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
  • Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effects of the present invention are exhibited. Of these, Rb 13 is preferably an arylalkyl group.
  • Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
  • Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
  • 2 to 8 are more preferable, 2 to 3 are more preferable
  • aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable
  • 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.
  • Rb 35 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.
  • the compound represented by the formula (B1-1) is also preferable.
  • Rb 11 and Rb 12 have the same meanings as Rb 11 and Rb 12 in the formula (B1-1).
  • Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, 7).
  • Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
  • the molecular weight of the nonionic thermobase 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.
  • the following compounds can be mentioned as specific examples of the compound which is a thermal base generator or other specific examples of the thermal base generator.
  • the content of the thermosetting agent is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
  • the thermobase generator one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
  • the photosensitive resin composition of the present invention was selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure. It is preferable to further contain at least one compound. In particular, at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (2-2) and the repeating unit represented by the formula (2-3) as the specific resin in the curable resin composition. When the specific resin containing the above is contained, it is preferable to further contain at least one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure.
  • the sulfonamide structure is a structure represented by the following formula (S-1).
  • R represents a hydrogen atom or an organic group
  • R may be bonded to another structure to form a ring structure
  • * may independently form a binding site with another structure.
  • the R is preferably the same group as R 2 in the following formula (S-2).
  • the compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, but a compound having one sulfonamide structure is preferable.
  • the compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group, and two or more of R 1 , R 2 and R 3 are bonded to each other. It may form a ring structure. It is preferable that R 1 , R 2 and R 3 are independently monovalent organic groups.
  • R 1 , R 2 and R 3 are hydrogen atoms, or alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxy groups, Examples thereof include a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
  • the alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
  • a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable.
  • examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
  • an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
  • As the alkoxysilyl group an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable.
  • Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
  • aryl group an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable.
  • the aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
  • heterocyclic group examples include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isooxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a pyrimidine ring.
  • R 1 is an aryl group and R 2 and R 3 are independently hydrogen atoms or alkyl groups are preferable.
  • Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanylamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1.
  • the thiourea structure is a structure represented by the following formula (T-1).
  • R 4 and R 5 each independently represent a hydrogen atom or a monovalent organic group, and R 4 and R 5 may be combined to form a ring structure, where R 4 is.
  • the ring structure may be formed by combining with other structures to which * is bonded, R 5 may be combined with other structures to which * is bonded to form a ring structure, and * may be independently and others. Represents the site of connection with the structure of.
  • R 4 and R 5 are independently hydrogen atoms.
  • R 4 and R 5 include a hydrogen atom, 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 carboxy group, and a carbonyl group.
  • examples thereof include an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these are combined.
  • the alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 6 carbon atoms is more preferable.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group and the like.
  • a cycloalkyl group having 5 to 10 carbon atoms is preferable, and a cycloalkyl group having 6 to 10 carbon atoms is more preferable.
  • examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
  • an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group and the like.
  • As the alkoxysilyl group an alkoxysilyl group having 1 to 10 carbon atoms is preferable, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferable.
  • Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group.
  • aryl group an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 12 carbon atoms is more preferable.
  • the aryl group may have a substituent such as an alkyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group and a naphthyl group.
  • heterocyclic group examples include a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isooxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a pyrimidine ring.
  • the compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferable.
  • the compound having a thiourea structure is preferably a compound represented by the following formula (T-2).
  • R 4 to R 7 each independently represent a hydrogen atom or a monovalent organic group, and at least two of R 4 to R 7 are bonded to each other to form a ring structure. You may.
  • R 4 and R 5 have the same meanings as R 4 and R 5 in formula (T-1), a preferable embodiment thereof is also the same.
  • R 6 and R 7 are independently monovalent organic groups.
  • the preferred embodiment of the monovalent organic group in R 6 and R 7 is the same as the preferred embodiment of the monovalent organic group in R 4 and R 5 in the formula (T-1). ..
  • Examples of compounds having a thiourea structure include N-acetylthiourea, N-allyl thiourea, N-allyl-N'-(2-hydroxyethyl) thiourea, 1-adamantyl thiourea, N-benzoyl thiourea, N, N'-.
  • Diphenylthiourea 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1- (3- (trimethoxysilyl) propyl) -3-methylthiourea, trimethyl Examples thereof include thiourea, tetramethylthiourea, N, N-diphenylthiourea, ethylenethiourea (2-imidazolinthione), carbimazole, and 1,3-dimethyl-2-thiohydranthin.
  • the total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10% by mass, preferably 0.1 to 5% by mass, based on the total mass of the photosensitive resin composition of the present invention. It is more preferably%, and further preferably 0.2 to 3% by mass.
  • the photosensitive resin composition of the present invention may contain only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more compounds. When only one type is contained, the content of the compound is preferably within the above range, and when two or more types are contained, the total amount thereof is preferably within the above range.
  • the curable resin composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the curable resin composition layer.
  • the migration inhibitor is not particularly limited, but heterocycles (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isooxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
  • triazole-based compounds such as 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole and 4-methylbenzotriazole, and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
  • an ion trap agent that traps anions such as halogen ions can also be used.
  • Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656.
  • the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.
  • the migration inhibitor include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the curable resin composition, and is 0. It is more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass.
  • the migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a polymerization inhibitor.
  • polymerization inhibitor examples include hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, and diphenyl-p-benzoquinone.
  • the content of the polymerization inhibitor is 0.01 to 20.0% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass.
  • the polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
  • a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
  • the metal adhesion improver include silane coupling agents, aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, ⁇ -ketoester compounds, amino compounds, etc. Can be mentioned.
  • silane coupling agent examples include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992.
  • Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent.
  • Et represents an ethyl group.
  • silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid.
  • aluminum-based adhesive aid examples include aluminum tris (ethylacetate acetate), aluminum tris (acetylacetoneate), ethylacetacetate aluminum diisopropirate, and the like.
  • the content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass.
  • the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention contains various additives such as a sensitizer such as N-phenyldiethanolamine, a photobase generator, a chain transfer agent, a surfactant, a higher fatty acid derivative, and an inorganic substance, if necessary. Particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregating agents and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.
  • the curable resin composition of the present invention may contain a sensitizer.
  • the sensitizer absorbs specific active radiation and becomes an electron-excited state.
  • the sensitizer in the electron-excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur.
  • the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
  • the sensitizer include sensitizers such as N-phenyldiethanolamine.
  • sensitizing dye As a sensitizer, you may use a sensitizing dye as a sensitizer.
  • the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.
  • the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass.
  • the sensitizer may be used alone or in combination of two or more.
  • the curable resin composition of the present invention may contain a chain transfer agent.
  • Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pp. 683-684.
  • As the chain transfer agent for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
  • a thiol compound can be preferably used.
  • the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention.
  • 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable.
  • the chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total amount is preferably in the above range.
  • Each type of surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability.
  • the surfactant various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used.
  • the following surfactants are also preferable.
  • the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit
  • the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.
  • the surfactant the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
  • fluorine-based surfactant examples include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479.
  • F482, F554, F780, RS-72-K above, manufactured by DIC Co., Ltd.
  • Florard FC430, FC431, FC171, Novec FC4430, FC4432 aboveve, manufactured by 3M Japan Ltd.
  • Surfron S-382 SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (above, Asahi Glass Co., Ltd.) ), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like.
  • the fluorine-based surfactant As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327 and the compounds described in paragraphs 0117 to 0132 of JP2011-132503 can also be used.
  • a block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant.
  • Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, such as Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. Can be mentioned.
  • 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 uniformity of coating film thickness and liquid saving property, and has good solubility in the composition.
  • silicone-based surfactant examples include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.).
  • TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Co., Ltd.), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.
  • hydrocarbon-based surfactant examples include Pionin A-76, New Calgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 manufactured by Yusho Co., Ltd.
  • anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
  • the content of the surfactant is 0.001 to 2.0% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass.
  • the surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total amount is preferably in the above range.
  • the curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.
  • a higher fatty acid derivative such as behenic acid or behenic acid amide
  • the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the curable resin composition of the present invention. Is preferable.
  • the higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total amount is preferably in the above range.
  • the resin composition of the present invention may contain inorganic particles.
  • specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
  • the average particle size of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, further preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferable.
  • the mechanical properties of the cured film may deteriorate.
  • the average particle size of the inorganic particles exceeds 2.0 ⁇ m, the resolution may decrease due to scattering of exposure light.
  • the composition of the present invention may contain an ultraviolet absorber.
  • an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
  • salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like
  • benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-.
  • Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxy-4-octoxybenzophenone and the like can be mentioned.
  • benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3).
  • 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, examples of triazine-based ultraviolet absorbers include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl).
  • the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
  • the composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
  • the resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
  • Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
  • Specific examples of the organic titanium compound are shown in I) to VII) below:
  • I) Titanium chelate compound Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the negative photosensitive resin composition has good storage stability and a good curing pattern can be obtained.
  • Specific examples are titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanionate, titanium diisopropoxyside bis (2,4-pentanionate)).
  • Titanium diisopropoxyside bis titanium diisopropoxyside bis (etramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
  • Titanium Alkoxy Titanium Compounds For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxide), Titanium Tetraisobutoxide, Titanium Tetraisopropoxyside, Titanium Tetramethoxide.
  • Titanium Tetramethoxypropoxyside Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis ⁇ 2,2- (Aryloxymethyl) Butokiside ⁇ ] etc.
  • Titanocene compounds for example, pentamethylcyclopentadienyl titanium trimethoxide, bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis ( ⁇ 5-2, 2).
  • Titanium oxide compound For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
  • Titanium tetraacetylacetone compound For example, titanium tetraacetylacetone.
  • Titanate Coupling Agent For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
  • the organic titanium compound at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound has better chemical resistance. It is preferable from the viewpoint of playing.
  • -Pyrrole-1-yl) phenyl) titanium is preferred.
  • 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 precursor of the cyclized resin. ..
  • the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition is excellent.
  • the composition of the present invention may contain an antioxidant.
  • an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material.
  • the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like.
  • the phenol compound any phenol compound known as a phenolic antioxidant can be used.
  • Preferred phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
  • a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
  • a phosphorus-based antioxidant can also be preferably used.
  • a phosphorus-based antioxidant tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like.
  • antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like.
  • the antioxidant the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used.
  • the composition of the present invention may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound whose site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound in which the protecting group is eliminated and functions as an antioxidant can be mentioned.
  • Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
  • Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like.
  • preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds represented by the general formula (3).
  • R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms
  • R6 represents an alkylene group having 2 or more carbon atoms
  • R7 represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom
  • k represents an integer of 1 to 4.
  • the compound represented by the general formula (3) suppresses oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin.
  • metal oxidation can be suppressed by the rust preventive action on the metal material.
  • k is more preferably an integer of 2 to 4.
  • R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-.
  • R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-.
  • Examples thereof include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent.
  • alkyl ether and -NH- from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is more preferable from the viewpoint of metal adhesion due to interaction with resin and metal complex formation. preferable.
  • Examples of the compound represented by the following general formula (3) include the following, but the compound is not limited to the following structure.
  • the amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin. If the amount added is less than 0.1 parts by mass, it is difficult to obtain the effect of improving the elongation characteristics after reliability and the adhesion to the metal material, and if it is more than 10 parts by mass, it is due to the interaction with the photosensitizer. , There is a risk of lowering the sensitivity of the resin composition. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
  • the water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.
  • Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.
  • the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties.
  • the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.
  • a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention.
  • Methods such as filtering the raw materials constituting the curable resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.
  • the curable resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
  • the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
  • ion exchange treatment and the like are preferably mentioned.
  • a conventionally known storage container can be used as the storage container for the curable resin composition of the present invention.
  • a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a layered bottle. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
  • the curable resin composition of the present invention can be prepared by mixing each of the above components.
  • the mixing method is not particularly limited, and a conventionally known method can be used.
  • the filter pore diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less. On the other hand, from the viewpoint of productivity, 5 ⁇ m or less is preferable, 3 ⁇ m or less is more preferable, and 1 ⁇ m or less is further preferable.
  • the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel.
  • filters having different pore diameters or materials may be used in combination.
  • various materials may be filtered a plurality of times.
  • circulation filtration may be used.
  • you may pressurize and perform filtration.
  • the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
  • 0.01 MPa or more and 1.0 MPa or less is preferable, 0.03 MPa or more and 0.9 MPa or less is more preferable, and 0.05 MPa or more and 0.7 MPa or less is further preferable.
  • impurities may be removed using an adsorbent.
  • Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • the curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
  • the cured film of the present invention is obtained by curing the curable resin composition of the present invention.
  • the film thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, or 1 ⁇ m or more. Further, the upper limit value can be 100 ⁇ m or less, and can be 30 ⁇ m or less.
  • the cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body.
  • the laminate of the present invention is preferably a laminate having two or more cured films and a metal layer between the cured films. Further, it is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films.
  • a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable.
  • the first cured film and the second cured film are both cured films of the present invention. For example, both the first cured film and the second cured film are curable of the present invention.
  • a preferred embodiment is a film obtained by curing the resin composition.
  • the curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film have the same composition.
  • the compositions may be present or have different compositions, but from the viewpoint of production suitability, the compositions having the same composition are preferable.
  • Such a metal layer is preferably used as a metal wiring such as a rewiring layer.
  • Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
  • Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above.
  • the cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially in microelectronics.
  • the method for producing a cured film of the present invention includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film. Is preferable. Further, the method for producing a cured film of the present invention further includes the film forming step, and further includes an exposure step for exposing the film and a developing step for developing the film (developing the film). Is more preferable. Further, the method for producing a cured film of the present invention includes the film forming step (and the developing step if necessary), and further includes a heating step of heating the film at 50 to 450 ° C. preferable.
  • Exposure step of exposing the film after the film forming step (c) Exposure Development step of developing the developed film
  • the method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention.
  • the method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after forming the cured film according to the above-mentioned method for producing the cured film. )-(D).
  • a laminated body can be obtained.
  • the production method includes a film forming step (layer forming step) in which the curable resin composition is applied to a substrate to form a film (layered).
  • the type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like. Further, these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable.
  • a plate-shaped base material for example, a plate-shaped base material (board) is used.
  • the shape of the base material is not particularly limited, and may be circular or rectangular, but is preferably rectangular.
  • These substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
  • HMDS hexamethyldisilazane
  • the size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
  • the resin layer or the metal layer serves as a base material.
  • Coating is preferable as a means for applying the curable resin composition to the base material.
  • the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method.
  • the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable.
  • a resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method.
  • the coating method can be appropriately selected depending on the shape of the substrate.
  • the spin coating method for circular substrates such as wafers, the spin coating method, spray coating method, inkjet method, etc. are preferable, and for rectangular substrates, the slit coating method or spray coating The method, the inkjet method and the like are preferable.
  • the spin coating method for example, it can be applied at a rotation speed of 500 to 2,000 rpm (revolutions per minute) for about 10 seconds to 1 minute.
  • a rotation speed for 10 to 180 seconds.
  • a plurality of rotation speeds can be combined and applied.
  • a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate can be preferably used in the present invention.
  • a step of removing the excess film at the edge of the base material may be performed. Examples of such a process include edge bead rinse (EBR), air knife, back rinse and the like.
  • EBR edge bead rinse
  • a pre-wetting step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
  • the production method of the present invention may include a step of forming the film (curable resin composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent.
  • the preferred drying temperature is 50 to 150 ° C., more preferably 70 ° C. to 130 ° C., still more preferably 90 ° C. to 110 ° C.
  • the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
  • the production method of the present invention may include an exposure step of exposing the film (curable resin composition layer).
  • the amount of exposure is not particularly determined as long as the curable resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ /. It is more preferable to irradiate with cm 2.
  • the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
  • the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h.
  • the curable resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays.
  • a broad (three wavelengths of g, h, and i rays) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.
  • the production method of the present invention may include a developing step of performing a developing process on the exposed film (curable resin composition layer). By developing, the unexposed portion (non-exposed portion) is removed.
  • the developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection of a developing solution from a nozzle, spray spraying, immersion of a developing solution in a base material, and the like, and ejection from a nozzle is preferably used.
  • the developing steps include a step in which the developer is continuously supplied to the base material, a step in which the developer is kept in a substantially stationary state on the base material, a step in which the developer is vibrated by ultrasonic waves or the like, and a combination thereof. Processes can be adopted.
  • the curable resin composition is a negative type curable resin composition
  • the developing solution is such that the unexposed portion (non-exposed portion) of the curable resin composition layer is removed, which is the curability of the present invention.
  • the resin composition is a positive curable resin composition, those from which the exposed portion (exposed portion) is removed can be used without particular limitation.
  • alkaline development the case where an alkaline developer is used as the developer
  • solvent development a developer containing 50% by mass or more of an organic solvent
  • the content of the organic solvent in the developing solution is preferably 10% by mass or less, more preferably 5% by mass or less, and 1% by mass or less with respect to the total mass of the developing solution. Is more preferable, and it is particularly preferable that the organic solvent is not contained.
  • the developing solution in alkaline development is more preferably an aqueous solution having a pH of 9 to 14.
  • Examples of the alkaline compound contained in the developing solution in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicate. Examples include potassium silicate, ammonia or amine.
  • amines examples include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide.
  • TMAH tetraethylammonium hydroxide
  • tetrabutylammonium hydroxide an alkaline compound containing no metal is preferable, and an ammonium compound is more preferable.
  • the alkaline compound may be only one kind or two or more kinds.
  • the content of the basic compound in the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass in the total mass of the developing solution. Is more preferable.
  • the developer contains 90% or more of an organic solvent.
  • the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3.
  • the ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
  • organic solvent examples include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
  • alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)
  • 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • Ke As tons for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc.
  • Dimethyl sulfoxide is preferably mentioned as the sulfoxides.
  • cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
  • the developing solution contains an organic solvent, one kind or a mixture of two or more kinds of organic solvents can be used.
  • the developer may further contain other components. Examples of other components include known surfactants and known defoamers.
  • the developer preferably has 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.
  • the method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the developer, the method of supplying the developer on the base material using a nozzle, paddle development, or continuous development. There is a way to supply.
  • the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoint of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developer with a straight nozzle or the method of continuously supplying the developer with a spray nozzle is preferable, and the developer is supplied to the image area.
  • the method of supplying with a spray nozzle is more preferable. Further, after the developing solution is continuously supplied by the straight nozzle, the base material is spun to remove the developing solution from the base material, and after spin drying, the developing solution is continuously supplied by the straight nozzle again, and then the base material is spun to use the developing solution as the base material. A step of removing from the top may be adopted, and this step may be repeated a plurality of times. Further, as a method of supplying the developer in the developing process, a step in which the developer is continuously supplied to the base material, a step in which the developer is kept in a substantially stationary state on the base material, and a step in which the developer is superposed on the base material. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.
  • the development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes.
  • the temperature of the developing solution at the time of development is not particularly specified, but it can be usually 10 to 45 ° C, preferably 20 to 40 ° C.
  • rinsing is preferably performed using an organic solvent different from the developing solution.
  • examples of the rinsing liquid in the case of solvent development include PGMEA (propylene glycol monomethyl ether acetate), IPA (isopropanol) and the like, and PGMEA is preferable.
  • rinsing is preferably performed using pure water.
  • the rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, still more preferably 5 seconds to 1 minute.
  • the temperature of the rinsing liquid at the time of rinsing is not particularly specified, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
  • Examples of the organic solvent when the rinsing solution contains an organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate.
  • alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid) E
  • toluene, xylene, anisole, limonene and the like dimethyl sulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene as alcohols.
  • glycols and the like and amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
  • the rinsing liquid contains an organic solvent
  • one type or a mixture of two or more types of organic solvent can be used.
  • cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferable, cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA and PGME are more preferable, and cyclohexanone and PGMEA are more preferable. More preferred.
  • the rinsing liquid contains an organic solvent
  • 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable.
  • the rinse liquid may be 100% by mass of an organic solvent.
  • the rinse solution may further contain other components.
  • other components include known surfactants and known defoamers.
  • the method of supplying the rinse liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinse liquid, the paddle development on the base material, the method of supplying the rinse liquid to the base material by a shower, and the base material.
  • the method of supplying with a spray nozzle is more preferable.
  • the type of 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 the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
  • a step of continuously supplying the rinse liquid to the base material a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material.
  • a process of vibrating with sound wave or the like and a process of combining them can be adopted.
  • the production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
  • the heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
  • the curable resin composition of the present invention contains a polymerizable compound other than the specific resin, and this step includes a curing reaction of an unreacted polymerizable compound other than the specific resin, a curing reaction of an unreacted polymerizable group in the specific resin, and the like. Can be advanced with.
  • the heating step for example, a base is generated by decomposition of the thermobase generator, and the polyimide precursor The cyclization reaction proceeds.
  • the heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is particularly preferable, 160 ° C. or higher is more preferable, and 170 ° C. or higher is most preferable.
  • the upper limit is preferably 450 ° C. or lower, more preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and particularly preferably 220 ° C. or lower.
  • the heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • the heating from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. °C / sec is more preferable.
  • 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 which the process of heating to the maximum heating temperature is started.
  • the temperature of the film (layer) after drying is higher than, for example, the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 30 to 200 ° C.
  • the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
  • the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that at this temperature, the polymerizable groups in the specific resin between the layers proceed with the cross-linking reaction.
  • Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed.
  • the heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547.
  • the pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps.
  • the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
  • the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
  • cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
  • the heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the specific resin.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
  • the heating means is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.
  • the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (curable resin composition layer) after the development treatment.
  • metal layer existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, and alloys containing these metals are exemplified. Copper and aluminum are more preferred, and copper is even more preferred.
  • the method for forming the metal layer is not particularly limited, and an existing method can be applied.
  • the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used.
  • photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
  • the thickness of the metal layer 0.01 to 100 ⁇ m is mentioned as an example in the thickest portion, 0.1 to 50 ⁇ m is preferable, and 1 to 10 ⁇ m is more preferable.
  • the production method of the present invention preferably further includes a laminating step.
  • the laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated curable resin composition layers all at once.
  • the developing step may be followed by (e) a metal layer forming step, and (d) may be heated each time, or the layers may be laminated a predetermined number of times and then collectively (d). ) May be heated.
  • the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.
  • the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step.
  • An example of the surface activation treatment is plasma treatment.
  • the laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times. Further, each layer in the laminating step may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.
  • the number of resin layers is 2 or more and 20 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is given as an example, and the number of resin layers is 3 or more and 7 or less. Is preferable, and 3 layers or more and 5 layers or less are more preferable.
  • the method for producing a cured film of the present invention may include a surface activation treatment step of surface activating at least a part of the metal layer and the photosensitive resin composition layer.
  • the surface activating treatment step is usually performed after the metal layer forming step, but it is also possible to perform the surface activating treatment step on the photosensitive resin composition layer after the exposure development step and then perform the metal layer forming step. Good.
  • the surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the photosensitive resin composition layer after exposure, or on the metal layer and the photosensitive resin after exposure. For both of the composition layers, each may be at least partially.
  • the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region of the metal layer in which the photosensitive resin composition layer is formed on the surface. ..
  • the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure.
  • the surface activation treatment includes plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, 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, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferable, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferable.
  • the energy is preferably 500 ⁇ 200,000J / m 2, more preferably 1000 ⁇ 100,000J / m 2, and most preferably 10,000 ⁇ 50,000J / m 2.
  • a cured film (resin layer) of the curable resin composition so as to cover the metal layer after the metal layer is provided.
  • Examples thereof include an embodiment in which the steps, (b) exposure steps, (c) development steps, and (e) metal layer forming steps are repeated in this order, and (d) heating steps are collectively provided at the end or in the middle.
  • the present invention also discloses a semiconductor device containing the cured film or laminate of the present invention.
  • the semiconductor device in which the curable resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.
  • the resin of the present invention contains the repeating unit represented by the above formula (1-1), and the repeating unit represented by the above formula (3-1), represented by the above formula (3-2). At least one repeating unit selected from the group consisting of the repeating unit represented by the above formula (3-3), the repeating unit represented by the above formula (3-4), and the repeating unit represented by the above formula (3-4). It is preferable to include it.
  • the resin of the present invention is represented by the repeating unit represented by the above formula (3-1), the repeating unit represented by the above formula (3-2), and the above formula (3-3). It is synonymous with the above-mentioned specific resin except that it contains a repeating unit and at least one repeating unit selected from the group consisting of the repeating unit represented by the above formula (3-4), and also has a preferable embodiment. The same is true.
  • the resin of the present invention is preferably used as the resin contained in the curable resin composition. Further, in a composition in which a conventional polyimide is used, for example, a composition for an interlayer insulating film, a part or all of the conventional polyimide can be used in place of the resin of the present invention without particular limitation. Since the resin of the present invention has excellent chemical resistance, the resin of the present invention is required to have chemical resistance, for example, a composition for forming an insulating film, a composition for forming a laminate, and the like. It is considered that the composition is preferably used in the composition used for the purpose.
  • reaction solution was diluted with 600 mL of ethyl acetate (CH 3 COOEt), transferred to a separating funnel, and washed with 300 mL of water, 300 mL of saturated aqueous sodium hydrogen carbonate, 300 mL of dilute hydrochloric acid, and saturated brine in that order.
  • the mixture was dried over 30 g of magnesium sulfate, concentrated using an evaporator, and vacuum dried to obtain 61.0 g of a dinitro compound (A-1). It was confirmed from the NMR spectrum that it was a dinitro compound (A-1).
  • the dinitro compound (A-1) was analyzed by 1 1 H-NMR. The results are shown below.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • PZ-1 structure represented by the following formula (PZ-1).
  • 2-Hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.37 g (50.4 mmol), diethylene glycol monoethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.90 g (21.6 mmol), pyridine ( 8.70 g (110 mmol) of Tokyo Chemical Industry Co., Ltd. and 0.03 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were subsequently added, and the mixture was stirred at a temperature of 60 ° C. for 4 hours.
  • the structure of PZ-2 is presumed to be the structure represented by the following formula (PZ-2). In the formula, * indicates the binding site with the oxygen atom to which R1 binds.
  • Diethylene glycol monoethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.66 g (72 mmol), pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 8.70 g (110 mmol), 2,2,6,6-tetramethylpiperidine 0.03 g of 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) was subsequently added, and the mixture was stirred at a temperature of 60 ° C. for 4 hours. Then, after cooling the mixture to ⁇ 20 ° C., 8.68 g (73 mmol) of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 90 minutes.
  • a white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, and then 4.78 g (15 mmol) of the compound represented by the above formula (BO-1) was added. Then, 11.9 g (45 mmol) of diamine (AA-1) dissolved in 60 mL of NMP was added dropwise over 2 hours. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours.
  • the polyimide precursor resin was then precipitated in 3 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes.
  • the polyimide precursor resin was obtained by filtration, stirred again in 3 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day.
  • the structure of PZ-3 is presumed to be a structure represented by the following formula (PZ-3).
  • the structure of PZ-4 is presumed to be a structure represented by the following formula (PZ-4).
  • * represents the binding site with the oxygen atom to which R1 binds.
  • Diethylene glycol monoethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.66 g (72 mmol) 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.51 g (50 mmol), pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 10.3 g (130 mmol) and 0.03 g of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) were subsequently added, and the mixture was stirred at a temperature of 60 ° C. for 4 hours.
  • the polyimide resin was precipitated in 3 liters of methanol and stirred at a speed of 1500 rpm for 30 minutes.
  • the polyimide resin was obtained by filtration, stirred again in 2 liters of methanol water for 30 minutes, and filtered again. Then, the obtained polyimide resin was dried under reduced pressure at 45 ° C. for 1 day.
  • the structure of PI-1 is presumed to be the structure represented by the following formula (PI-1).
  • the polyimide resin was precipitated in 3 liters of methanol and stirred at a speed of 1500 rpm for 30 minutes.
  • the polyimide resin was obtained by filtration, stirred again in 2 liters of methanol water for 30 minutes, and filtered again. Then, the obtained polyimide resin was dried under reduced pressure at 45 ° C. for 1 day.
  • the structure of PI-2 is presumed to be the structure represented by the following formula (PI-2).
  • the reaction was precipitated in 1 liter of methanol and stirred at a rate of 3000 rpm for 15 minutes.
  • the resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again.
  • the obtained resin was dried under reduced pressure at 40 ° C. for 1 day.
  • the structure of PI-3 is presumed to be the structure represented by the following formula (PI-3).
  • CP-1 The weight average molecular weight (Mw) of CP-1 was 32100, and the number average molecular weight (Mn) was 15500.
  • the structure of CP-1 is presumed to be the structure represented by the following formula (CP-1).
  • -PZ-1 to PZ-5 Polyimide precursor resins PZ-1 to PZ-5 synthesized above.
  • -PI-1 to PI-3 Polyimide resins PI-1 to PI-3 synthesized above
  • CP-1 to CP-3 Comparative polyimide CP-1 synthesized above, comparative polyimide precursors CP-2 to CP-3
  • DMSO / GBL dimethyl sulfoxide-GBL: ⁇ -butyrolactone-EL: ethyl lactate-NMP: N-methylpyrrolidone
  • GBL 20: 80 (mass ratio). It shows that they were mixed and used in proportion.
  • Each curable resin composition or comparative composition prepared in each Example and Comparative Example was applied on a silicon wafer by a spin coating method to form a curable resin composition layer.
  • the silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a curable resin composition layer having a uniform thickness of 15 ⁇ m on the silicon wafer.
  • the curable resin composition layer on the silicon wafer was entirely exposed to an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed curable resin composition layer (resin layer) was subjected to nitrogen.
  • the cured layer (resin layer) of the curable resin composition layer is heated at a heating rate of 10 ° C./min in an atmosphere at the temperature shown in the “Curing conditions” column of Table 1 for 180 minutes.
  • Got The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
  • Chemical solution Mixture of dimethyl sulfoxide (DMSO) and 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio)
  • Evaluation conditions Immerse the resin layer in the chemical solution at 75 ° C. for 15 minutes before and after immersion. The dissolution rate (nm / min) was calculated by comparing the film thicknesses of the above.
  • the evaluation was performed according to the following evaluation criteria, and the evaluation results are listed in the "Chemical resistance" column of Table 1. It can be said that the lower the dissolution rate, the better the chemical resistance.
  • D The dissolution rate was 400 nm / min or more.
  • the curable resin composition layer after the above exposure is heated at a heating rate of 10 ° C./min under a nitrogen atmosphere to reach the temperature described in the column of "curing conditions" in Table 1, and then 3 Heated for hours.
  • the cured resin composition layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer.
  • the peeled cured film was punched out using a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm.
  • the elongation rate of the obtained test piece in the longitudinal direction was adjusted to JIS-K6251 using a tensile tester (Tencilon) in an environment with a crosshead speed of 300 mm / min, 25 ° C., and 65% RH (relative humidity). Measured according to. The measurement was carried out 5 times each, and the arithmetic mean value of the elongation rate (breaking elongation rate) when the test piece was broken in each of the 5 measurements was used as an index value. The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 1. It can be said that the larger the index value, the better the film strength of the cured film. -Evaluation criteria- A: The above index value was 60% or more. B: The index value was 55% or more and less than 60%. C: The index value was 50% or more and less than 55%. D: The index value was less than 50%.
  • the film thickness was determined as an arithmetic mean value obtained by measuring the film thickness at 10 points on the coated surface with an ellipsometer (KT-22 manufactured by Foothill). -Measurement of film thickness after aging-
  • the curable resin composition or the comparative composition was placed in a glass container, sealed, and allowed to stand in a light-shielded environment at 25 ° C. for 14 days, and then the pre-aging film thickness was determined.
  • a curable resin composition layer was formed by applying it on a silicon wafer by a spin coating method using the same rotation speed as in the case of.
  • the silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C.
  • the curable resin composition containing the specific resin according to the present invention has excellent chemical resistance.
  • the comparative compositions according to Comparative Examples 1 to 3 do not contain a specific resin. It can be seen that the comparative compositions according to Comparative Examples 1 to 3 are inferior in chemical resistance.
  • Example 101 The curable resin composition according to Example 1 was spun and applied to the surface of the thin copper layer of the resin base material having the thin copper layer formed on the surface so as to have a film thickness of 20 ⁇ m.
  • the curable resin composition applied to the resin substrate was dried at 100 ° C. for 2 minutes and then exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). The exposure was carried out through a mask of a square pattern (square pattern of 100 ⁇ m each in length and width, number of repetitions of 10) at a wavelength of 365 nm and an exposure amount of 400 mJ / cm 2 to prepare a square remaining pattern.

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Abstract

L'invention concerne : une composition de résine durcissable comprenant un solvant et une résine comprenant une unité de répétition représentée par la formule (1-1) et au moins une unité de répétition choisie dans le groupe constitué par une unité de répétition représentée par la formule (2-1), une unité de répétition représentée par la formule (2-2), une unité de répétition représentée par la formule (2-3) et une unité de répétition représentée par la formule (2-4); un film durci formé par durcissement de la composition de résine durcissable; un stratifié comprenant le film durci; un procédé de production du film durci; un dispositif à semi-conducteur comprenant le film durci ou le stratifié; et une nouvelle résine ayant une structure spécifique.
PCT/JP2020/045077 2019-12-05 2020-12-03 Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et résine Ceased WO2021112189A1 (fr)

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JP2021562724A JP7425088B2 (ja) 2019-12-05 2020-12-03 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイス、及び、樹脂
KR1020227018621A KR102741857B1 (ko) 2019-12-05 2020-12-03 경화성 수지 조성물, 경화막, 적층체, 경화막의 제조 방법, 반도체 디바이스, 및, 수지
CN202080084112.3A CN114761466B (zh) 2019-12-05 2020-12-03 固化性树脂组合物、固化膜、层叠体、固化膜的制造方法、半导体器件及树脂

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WO2023120037A1 (fr) 2021-12-23 2023-06-29 富士フイルム株式会社 Procédé de production de corps assemblé, corps assemblé, procédé de production de stratifié, stratifié, procédé de production de dispositif, dispositif et composition pour former une partie précurseur contenant du polyimide
WO2023162687A1 (fr) 2022-02-24 2023-08-31 富士フイルム株式会社 Composition de résine, article durci, stratifié, procédé de production d'article durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2023190064A1 (fr) 2022-03-29 2023-10-05 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2024071237A1 (fr) 2022-09-30 2024-04-04 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2024071380A1 (fr) 2022-09-30 2024-04-04 富士フイルム株式会社 Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, et dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci
WO2024070963A1 (fr) 2022-09-30 2024-04-04 富士フイルム株式会社 Procédé de production de film, composition de résine photosensible, procédé de production de produit durci, produit durci et stratifié

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Publication number Priority date Publication date Assignee Title
WO2023120037A1 (fr) 2021-12-23 2023-06-29 富士フイルム株式会社 Procédé de production de corps assemblé, corps assemblé, procédé de production de stratifié, stratifié, procédé de production de dispositif, dispositif et composition pour former une partie précurseur contenant du polyimide
WO2023162687A1 (fr) 2022-02-24 2023-08-31 富士フイルム株式会社 Composition de résine, article durci, stratifié, procédé de production d'article durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2023190064A1 (fr) 2022-03-29 2023-10-05 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2024071237A1 (fr) 2022-09-30 2024-04-04 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2024071380A1 (fr) 2022-09-30 2024-04-04 富士フイルム株式会社 Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, et dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci
WO2024070963A1 (fr) 2022-09-30 2024-04-04 富士フイルム株式会社 Procédé de production de film, composition de résine photosensible, procédé de production de produit durci, produit durci et stratifié

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TW202128841A (zh) 2021-08-01
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JPWO2021112189A1 (fr) 2021-06-10
KR20220098165A (ko) 2022-07-11
CN114761466B (zh) 2024-12-10
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