WO2021246459A1 - Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

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

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Publication number
WO2021246459A1
WO2021246459A1 PCT/JP2021/021069 JP2021021069W WO2021246459A1 WO 2021246459 A1 WO2021246459 A1 WO 2021246459A1 JP 2021021069 W JP2021021069 W JP 2021021069W WO 2021246459 A1 WO2021246459 A1 WO 2021246459A1
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group
preferable
compound
formula
acid
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PCT/JP2021/021069
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French (fr)
Japanese (ja)
Inventor
敦靖 野崎
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富士フイルム株式会社
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Priority to KR1020227042232A priority Critical patent/KR20230005971A/en
Priority to JP2022528879A priority patent/JPWO2021246459A1/ja
Publication of WO2021246459A1 publication Critical patent/WO2021246459A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/16Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/34Layered products comprising a layer of synthetic resin comprising polyamides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/02Polyamines
    • C08G73/0233Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular 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
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22Polybenzoxazoles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/35Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353Five-membered rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/541Silicon-containing compounds containing oxygen
    • C08K5/5415Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/02Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/02Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/025Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/02Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions 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
    • C08L79/02Polyamines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions 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
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00Compositions 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
    • C08L79/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/075Silicon-containing compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/075Silicon-containing compounds
    • G03F7/0757Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20Exposure; Apparatus therefor

Definitions

  • the present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.
  • Polyimide or polybenzoxazole is applied to various applications because it has excellent heat resistance and insulating properties.
  • the application is not particularly limited, and examples thereof include a semiconductor device for mounting as a material for an insulating film or a sealing material, or a protective film. It is also used as a base film and coverlay for flexible substrates.
  • the polyimide or polybenzoxazole is a form of a curable resin composition containing at least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor.
  • a curable resin composition is applied to a base material by, for example, coating to form a resin film, and then exposed, developed, heated or the like as necessary to form a cured film on the base material.
  • the polyimide precursor and the polybenzoxazole precursor are cyclized by heating, for example, and become polyimide and polybenzoxazole in the cured membrane, respectively.
  • the curable resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied curable resin composition at the time of application. It can be said that it has excellent manufacturing adaptability.
  • the above-mentioned curable resin composition is expected to be increasingly applied in industry.
  • Patent Document 1 describes an adhesive composition for adhering a semiconductor element to a support member, wherein (A) a thermoplastic resin having a carboxyl group and / or a hydroxyl group, and (B) an oxazoline group in the molecule.
  • An adhesive composition containing (C) a thermosetting resin and a compound having the above is described.
  • Patent Document 2 describes a polyimide having a specific structure.
  • the metal include metals contained as a metal layer such as a conductive layer, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten, and copper, aluminum and these. Alloys containing metals are preferred, copper or alloys containing copper are more preferred, and copper is even more preferred. For example, in a laminated body including a metal layer and a cured film in contact with the metal layer, improvement in adhesion between the metal layer and the cured film is required.
  • the present invention provides a curable resin composition capable of obtaining a cured film having excellent adhesion to a metal, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and production of the cured film. It is an object of the present invention to provide a method and a semiconductor device including the cured film or the laminate.
  • ⁇ 1> At least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide and a polybenzoxazole.
  • ⁇ 2> The curable resin composition according to ⁇ 1>, wherein the content of the carboxy group in the resin is 1.0 mmol / g or less.
  • ⁇ 3> The curable resin composition according to ⁇ 1> or ⁇ 2>, wherein the compound having an oxazoline group is a compound containing two or more oxazoline groups in its structure.
  • ⁇ 4> The compound according to any one of ⁇ 1> to ⁇ 3>, wherein the compound having an oxazoline group contains at least one selected from the group consisting of an alkoxysilyl group, a radically polymerizable group and an azole group.
  • ⁇ 5> The curable resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the compound having an oxazoline group is a resin.
  • ⁇ 6> The curable resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the compound containing the acid group and the alkoxysilyl group is a resin.
  • the compound containing the acid group and the alkoxysilyl group comprises at least one group selected from the group consisting of a radically polymerizable group and an azole group, and is selected from any one of ⁇ 1> to ⁇ 6>.
  • the curable resin composition according to the above. ⁇ 8> The curable resin according to any one of ⁇ 1> to ⁇ 7>, which comprises at least one compound selected from the group consisting of a thermosetting agent, a photobase generating agent, and an onium salt. Composition. ⁇ 9> The curable resin composition according to any one of ⁇ 1> to ⁇ 8>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 10> A cured film obtained by curing the curable resin composition according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 11> A laminate containing two or more layers of the cured film according to ⁇ 10> and containing a metal layer between any of the cured films.
  • ⁇ 12> 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 ⁇ 9> to a substrate to form a film.
  • the method for producing a cured film according to ⁇ 12> which comprises an exposure step for exposing the film and a developing step for developing the film.
  • ⁇ 14> The method for producing a cured film according to ⁇ 12> or ⁇ 13>, which comprises a heating step of heating the film at 50 to 450 ° C.
  • a semiconductor device comprising the cured film according to ⁇ 10> or the laminate according to ⁇ 11>.
  • a curable resin composition capable of obtaining a cured film having excellent adhesion to a metal, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the cured film. And a semiconductor device including the cured film or the laminate.
  • 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 intended action of the process can be achieved.
  • the notation not describing substitution and non-substitution also 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).
  • exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. 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.
  • Any, 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 photosensitive layer, the direction from the base material to the photosensitive layer is referred to as “upper”.
  • the opposite direction is referred to as "down”.
  • the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Further, 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 atmospheric pressure)
  • the relative humidity is 50% RH.
  • a combination of preferred embodiments is a more preferred embodiment.
  • the curable resin composition of the present invention is at least one resin (hereinafter, also referred to as "specific resin") selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, polyimide and polybenzoxazole, and oxazoline. It contains a compound having a group and a compound containing an acid group and an alkoxysilyl group.
  • the curable resin composition of the present invention may be a negative type curable resin composition or a positive type curable resin composition, but 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 developer when a layer formed from the curable resin composition is exposed.
  • the positive type curable resin composition refers to a composition in which an exposed portion (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 at least one selected from the group consisting of a thermosetting agent, a photobase generating agent and an onium salt, which will be described later, from the viewpoint of the film strength of the obtained cured film. It preferably contains a compound.
  • a cured film having excellent adhesion to a metal can be obtained.
  • the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
  • the curable resin composition of the present invention contains a compound having an oxazoline group and a compound containing an acid group and an alkoxysilyl group, so that the obtained cured film has excellent adhesion to a metal.
  • the resin having a siloxane bond formed by the bond of the alkoxysilyl group contained in the cured film obtained by the reaction of the acid group and the oxazoline group includes a structure derived from the oxazoline group. It will be. It is presumed that a cured film having excellent adhesion can be obtained by the interaction between the structure derived from the oxazoline group and the specific resin.
  • the oxazoline group is bifunctional or higher, between the acid groups in the compound having an acid group and an alkoxysilyl group, or between the acid group in the compound having an acid group and an alkoxysilyl group and the acid group in the specific resin. It is considered that a crosslinked structure can be formed and the adhesion is further excellent.
  • the compound having an oxazoline group has a polymerizable group other than the oxazoline group, the polymerization of the compounds having the oxazoline group, or, for example, a cross-linking agent (also referred to as a polymerizable compound) or a specific resin having a polymerizable group and oxazoline.
  • the specific resin or the resin formed by the polymerization of the polymerizable compound contains a structure derived from an oxazoline group by polymerization with a compound having a group, it is considered that the adhesion is further excellent.
  • the compound having an oxazoline group contains an azole group, it is considered that the adhesion to the metal is further excellent because the azole group is coordinated to the metal.
  • the chemical resistance is also improved by cross-linking the oxazoline group with the acid group in the specific resin.
  • Patent Documents 1 and 2 do not describe or suggest a curable resin composition containing a compound having an oxazoline group and a compound containing an acid group and an alkoxysilyl group.
  • the curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor.
  • the curable resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.
  • the specific resin has a polymerizable group.
  • the polymerizable group in the specific resin include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group and an alkoxymethyl group.
  • a group having an ethylenically unsaturated bond is preferable.
  • the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group.
  • Examples thereof include an acryloyloxy group, and a (meth) acryloyloxy group is preferable.
  • the specific resin has a polymerizable group that can be polymerized with the compound having an oxazoline group.
  • the specific resin has a radical polymerizable group and the compound having an oxazoline group has a radical polymerizable group, or the specific resin has an epoxy group and the specific resin has an epoxy group. Examples thereof include a combination in which a compound having an oxazoline group has an epoxy group.
  • the polymerization of the polymerizable group in the specific resin and the polymerizable group in the compound having an oxazoline group in the cured film further improves the adhesion of the obtained cured film to the metal. ..
  • the specific resin When the compound containing an acid group and an alkoxysilyl group has a polymerizable group, the specific resin preferably has a polymerizable group that can be polymerized with the polymerizable group in the compound containing the acid group and the alkoxysilyl group.
  • the specific resin has a radically polymerizable group
  • the compound containing an acid group and an alkoxysilyl group has a radically polymerizable group
  • the specific resin has an epoxy group.
  • a combination in which a compound containing an acid group and an alkoxysilyl group has an epoxy group and the like can be mentioned.
  • the polymerizable group in the specific resin and the polymerizable group in the compound containing the acid group and the alkoxysilyl group are polymerized in the cured film, and further, the acid group in the compound containing the acid group and the alkoxysilyl group.
  • the oxazoline group in the compound having an oxazoline group are bonded to each other, so that it is considered that the adhesion of the obtained cured film to the metal is further improved.
  • the compound having an oxazoline group preferably has an alkoxysilyl group.
  • the polymerizable group in the specific resin and the polymerizable group in the compound containing the acid group and the alkoxysilyl group are polymerized in the cured film, and the alkoxysilyl group in the compound containing the acid group and the alkoxysilyl group is used. Since the alkoxysilyl group in the compound having an oxazoline group is condensed, the bond between each compound is strengthened, and it is considered that the adhesion of the obtained cured film to the metal is further improved.
  • the specific resin preferably contains a radically polymerizable group.
  • the curable resin composition preferably contains a photoradical polymerization initiator described later as a photosensitizer, contains a photoradical polymerization initiator described later as a photosensitizer, and is described later. It is more preferable to contain the radical cross-linking agent described below, and it is further preferable to contain the photoradical polymerization initiator described below as the photosensitizer, the radical cross-linking agent described below, and the sensitizer described below. From such a curable resin composition, for example, a negative photosensitive layer is formed.
  • the specific resin may have a polar conversion group such as an acid-decomposable group.
  • the curable resin composition preferably contains a photoacid generator described later as a photosensitive agent. From such a curable resin composition, for example, a chemically amplified positive type photosensitive layer or a negative type photosensitive layer is formed.
  • the content of the carboxy group in the specific resin is also preferably 1.0 mmol / g or less. According to the above aspect, the developability is improved when a developer containing an organic solvent is used as the developer.
  • the content of the carboxy group in the specific resin is preferably 0.001 to 1.0 mmol / g, more preferably 0.01 to 0.8 mmol / g. According to the above aspect, the developability when a developer containing an organic solvent is used as the developer is improved, and the compound having an oxazoline group and the specific resin can form a bond. It is considered that the cured film is also excellent in adhesion to metal.
  • the polyimide precursor used in the present invention is not particularly specified, such as its type, but preferably contains a repeating unit represented by the following formula (2). Equation (2) In formula (2), A 1 and A 2 independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, and R 113. And R 114 independently represent a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 in the formula (2) independently represent an oxygen atom or NH, and an oxygen atom is preferable.
  • R 111 in the formula (2) represents a divalent organic group.
  • the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified.
  • a cyclic aliphatic group having 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • a group represented by —L—Ar— is exemplified.
  • Ar is an aromatic group independently
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO 2- or NHCO-, or a group consisting of a combination of two or more of the above.
  • R 111 is preferably derived from diamine.
  • the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof.
  • the diamine containing the above is preferable, and the diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable.
  • aromatic groups include:
  • diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-,1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl;
  • diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferable.
  • diamines can also be preferably used.
  • a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 is also preferably used.
  • R 111 is preferably represented by ⁇ Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film.
  • Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO 2- or NHCO-, or a group consisting of a combination of two or more of the above.
  • Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group having a fluorine atom are carbon atoms and optionally 1 or substituted by 2, -O -, - CO - , - S- or SO 2 - are preferred.
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61).
  • a divalent organic group represented by the formula (61) is more preferable.
  • Equation (51) In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoro. It is a methyl group.
  • 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 or trifluoromethyl groups, respectively.
  • Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.
  • R 111 may have a structure containing a polymerizable group.
  • R 111 may have a structure derived from a diamine compound having a polymerizable group.
  • the diamine compound having a polymerizable group is not particularly limited, but is preferably a compound containing an aromatic ring structure, and is a compound having a structure in which a structure containing an amino group and a polymerizable group is directly linked to the aromatic ring structure. Is more preferable.
  • an ethylenically unsaturated group, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group and a maleimide are preferable.
  • a group, a vinylphenyl 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.
  • R 111 has a structure containing a polymerizable group
  • R 111 has a structure represented by the following formula (1-1).
  • Y 1 represents an n + divalent group containing an aromatic hydrocarbon group
  • P 1 represents a group containing a polymerizable group
  • n represents an integer of 1 or more
  • * represents each.
  • Y 1 represents an n + divalent group containing an aromatic hydrocarbon group.
  • Aromatic hydrocarbon group for Y 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.
  • binding site of two * and according to equation (1-1) is preferably either an aromatic hydrocarbon group.
  • binding site of the P 1 is preferably either an aromatic hydrocarbon group. That is, it is preferable that P 1 is directly bonded to the aromatic hydrocarbon ring structure contained in Y 1.
  • Y 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-mentioned formulas (A2-1) to Y1. 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 P 1 in the formula (1-1) It may be a binding site, and * independently represents a binding site with another structure.
  • Y 1 preferably contains a structure represented by any of the formulas (A2-1) to (A2-4), and is preferably the formula (A2-2) or the formula (A2-2). It is more preferable to include the structure represented by any one of A2-4).
  • R A211 ⁇ R A214 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, 3 to 12 carbon atoms It is preferable to represent a cyclic alkyl group, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a cyano group, an alkyl halide group having 1 to 3 carbon atoms, or a halogen atom. From the viewpoint of solvent solubility, hydrogen is used.
  • alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkyl halide groups having 1 to 3 carbon atoms are more preferable, and hydrogen atoms or alkyl groups having 1 to 6 carbon atoms are more preferable.
  • R A221 ⁇ R A224 have the same meanings as R A211 ⁇ R A214 in formula (A2-1), preferable embodiments thereof are also the same.
  • R A231 ⁇ R A238 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, a halogenated alkyl 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, and 1 to 6 carbon atoms.
  • Alkoxy group of 6 or an alkyl halide group having 1 to 3 carbon atoms is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable.
  • 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.
  • 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. Is preferable, and it is more preferable to represent a single bond or —O—.
  • 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 divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, but may be a divalent aromatic hydrocarbon. It is preferably a group.
  • the heterocyclic group for example, a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable, and a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable, and a pyrrolidine ring, More preferably, a group obtained by removing two hydrogen atoms from a ring structure such as a tetrahydrofuran ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, a piperidine ring, a tetrahydropyran ring, a pyridine ring, or a morpholin ring.
  • heterocycles may further form a fused ring with another heterocycle or a hydrocarbon ring.
  • the number of ring members of the heterocycle is preferably 5 to 10, and more preferably 5 or 6.
  • the heteroatom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
  • Examples of 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 chlorine atom or a bromine atom is preferable.
  • R A241 ⁇ R A248, L A241 have the same meanings as R A231 ⁇ R A238, L A231 in formula (A2-3), preferable embodiments thereof are also the same.
  • R A251 ⁇ R A258 have the same meanings as R A211 ⁇ R A214 in formula (A2-1), preferable embodiments thereof are also the same.
  • At least one of R A211 ⁇ R A214 is preferably a binding site for P 1 in formula (1-1), one of the P of the R A211 ⁇ R A214 more preferably a binding site with 1, it is preferred that R A213 is a bond site to the P 1.
  • at least one of R A 221 ⁇ R A224 is preferably a binding site for P 1 in formula (1-1), one of the P of the R A221 ⁇ R A224 more preferably a binding site with 1, it is preferred that R a 223 is a binding site between the P 1.
  • At least one of R A231 ⁇ R A238, is preferably a binding site for P 1 in formula (1-1), two of R A231 ⁇ R A238, the more preferably a binding site of the P 1, bract one of R A231 ⁇ R A234, more preferably two one meter of the R A235 ⁇ R A238 is a binding site of the P 1, R A231 and two of R A238, it is particularly preferred that the binding site of the P 1.
  • At least one of R A 241 ⁇ R A248, is preferably a binding site for P 1 in formula (1-1), two of R A241 ⁇ R A248, the more preferably a binding site of the P 1, bract one of R A241 ⁇ R A244, more preferably two one meter of the R A245 ⁇ R A248 is a binding site of the P 1, R A241 and two of R A248, it is particularly preferred that the binding site of the P 1.
  • At least one of R A251 ⁇ R A258, is preferably a binding site for P 1 in formula (1-1), two of R A251 ⁇ R A258, the more preferably a binding site of the P 1, bract one of R A251 ⁇ R A254, more preferably two one meter of the R A255 ⁇ R A258 is a binding site of the P 1, R A253 and two of R A257, it is particularly preferred that the binding site of the P 1.
  • the two * are the * in the formula (1-1), respectively. That is, it is preferable that the two nitrogen atoms to which R 111 in the formula (2) is bonded are directly bonded to the positions represented by the two * in the formulas (A2-1) to (A2-5).
  • Y 1 is preferably a group represented by the following formula (Y-1) or (Y-2).
  • R Y11 , R Y12, R Y13 each has the same meaning as R A211, R A212 and R A214 in formula (A2-1), preferable embodiments thereof are also the same.
  • R Y21 ⁇ R Y26 each of R Y21 ⁇ R Y26, have the same meanings as R A242 ⁇ R A247 in formula (A2-4), preferable embodiments thereof are also the same.
  • * is the binding site with the two nitrogen atoms to which R 111 in the formula (2) is bonded
  • # is the formula (1-1), respectively. the binding site of P 1 in, respectively.
  • P 1 represents a group containing a polymerizable group.
  • a polymerizable group an ethylenically unsaturated group, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group and a maleimide are preferable.
  • a group, a vinylphenyl 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 number of polymerizable groups contained in P 1 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.
  • P 1 is preferably a group represented by the following formula (P-1).
  • L 1 represents a single bond or m + 1 valent linking group
  • a 2 represents a polymerizable group
  • m represents an integer of 1 or more
  • * represents a binding site with Y 1. ..
  • L 1 is preferably a single bond, a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N- , or a group in which two or more of these are bonded, preferably a single bond.
  • a bond, or a hydrocarbon group, an ether bond, a carbonyl group, -NR N- , or a group in which two or more of these are bonded is more preferable.
  • 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 these combinations
  • 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. It is particularly preferable, and 1 is most preferable.
  • P 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 Y 1.
  • a 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, and L 2 is a hydrocarbon group or a hydrocarbon group and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N- , or.
  • 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.
  • 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.
  • the (poly) alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group. Further, in the present invention, the polyalkyleneoxy group means a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the sequence 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.
  • 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.
  • 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. Especially preferable.
  • 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, an amide bond, or a carbonate bond, and an ester bond, a urethane bond, a urea bond, or an amide bond is more preferable.
  • the direction of these bonds is not limited.
  • the binding site with L 2 in Z 1 may be a carbon atom or an oxygen atom in the ester bond.
  • R 115 in the formula (2) represents a tetravalent organic group.
  • a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
  • * independently represents a binding site with another structure.
  • R 112 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or substituted with a fluorine atom, —O—, —CO—, —S—, —SO.
  • NHCO- and preferably a group selected from a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO. More preferably, it is a group selected from-, -S- and SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2-, -O-, -CO. -, - and more preferably a divalent radical selected from the group consisting of - S-, and SO 2.
  • R 115 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).
  • R 115 represents a tetravalent organic group.
  • a preferred range of R 115 has the same meaning as R 115 in formula (2), and preferred ranges are also the same.
  • tetracarboxylic acid dianhydride examples include pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-.
  • PMDA pyromellitic acid dianhydride
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.
  • R 111 and R 115 has an OH group. More specifically, as R 111 , a residue of a bisaminophenol derivative can be mentioned.
  • R 113 and R 114 independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and both contain a polymerizable group. preferable.
  • a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like.
  • the polymerizable group in the specific resin include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and a methylol.
  • examples include a group and an amino group.
  • the radically polymerizable group of the polyimide precursor or the like a group having an ethylenically unsaturated bond is preferable.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III) and the like, and a group represented by the following formula (III) is preferable.
  • R200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
  • * represents a binding site with another structure.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a polyalkyleneoxy group. Examples of suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butanjiyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group.
  • the polyalkyleneoxy group means a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the sequence 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. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable. Further, the 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, and even more preferably 2 to 6.
  • the polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance.
  • a group bonded to an oxy group 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.
  • R 113 and R 114 are each independently a hydrogen atom or a monovalent organic group.
  • the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one.
  • Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned.
  • the acidic group is preferably an OH group. It is also more preferable that R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.
  • R 113 or R 114 is preferably a monovalent organic group.
  • the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
  • the alkyl group preferably has 1 to 30 carbon atoms.
  • the alkyl group may be linear, branched or cyclic.
  • linear or branched alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group.
  • Isobutyl group isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2- (2-ethoxyethoxy) ethoxy) ) Ethoxy group is mentioned.
  • the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
  • Examples of the cyclic alkyl group of the monocycle include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
  • Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
  • aromatic group examples include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene.
  • the benzene ring is most preferred.
  • R 113 is a hydrogen atom or R 114 is a hydrogen atom
  • R 113 is a hydrogen atom
  • R 114 is a hydrogen atom
  • the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond.
  • the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
  • At least one of R 113 and R 114 may be a polar conversion group such as an acid-degradable group.
  • the acid-degradable group is not particularly limited as long as it is decomposed by the action of an acid to form an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group or a silyl ether group.
  • a tertiary alkyl ester group or the like is preferable, and an acetal group is more preferable from the viewpoint of exposure sensitivity.
  • the acid-degradable group examples include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl.
  • examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
  • the polyimide precursor has a fluorine atom in the structural unit.
  • the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
  • the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
  • the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
  • the repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors and the like used in the present invention is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further widened. Equation (2-A) In formula (2-A), A 1 and A 2 represent oxygen atoms, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently. Representing a hydrogen atom or a monovalent organic group , at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are polymerizable groups.
  • a 1, A 2, R 111 , R 113 and R 114 each independently have the same meaning as A 1, A 2, R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same .
  • R 112 has the same meaning as R 112 in formula (5), and preferred ranges are also the same.
  • the polyimide precursor may contain one kind of repeating structural unit represented by the formula (2), but may also contain two or more kinds. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).
  • polyimide precursor in the present invention a polyimide precursor in which 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all repeating units is a repeating unit represented by the formula (2) is used. Illustrated.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000.
  • the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
  • the degree of dispersion of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more.
  • the upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
  • the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
  • the polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide that is soluble in a developing solution containing an organic solvent as a main component.
  • the alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and 0.5 g or more from the viewpoint of pattern formability.
  • a polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable.
  • the upper limit of the dissolved amount is not particularly limited, but is preferably 100 g or less.
  • the polyimide is preferably a polyimide having a plurality of imide structures in the main chain from the viewpoint of the film strength and the insulating property of the obtained organic film.
  • the "main chain” refers to the relatively longest bound chain among the molecules of the polymer compound constituting the resin, and the “side chain” refers to other bound chains.
  • the polyimide preferably has a fluorine atom.
  • the fluorine atom is preferably contained in, for example, R 132 in the repeating unit represented by the formula (4) described later, or R 131 in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula (4) described later. It is more preferable that it is contained as an alkyl fluoride group in R 132 in the repeating unit represented by 4) or in R 131 in the repeating unit represented by the formula (4) described later.
  • the amount of fluorine atoms with respect to the total mass of the polyimide is preferably 1 to 50 mol / g, more preferably 5 to 30 mol / g.
  • the polyimide preferably has a silicon atom.
  • the silicon atom is preferably contained in R 131 in the repeating unit represented by the formula (4) described later, and is organically modified (poly ) in R 131 in the repeating unit represented by the formula (4) described later. ) It is more preferable that it is contained as a siloxane structure. Further, the silicon atom or the organically modified (poly) siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
  • the amount of silicon atoms with respect to the total mass of the polyimide is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.
  • the polyimide preferably has an ethylenically unsaturated bond.
  • the polyimide may have an ethylenically unsaturated bond at the end of the main chain or may have it in the side chain, but it is preferable to have it in the side chain.
  • the ethylenically unsaturated bond is preferably radically polymerizable.
  • the ethylenically unsaturated bond is preferably contained in R 132 in the repeating unit represented by the formula (4) described later or R 131 in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula described later.
  • R 132 in the repeating unit represented by (4) or R 131 in the repeating unit represented by the formula (4) described later is contained as a group having an ethylenically unsaturated bond.
  • ethylenically unsaturated bond ethylene R 131 in the repeating unit represented by the preferably contained in R 131 in the repeating unit represented by the formula (4) described later, which will be described later Equation (4) It is more preferably contained as a group having a sex unsaturated bond.
  • Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group. Examples thereof include an acryloyloxy group and a group represented by the following formula (IV).
  • R 20 represents a hydrogen atom or a methyl group, a methyl group is preferable.
  • (Poly) alkyleneoxy group having 2 to 30 carbon atoms the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12 and 1). ⁇ 6 is more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined is represented.
  • R 21 is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1).
  • L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) alkyleneoxy group having 2 to 30 carbon atoms, or a group having two or more bonds thereof, and is X.
  • Indicates an oxygen atom or a sulfur atom * represents a bond site with another structure
  • represents a bond site with an oxygen atom to which R 201 in the formula (III) is bonded.
  • a preferred embodiment of the alkylene group having 2 to 12 carbon atoms in L or the (poly) alkyleneoxy group having 2 to 30 carbon atoms is the above-mentioned R 21 having 2 to 12 carbon atoms. This is the same as the preferred embodiment of the alkylene group of 12 or the (poly) alkyleneoxy group having 2 to 30 carbon atoms.
  • X is preferably an oxygen atom.
  • * is synonymous with * in the formula (IV), and the preferred embodiment is also the same.
  • the structure represented by the formula (R1) comprises, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reacting.
  • the structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
  • the structure represented by the formula (R3) is obtained by reacting, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).
  • a polyimide having a hydroxy group such as a phenolic hydroxy group
  • a compound having a glycidyl group and an ethylenically unsaturated bond for example, glycidyl methacrylate.
  • the polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance.
  • a group bonded to an oxy group 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.
  • * represents a binding site with another structure, and is preferably a binding site with the main chain of polyimide.
  • the amount of the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g. From the viewpoint of production suitability, the amount of ethylenically unsaturated bonds with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and preferably 0.0005 to 0.05 mol / g. More preferred.
  • the polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
  • the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
  • the crosslinkable group other than the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by the formula (4) described later, for example.
  • the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g. From the viewpoint of production suitability, the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. It is more preferably g.
  • the polyimide may have a polar conversion group such as an acid-decomposable group.
  • the acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R 113 and R 114 in the above formula (2), and the preferred embodiment is also the same.
  • the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more from the viewpoint of improving developability. Is more preferable.
  • the acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
  • the acid value of the polyimide is preferably 2 to 35 mgKOH / g, and 3 to 30 mgKOH. / G is more preferable, and 5 to 20 mgKOH / g is even more preferable.
  • the acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
  • an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of achieving both storage stability and developability.
  • the pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa.
  • pKa is a value calculated by ACD / ChemSketch (registered trademark) unless otherwise specified.
  • the values published in "Revised 5th Edition Chemistry Handbook Basics" edited by the Chemical Society of Japan may be referred to.
  • the acid group is a polyvalent acid such as phosphoric acid
  • the above pKa is the first dissociation constant.
  • the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.
  • the polyimide preferably has a phenolic hydroxy group.
  • the polyimide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
  • the phenolic hydroxy group is preferably contained in, for example, R 132 in the repeating unit represented by the formula (4) described later or R 131 in the repeating unit represented by the formula (4) described later.
  • the amount of the phenolic hydroxy group with respect to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.
  • the polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably contains a repeating unit represented by the following formula (4), and is represented by the formula (4). It is more preferable that the compound contains a repeating unit and has a polymerizable group.
  • Equation (4) In formula (4), R 131 represents a divalent organic group and R 132 represents a tetravalent organic group. When having a polymerizable group, the polymerizable group may be located at at least one of R 131 and R 132 , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be located in.
  • Equation (4-1) In formula (4-1), R 133 is a polymerizable group, and the other groups are synonymous with formula (4). Equation (4-2) At least one of R 134 and R 135 is a polymerizable group, when it is not a polymerizable group, it is an organic group, and the other group is synonymous with the formula (4).
  • the polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.
  • R 131 represents a divalent organic group.
  • the divalent organic group the same group as R 111 in the formula (2) is exemplified, and the preferred range is also the same.
  • examples of R 131 include diamine residues remaining after removal of the amino group of diamine.
  • examples of the diamine include aliphatic, cyclic aliphatic or aromatic diamines. Specific examples include the example of R 111 in the formula (2) of the polyimide precursor.
  • R 131 is a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the generation of warpage during firing.
  • a diamine residue containing two or more of an ethylene glycol chain and / or a propylene glycol chain in one molecule is more preferable, and a diamine residue containing no aromatic ring is more preferable.
  • Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine® KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) Examples thereof include, but are not limited to, propoxy) propane-2-amine and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propane-2-amine.
  • R 132 represents a tetravalent organic group.
  • the tetravalent organic group the same group as R 115 in the formula (2) is exemplified, and the preferable range is also the same.
  • examples of R 132 include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Specific examples include the example of R 115 in the formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
  • R 131 and R 132 It is also preferable to have an OH group in at least one of R 131 and R 132. More specifically, as R 131 , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the above (DA-1) to (DA-18) are preferable examples. As R 132 , the above-mentioned (DAA-1) to (DAA-5) are more preferable examples.
  • the polyimide has a fluorine atom in the structural unit.
  • the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.
  • the polyimide may be copolymerized with an aliphatic group having a siloxane structure.
  • the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
  • the main chain end of the polyimide may be sealed with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound.
  • an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound.
  • monoamine acid anhydride
  • monocarboxylic acid monoacid chloride compound or monoactive ester compound.
  • monoactive ester compound preferable.
  • monoamine it is more preferable to use monoamine, and preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7.
  • the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, the insulating property, etc. of the obtained organic film. More preferably, it is 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, for example, by the following method. The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm -1, which is the absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350 ° C.
  • the polyimide may include the repeating structural unit of the above formula (4), all comprising one type of R 131 or R 132, and the above formula (4) containing two or more different types of R 131 or R 132. May include repeating units of. Further, the polyimide may contain other types of repeating structural units in addition to the repeating unit of the above formula (4).
  • the polyimide is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound (partially replaced with a terminal encapsulant which is a monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partly an acid) at a low temperature.
  • a polyimide precursor is obtained by using a method such as a method of reacting with a terminal encapsulant (replacement with an end-capping agent), which is completely imidized by a known imidization reaction method, or an imide in the middle.
  • Synthesis using a method of stopping the conversion reaction and introducing a partially imidized structure and further, a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor.
  • a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor.
  • Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrix5218 (manufactured by HUNTSMAN Co., Ltd.).
  • the weight average molecular weight (Mw) of the polyimide is 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and 10,000 to 30,000. More preferred. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polyimides are contained, it is preferable that the weight average molecular weight of at least one kind of polyimide is in the above range.
  • the polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but preferably contains a repeating unit represented by the following formula (3).
  • Equation (3) R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. show.
  • R 123 and R 124 are synonymous with R 113 in the formula (2), respectively, and the preferable range is also the same. That is, at least one is preferably a polymerizable group.
  • R 121 represents a divalent organic group.
  • the divalent organic group a group containing at least one of an aliphatic group and an aromatic group is preferable.
  • the aliphatic group a linear aliphatic group is preferable.
  • R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
  • a dicarboxylic acid residue a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
  • a dicarboxylic acid containing an aliphatic group a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two -COOH are preferable.
  • a dicarboxylic acid consisting of is more preferable.
  • the carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, and 4 to 20. It is more preferably 15, and particularly preferably 5 to 10.
  • the linear aliphatic group is preferably an alkylene group.
  • dicarboxylic acid containing a linear aliphatic group examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Didimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimeric acid, sverin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, s
  • Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
  • dicarboxylic acid containing an aromatic group a dicarboxylic acid having the following aromatic groups is preferable, and a dicarboxylic acid consisting of only the following aromatic groups and two -COOH is more preferable.
  • A is -CH 2- , -O-, -S-, -SO 2- , -CO-, -NHCO-, -C (CF 3 ) 2- , and -C (CH 3 ) 2- Represents a divalent group selected from the group consisting of, and * represents a binding site with another structure independently.
  • dicarboxylic acid containing an aromatic group examples include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
  • R 122 represents a tetravalent organic group.
  • the tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferable range is also the same.
  • R 122 is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'.
  • bisaminophenol derivatives having the following aromatic groups are preferable.
  • X 1 represents -O-, -S-, -C (CF 3 ) 2- , -CH 2- , -SO 2- , -NHCO-, and * and # represent other structures, respectively.
  • R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Further, it is also preferable that R 122 has a structure represented by the above formula.
  • any two of the four * and # in total are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, and preferably R 122 in another 2 Exemplary ethynylphenylbiadamantane derivatives (3) is a binding site to the oxygen atom bonding, two * is a bond sites with an oxygen atom R 122 are attached in the formula (3) , And two # are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, or two * are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded.
  • the site is a site and the two #s are the bonding sites with the oxygen atom to which the R 122 in the formula (3) is bonded, and the two * are the oxygen to which the R 122 in the formula (3) is bonded. It is more preferable that it is a bond site with an atom and the two #s are bond sites with a nitrogen atom to which R 122 in the formula (3) is bonded.
  • R 1 is a hydrogen atom, an alkylene, a substituted alkylene, -O-, -S-, -SO 2- , -CO-, -NHCO-, a single bond, or the following formula (A-). It is an organic group selected from the group of sc).
  • R 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
  • R 3 is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
  • phenolic hydroxy original ortho i.e., to have also substituent R 3 is believed to closer the distance of the carbonyl carbon and hydroxy original amide bond, It is particularly preferable in that the effect of increasing the cyclization rate when cured at a low temperature is further enhanced.
  • R 2 is an alkyl group and R 3 is an alkyl group has high transparency to i-rays and a high cyclization rate when cured at a low temperature. The effect can be maintained, which is preferable.
  • R 1 is an alkylene or a substituted alkylene.
  • the alkylene and the substituted alkylene according to R 1 include linear or branched alkyl groups having 1 to 8 carbon atoms, among which -CH 2- and -CH (CH 3 ).
  • -, -C (CH 3 ) 2 has sufficient solubility in a solvent while maintaining the effects of high transparency to i-rays and high cyclization rate when cured at low temperature. It is more preferable in that an excellent polybenzoxazole precursor can be obtained.
  • the polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3). It is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the occurrence of warpage due to ring closure can be suppressed.
  • SL diamine residue represented by the following formula
  • Z has an a structure and a b structure
  • R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • R 2s is a hydrocarbon group having 1 to 10 carbon atoms.
  • at least one of R 3s, R 4s , R 5s , and R 6s is an aromatic group
  • the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different.
  • the polymerization of the a structure and the b structure may be block polymerization or random polymerization.
  • the mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.
  • preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups.
  • the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
  • the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is used as the repeating structural unit. It is also preferable to include it. Examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (2).
  • the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further, when used in a composition described later, for example. It is preferably 22,000 to 28,000.
  • the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
  • the degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, still more preferably 1.6 or more.
  • the upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.
  • the polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X). It is more preferable that the compound has a polymerizable group. As the polymerizable group, a radically polymerizable group is preferable. Further, it may be a compound represented by the following formula (X) and having a polar conversion group such as an acid-degradable group. In formula (X), R 133 represents a divalent organic group and R 134 represents a tetravalent organic group.
  • the polar converting group such as a polymerizable group or an acid-degradable group may be located at at least one of R 133 and R 134 , and may be located at least one of the following. It may be located at the terminal of polybenzoxazole as shown in the formula (X-1) or the formula (X-2). Equation (X-1) In formula (X-1), at least one of R 135 and R 136 is a polar converting group such as a polymerizable group or an acid-degradable group, and is not a polar converting group such as a polymerizable group or an acid-degradable group.
  • R 137 is a polar converting group such as a polymerizable group or an acid-degradable group, the other is a substituent, and the other group is synonymous with the formula (X).
  • a polar converting group such as a polymerizable group or an acid-degradable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the above-mentioned polyimide precursor or the like.
  • R 133 represents a divalent organic group.
  • the divalent organic group include aliphatic or aromatic groups. Specific examples include the example of R 121 in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that of R 121.
  • R 134 represents a tetravalent organic group.
  • the tetravalent organic group include R 122 in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that of R 122.
  • four conjugates of a tetravalent organic group exemplified as R 122 combine with a nitrogen atom and an oxygen atom in the above formula (X) to form a fused ring.
  • R 134 is the following organic group, it forms the following structure.
  • Polybenzoxazole preferably has an oxazole formation rate of 85% or more, more preferably 90% or more.
  • the oxazole formation rate is 85% or more, the membrane shrinkage due to ring closure that occurs when oxazoled by heating is reduced, and the occurrence of warpage can be suppressed more effectively.
  • the polybenzoxazole may comprise a repeating structural unit of formula (X), all comprising one R 131 or R 132 , comprising two or more different types of R 131 or R 132. It may include the repeating unit of X). Further, the polybenzoxazole may contain other types of repeating structural units in addition to the repeating unit of the above formula (X).
  • the resulting polybenzoxazole for example, a bis-aminophenol derivative, a dicarboxylic acid or the dicarboxylic acid containing R 133, is reacted with a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives, the polybenzoxazole precursor ,
  • a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives the polybenzoxazole precursor .
  • This can be obtained by oxazole using a known oxazole reaction method.
  • a dicarboxylic acid an active ester-type dicarboxylic acid derivative that has been previously reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield or the like.
  • the weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is in the above range.
  • a polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
  • it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
  • an organic solvent in the reaction.
  • 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 may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, promotion of cyclization reaction by acting a catalyst), or directly. , Polyimide may be synthesized.
  • non-halogen catalyst a known amidation catalyst containing no halogen atom can be used without particular limitation.
  • a boroxin compound, an N-hydroxy compound, a tertiary amine, a phosphoric acid ester, or an amine can be used.
  • carbodiimide compounds such as salts and urea compounds.
  • the carbodiimide compound include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide and the like.
  • a polyimide precursor or the like is used as an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. It is preferable to seal the end of the resin. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-.
  • a step of precipitating a solid may be included in the production of a polyimide precursor or the like.
  • the polyimide precursor or the like in the reaction solution can be precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
  • the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.
  • the content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the composition. It is more preferably 50% by mass or more, and even more preferably 50% by mass or more.
  • the resin content in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less, based on the total solid content of the composition. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
  • the composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • the curable resin composition of the present invention preferably contains at least two kinds of resins.
  • the curable resin composition of the present invention may contain two or more kinds of a specific resin and another resin described later in total, or may contain two or more kinds of a specific resin, but is specific. It is preferable to contain two or more kinds of resins.
  • the curable resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimide precursors having different structures derived from dianhydride (R 115 in the above formula (2)). It is preferable to contain the polyimide precursor of.
  • the composition of the present invention may contain the above-mentioned specific resin and another resin (hereinafter, also simply referred to as “other resin”) different from the specific resin.
  • other resins include polyamide-imide, polyamide-imide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, acrylic resin and the like.
  • acrylic resin by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained.
  • the composition may be obtained 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 solvent resistance of an organic film, and the like.
  • the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the composition. It is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, still more preferably 10% by mass or more. ..
  • the content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass, based on the total solid content of the composition. It is more preferably less than or equal to, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the content of the other resin may be low.
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the composition. Further, it is more preferably 5% by mass or less, further 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 composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
  • the curable resin composition of the present invention contains a compound having an oxazoline group.
  • the hydrogen atom in the oxazoline group may be substituted with a known substituent.
  • an embodiment in which the compound having an oxazoline group has an unsubstituted oxazoline group as the oxazoline group is also one of the preferred embodiments of the present invention.
  • the oxazoline group is preferably a group represented by the following formula (1-1).
  • R 1 to R 4 independently represent a hydrogen atom or a substituent, and * represents a binding site with another structure.
  • R 1 to R 4 are all hydrogen atoms or alkyl groups. Examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms.
  • the compound having an oxazoline group may be a compound containing only one oxazoline group in the structure, but from the viewpoint of adhesion of the cured film to the metal, the compound containing two or more oxazoline groups in the structure is used. It is preferable to have.
  • the compound having an oxazoline group preferably contains a polymerizable group.
  • the polymerizable group include known polymerizable groups such as a radically polymerizable group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group and a (blocking) isocyanate group.
  • the compound having an oxazoline group has at least one group selected from the group consisting of a radically polymerizable group and an alkoxysilyl group as the polymerizable group. It is preferable to include it.
  • the alkoxysilyl group may be any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group, but a trialkoxysilyl group is preferable from the viewpoint of adhesion of the cured film to the metal.
  • a trialkoxysilyl group is preferable from the viewpoint of adhesion of the cured film to the metal.
  • an alkoxy group in the alkoxysilyl group an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and an ethoxy group is further preferable.
  • a group having an ethylenically unsaturated bond is preferable.
  • the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group.
  • Acryloyloxy groups are preferred.
  • the compound having an oxazoline group preferably contains an azole group. According to the above aspect, it is considered that the adhesion with the metal is further improved by coordinating the azole group with a metal such as copper.
  • the azole group in the compound having an oxazoline group is a complex 5-membered ring compound containing one or more nitrogen atoms as a ring member, and hydrogen from a complex 5-membered ring compound which may have a substituent or a fused ring structure.
  • It may be a group having a structure excluding one or more atoms, but it is a complex 5-membered ring compound containing only one or more nitrogen atoms and one or a plurality of carbon atoms as ring members, and has a substituent. It is preferable that the group has a structure in which one or more hydrogen atoms are removed from the complex 5-membered ring compound which may be used.
  • the azole groups include a pyrrole ring, a pyrazole ring, an indazole ring, an imidazole ring, a benzimidazole ring, a 1,2,3-triazole ring, and a 1,2,4-triazole ring.
  • the azole group in the compound having an oxazoline group is preferably a group represented by the following formula (B-1) or the following formula (B-2).
  • RB1 represents a binding site with another structure, a hydrogen atom or a monovalent organic group
  • R B7 represents a binding site, a hydrogen atom or a monovalent organic group with other structures, of R B1 and R B7 contained in the formula (B1), the binding site of the at least one other structure Represents;
  • RB2 to RB6 independently represent a bond site with another structure, a hydrogen atom or a monovalent organic group
  • the binding site of the R B8 other structures represent a hydrogen atom or a monovalent organic group, of R B2 ⁇ R B6 and R B8 included in the formula (B2), at least One represents a binding site with another structure.
  • RB1 represents a binding site with another structure, a hydrogen atom or a monovalent organic group, and is more preferably a binding site with another structure.
  • the monovalent organic group represented by R B1 not particularly limited, but as long as the effect of the present invention are obtained can be used known organic group, a hydrocarbon group or a carboxy group It is preferably an alkyl group or a carboxy group, more preferably.
  • the number of carbon atoms of the hydrocarbon group or the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 4.
  • it is preferable that three of Z B1 to Z B4 are nitrogen atoms and one is CR B7 ⁇ .
  • Z B1 and Z B3 nitrogen atoms
  • Z B1 and Z B2 nitrogen atoms
  • Z B3 and Z B4 CR.
  • RB7 is preferably a hydrogen atom or a monovalent organic group.
  • RB7 is preferably a binding site with another structure.
  • a preferred embodiment of the monovalent organic group in R B7 is similar to the preferred embodiment of the monovalent organic group in the above R B1.
  • R B1 and R B7 contained in the formula (B1) at least one represents a bonding site with the other structures, it is preferable that at least R B1 represents a binding site with another structure. Further, in the equation (B1), only the R B1 represents a binding site with another structure, embodiments each represent R B7 independently a hydrogen atom or a monovalent organic group, preferred embodiments of the present invention 1 It is one.
  • Z B5 and Z B6 when Z B5 and Z B6 is representative of the either nitrogen atom, it is preferred that R B6 represents a binding site with another structure.
  • a mode in which both Z B5 and Z B6 represent a nitrogen atom and only RB6 represents a binding site with another structure is also one of the preferred embodiments of the present invention. be.
  • RB2 to RB5 each independently represent a hydrogen atom or a monovalent organic group.
  • a preferred embodiment of the monovalent organic group in R B2 ⁇ R B5 is the same as the preferred embodiment of the monovalent organic group in the above R B1.
  • a preferred embodiment of the monovalent organic group in R B6 are the same as the preferred embodiment of the monovalent organic group in the above R B1. In other cases, RB6 preferably represents a binding site with another structure.
  • R B8 preferably represents a binding site with another structure.
  • the other represents a hydrogen atom or a monovalent organic group.
  • a preferred embodiment of the monovalent organic group in R B8 are the same as the preferred embodiment of the monovalent organic group in the above R B1.
  • R B2 ⁇ R B6 and R B8 included in the formula (B2) at least one represents a binding site with another structure, at least R B6 or R B8 represents a binding site with another structure Is preferable. Further, in the formula (B-2), only one of RB6 and RB8 represents a binding site with another structure, and the other of RB6 and RB8 and RB2 to RB5 are independently hydrogen atoms. Alternatively, an embodiment representing a monovalent organic group is also one of the preferred embodiments of the present invention.
  • the azole group is preferably a group represented by any of the following formulas (B-3) to (B-6).
  • RB9 to RB20 each independently represent a hydrogen atom or a monovalent organic group, and * represents a binding site with another structure.
  • (B-3) ⁇ formula (B-6) preferred embodiments of the monovalent organic group in R B9 ⁇ R B20 are the same as the preferred embodiment of the monovalent organic group in the above R B1.
  • the compound having an oxazoline group may be a compound having a molecular weight of less than 2,000 (hereinafter, also referred to as “oxazoline group-containing low molecular weight compound”) or a resin (hereinafter, also referred to as “oxazoline group-containing resin”). May be. Further, from the viewpoint of adhesion of the cured film to the metal, it is also preferable that the curable resin composition contains both an oxazoline group-containing low molecular weight compound and an oxazoline group-containing resin. From the viewpoint of adhesion, the compound having an oxazoline group is preferably a resin.
  • the molecular weight of the oxazoline group-containing low molecular weight compound is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.
  • the number of oxazoline groups in the oxazoline group-containing low molecular weight compound is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. From the viewpoint of adhesion, the number of oxazoline groups in the oxazoline group-containing low molecular weight compound is preferably 2 to 10, more preferably 2 to 4, and even more preferably 2.
  • a compound represented by the following formula (BL-1) or formula (BL-2) is preferable.
  • R 1 to R 4 independently represent a hydrogen atom or a substituent
  • R 5 represents a substituent.
  • R 1 to R 4 independently represent a hydrogen atom or a substituent
  • L 1 represents a single bond or an n + 1 valent linking group
  • n represents an integer of 2 or more.
  • R 1 to R 4 are independently synonymous with R 1 to R 4 in the formula (1-1), and the preferred embodiments are also the same.
  • R 5 represents a substituent, an azole group described above or, preferably a group containing a polymerizable group include more be a group containing a polymerizable group described above preferable. Further, embodiments R 5 is a vinyl group is one of the preferred embodiments of the present invention.
  • R 1 to R 4 are independently synonymous with R 1 to R 4 in the formula (1-1), and the preferred embodiments are also the same.
  • L 1 represents a single bond or an n + 1 valent linking group, and a single bond or a hydrocarbon group is preferable.
  • the hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but an aromatic hydrocarbon group or a saturated aliphatic hydrocarbon group is preferable, and an aromatic hydrocarbon group is preferable.
  • a group is more preferable, and a group obtained by removing n + 1 hydrogen atoms from the benzene ring is further preferable.
  • n represents an integer of 2 or more, preferably an integer of 2 to 10, more preferably an integer of 2 to 4, and even more preferably 2.
  • the weight average molecular weight of the oxazoline group-containing resin is preferably 3,000 to 150,000, more preferably 3,000 to 80,000, and even more preferably 6,000 to 50,000. ..
  • the molar amount of the oxazoline group in 1 g of the oxazoline group-containing resin is preferably 0.001 to 10 mmol / g, more preferably 0.1 to 10 mmol / g, and 0.5 to 9 mmol / g. Is even more preferable.
  • the oxazoline group-containing resin is preferably a resin having a repeating unit containing an oxazoline group.
  • a repeating unit represented by the following formula (BO-1) is preferable.
  • BO-1 a repeating unit represented by the following formula (BO-1) is preferable.
  • L B represents a single bond or a divalent linking group
  • X B represents an oxazoline group
  • R B represents a hydrogen atom or a methyl group.
  • L B represents a single bond.
  • 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.
  • (BO-1) the details of the oxazoline group is X B is as described above, a group represented by the formula (1-1) is preferred.
  • R B is preferably a methyl group.
  • the oxazoline group-containing resin preferably further contains other repeating units that are different from the repeating units containing the oxazoline group.
  • the other repeating unit include a repeating unit containing an azole group, a repeating unit containing a polymerizable group, and the like.
  • the oxazoline group-containing resin preferably contains a repeating unit represented by the following formula (BA-1) as a repeating unit containing an azole group.
  • BA-1 a repeating unit represented by the following formula (BA-1) as a repeating unit containing an azole group.
  • L 3 represents a single bond or a divalent linking group
  • X 3 represents an azole group
  • R represents a hydrogen atom or a methyl group.
  • L 3 represents a single bond or a divalent linking group.
  • a group represented by a bond with at least one group selected from the group is preferable, and a hydrocarbon group is more preferable.
  • the above RN is as described above.
  • As the hydrocarbon group a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
  • the hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
  • L 3 is a single bond, preferably a group represented by the following formula (BA-1-1) a group or the following formula represented (BA-1-2).
  • BA-1-1) or formula (BA-1-2) L 4 represents a divalent linking group
  • L 5 represents a single-bonded or divalent linking group
  • L 6 represents a divalent linking group.
  • L 7 represents a single bond or a divalent linking group
  • * represents a bonding site with a carbonyl group in the formula (BA-1)
  • a 1 and A 2 represent -O- or -NR. It represents N ⁇
  • # represents the binding site with X 3 in (BA-1).
  • a group represented by a bond with at least one group selected from the group consisting of NR N ⁇ is preferable, and a hydrocarbon group is more preferable.
  • the above RN is as described above.
  • As the hydrocarbon group a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
  • the hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
  • L 5 represents a single bond.
  • L 5 is a divalent linking group
  • a group represented by a bond with at least one group selected from the group consisting of and -NR N- is preferable, and a hydrocarbon group is more preferable.
  • L 6 is synonymous with L 4 in the formula (BA-1-1), and the preferred embodiment is also the same.
  • L 7 is preferably a divalent linking group.
  • L 7 is a divalent linking group
  • the preferred embodiment of L 7 is the same as the preferred embodiment when L 5 is a divalent linking group in the above formula (BA-1-1).
  • a 1 and A 2 represent -O- or -NR N- , and -O- is preferable.
  • RN is as described above.
  • the oxazoline group-containing resin may contain only one type of repeating unit represented by the formula (BA-1), or may contain two or more types.
  • the molar amount of the azole group contained in 1 g of the oxazoline group-containing resin is preferably 0.001 to 10 mmol / g, preferably 0.1 to 8 mmol / g. Is more preferable.
  • the oxazoline group-containing resin preferably contains a repeating unit represented by the following formula (BA-2) as a repeating unit containing a polymerizable group.
  • BA-2 a repeating unit represented by the following formula (BA-2) as a repeating unit containing a polymerizable group.
  • BA-2 A 3 is -O- or -NR N - represents, L P1 represents a divalent linking group, X P1 represents a polymerizable group, R represents a hydrogen atom or a methyl group show.
  • a 3 is -O- or -NR N - represents, -O- it is preferable.
  • RN is as described above.
  • a group represented by a bond with at least one group selected from the group consisting of 2- and -NR N- is preferable, and a hydrocarbon group is more preferable.
  • the above RN is as described above.
  • As the hydrocarbon group a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
  • the hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
  • X P1 represents a polymerizable group, alkoxysilyl group, an epoxy group, oxetanyl group or preferably a radical polymerizable group, alkoxysilyl group is more preferable.
  • Preferred embodiments of the alkoxysilyl group and the radically polymerizable group are as described above.
  • the oxazoline group-containing resin may contain only one type of repeating unit represented by the formula (BA-2), or may contain two or more types.
  • the oxazoline group-containing resin contains a repeating unit represented by a plurality of kinds of formulas (BA-2) having different polymerizable groups.
  • the oxazoline group-containing resin contains a repeating unit represented by the formula (BA-2) containing an alkoxysilyl group as a polymerizable group and a group different from the alkoxysilyl group as a polymerizable group (BA-). It is preferable to include the repeating unit represented by 2).
  • the molar amount of the polymerizable group in 1 g of the oxazoline group-containing resin is preferably 0.001 to 10 mmol / g, preferably 0.01 to 5 mmol. It is more preferably / g.
  • the oxazoline group-containing resin may further have another repeating unit different from the repeating unit represented by the above formula (BA-1) or the formula (BA-2).
  • Other repeating units include, for example, repeating units derived from styrene or substituted styrene.
  • Specific examples of the compound having an oxazoline group include, but are not limited to, the compound used in the examples.
  • the content of the compound having an oxazoline group is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, based on the total solid content of the curable resin composition of the present invention. It is preferably 0.15 to 2% by mass, more preferably 0.15 to 2% by mass.
  • the curable resin composition of the present invention may contain only one compound having an oxazoline group, or may contain two or more compounds. When two or more compounds having an oxazoline group are contained, the total amount is preferably in the above range.
  • the curable resin composition of the present invention contains a compound containing an acid group and an alkoxysilyl group.
  • a carboxy group, a phenolic hydroxy group and an aromatic thiol group are preferable, and a carboxy group is more preferable.
  • the preferred embodiment of the alkoxysilyl group in the compound containing an acid group and the alkoxysilyl group is the same as the preferred embodiment of the alkoxysilyl group in the above-mentioned compound having an oxazoline group.
  • the compound containing an acid group and an alkoxysilyl group contains a polymerizable group different from the alkoxysilyl group.
  • the polymerizable group different from the alkoxysilyl group include known polymerizable groups such as a radically polymerizable group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group and a (blocking) isocyanate group, and a radically polymerizable group.
  • an epoxy group is preferable, and a radically polymerizable group is more preferable.
  • the compound containing an acid group and an alkoxysilyl group preferably contains an azole group.
  • the azole group examples include the azole groups described in the above-mentioned compounds having an oxazoline group, and the same applies to preferred embodiments.
  • the compound containing an acid group and an alkoxysilyl group contains at least one group selected from the group consisting of a radically polymerizable group and an azole group. Is preferable.
  • the compound containing an acid group and an alkoxysilyl group may be a compound having a molecular weight of less than 2,000 (hereinafter, also referred to as “low molecular weight compound C”) or a resin (hereinafter, also referred to as “resin C”). May be. Further, from the viewpoint of the adhesion of the cured film to the metal, it is also preferable that the curable resin composition contains both the low molecular weight compound C and the resin C. From the viewpoint of adhesion, the compound containing an acid group and an alkoxysilyl group is preferably a resin.
  • the molecular weight of the low molecular weight compound C is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.
  • the number of acid groups in the low molecular weight compound C is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.
  • the number of alkoxysilyl groups in the low molecular weight compound C is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.
  • the weight average molecular weight of the resin C is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, and even more preferably 5,000 to 50,000.
  • the molar amount of the acid group in 1 g of the resin C is preferably 0.01 mmol / g to 15 mmol / g, more preferably 0.05 mmol / g to 10 mmol / g, and 0.1 to 3 mmol / g. Is more preferable.
  • the molar amount of the alkoxysilyl group in 1 g of the resin C is preferably 0.001 to 10 mmol / g, more preferably 0.01 to 10 mmol / g, and 0.1 to 5 mmol / g. Is more preferable.
  • the resin C is preferably a resin having a repeating unit containing an acid group and a repeating unit containing an alkoxysilyl group, or a resin having a repeating unit containing an acid group and an alkoxysilyl group, preferably an acid group. It is more preferable that the resin has a repeating unit containing the above and a repeating unit containing an alkoxysilyl group.
  • a repeating unit represented by the following formula (CA-1) or formula (CA-2) is preferable.
  • CA-1) or Formula (CA-2) A C is -O- or -NR N - represents, L C represents a divalent linking group, X C denotes a group, R represents Represents a hydrogen atom or a methyl group.
  • CA-2 it is preferred that A C is -O-.
  • the above RN is as described above.
  • the hydrocarbon group a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
  • the hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
  • X C is a carboxy group, a phenolic hydroxy group or an aromatic thiol group is preferred, a carboxyl group is more preferable.
  • a repeating unit represented by the above formula (BA-2), wherein XP1 is an alkoxysilyl group is preferably mentioned.
  • the resin C may have a repeating unit containing an azole group.
  • the repeating unit containing an azole group in the resin C the repeating unit represented by the above formula (BA-1) is preferably mentioned.
  • the molar content of the azole group in 1 g of the resin C is preferably 0.001 to 10 mmol / g, and preferably 0.1 to 5 mmol / g. More preferred.
  • the resin C may further have other repeating units.
  • a repeating unit represented by the above formula (BA-2) X P1 can be mentioned a repeating unit such as a different polymerizable group and alkoxysilyl group.
  • the content of the compound containing an acid group and an alkoxysilyl group is preferably 0.05 to 10% by mass, preferably 0.10 to 5% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.15 to 2% by mass, and even more preferably 0.15 to 2% by mass.
  • the curable resin composition may contain only one kind of compound containing an acid group and an alkoxysilyl group, or may contain two or more kinds. When two or more compounds containing an acid group and an alkoxysilyl group are contained, the total amount is preferably in the above range.
  • the curable resin composition is a compound having an azole group and does not fall under any of the above-mentioned compounds having an oxazoline group and compounds containing an acid group and an alkoxysilyl group (“other compounds having an azole group”). Also referred to as "compound").
  • the preferred embodiment of the azole group in the other compound having an azole group is the same as the preferred embodiment of the azole group in the above-mentioned compound having an oxazoline group.
  • the other compound having an azole group is preferably a compound having no polymerizable group. The details of the polymerizable group are synonymous with the polymerizable group in the above-mentioned compound having an oxazoline group.
  • the other compound having an azole group is preferably a compound represented by the following formula (AZ-1) or the following formula (AZ-2).
  • Z 1 and Z 3 is a nitrogen atom
  • Z 1 and Z 3 are nitrogen atoms
  • R 1 is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
  • the hydrocarbon group or the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms.
  • R 7 is the same as that of R 1.
  • R 2 to R 6 and R 8 are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and a hydrogen atom. Is particularly preferable.
  • the molecular weight of the other compound having an azole group is preferably 67 to 500, more preferably 68 to 300.
  • the content of the other compound having an azole group is preferably 0.05 to 10% by mass, preferably 0.10 to 5% by mass, based on the total solid content of the curable resin composition of the present invention. Is more preferable, and 0.15 to 2% by mass is further preferable.
  • the curable resin composition may contain only one kind of other compounds having an azole group, or may contain two or more kinds. When two or more other compounds having an azole group are contained, the total amount is preferably in the above range.
  • the curable resin composition of the present invention may contain the above-mentioned compound having an oxazoline group and a silane coupling agent (“other silane coupling agent”) different from any of the compounds containing an acid group and an alkoxysilyl group. good.
  • a silane coupling agent a compound having an alkoxysilyl group and no acid group and an oxazoline group is preferable.
  • a resin containing a repeating unit containing an alkoxysilyl group may be used as another silane coupling agent.
  • the resin may further contain repeating units containing a polymerizable group different from alkoxysilyl. Examples of the repeating unit containing the alkoxysilyl group and the repeating unit containing a polymerizable group different from the alkoxysilyl include the repeating unit represented by the above formula (BA-2).
  • Examples of other silane coupling agents 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, and International Publication No. 2011/080992.
  • the above-mentioned compounds having an oxazoline group and compounds not falling under any of the compounds containing an acid group and an alkoxysilyl group can be mentioned.
  • silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358.
  • examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid.
  • Et represents an ethyl group.
  • the content of the other silane coupling agent is preferably 0.05 to 10% by mass, preferably 0.10 to 5% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.15 to 2% by mass, and even more preferably 0.15 to 2% by mass.
  • the curable resin composition may contain only one type of other silane coupling agent, or may contain two or more types. When two or more other silane coupling agents are contained, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably 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, cyclic 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.
  • alkyl oxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)
  • alkyl oxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) Ethyl ethoxyacetate, etc.)
  • 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • 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.
  • cyclic hydrocarbons for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene 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.
  • a combination of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and ⁇ -butyrolactone is also preferable.
  • the curable resin composition of the present invention preferably contains esters, and more preferably contains a lactone-based solvent.
  • the lactone-based solvent refers to a solvent containing a lactone structure, and examples thereof include ⁇ -butyrolactone, ⁇ -caprolactone, and ⁇ -valerolactone.
  • the content of the lactone-based solvent with respect to the total mass of the solvent is not particularly limited, but is preferably 30 to 100% by mass, more preferably 40 to 95% by mass, and more preferably 50 to 90% by mass. More preferred.
  • 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 preferably 10 to 70% by mass, and even 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 be contained in only one kind, or may be contained in two or more kinds. When two or more kinds of solvents are contained, the total is preferably in the above range.
  • the composition of the present invention preferably contains a photosensitive agent.
  • a photosensitive agent a photopolymerization initiator is preferable.
  • the composition of the present invention preferably contains a photopolymerization initiator as the photosensitive agent.
  • 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.
  • it may be an active agent that causes some action with a photoexcited sensitizer and generates an active radical.
  • the photoradical polymerization initiator the oxime compound described later is preferable.
  • 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, hexaarylbiimidazoles, oxime derivatives and the like.
  • Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azido compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned.
  • the description in paragraphs 0165 to 0182 of JP-A-2016-027357 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.
  • ketone compound for example, the compound described in paragraph 0087 of JP-A-2015-087611 is exemplified, and the content thereof is 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 No. 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 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (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 and IRGACURE-784EG (both manufactured by BASF).
  • the photoradical polymerization initiator is more preferably an oxime compound.
  • the oxime compound By using the oxime compound, it becomes possible to improve the exposure latitude 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-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimimino-1-phenylpropane-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 PTOMER N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014052).
  • a radical polymerization initiator 2) is also preferably used.
  • TR-PBG-304 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
  • ADEKA Arklus NCI-831 and ADEKA Arklus NCI-930 manufactured by ADEKA Corporation
  • 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 includes the compounds described in JP-A-2010-262028, the 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 Japanese Patent Publication No. 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 includes 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, and a triaryl.
  • a trihalomethyltriazine compound Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxadiazole compound, 3-aryl substituted coumarin compound.
  • Compounds are preferred.
  • 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 a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, a metallocene compound or an oxime compound is further preferable, and an oxime compound is further 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).
  • -Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanol-1, alkylanthraquinone, etc.
  • 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 I 04, 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. 2015/125469 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 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 composition of the present invention contains a photoacid generator as a photosensitive agent.
  • a photoacid generator for example, acid is generated in the exposed portion of the composition layer, the solubility of the exposed portion in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed portion is formed by the developing solution. A positive pattern to be removed can be obtained.
  • the composition contains a photoacid generator and a polymerizable compound other than the radically polymerizable compound described later, for example, the acid generated in the exposed portion promotes the crosslinking reaction of the polymerizable compound. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion. According to such an embodiment, a negative pattern can be obtained.
  • 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-nitrobenzylsulfonate.
  • the quinone-diazide compound includes 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 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 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.
  • the photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
  • oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-). It is preferably the oxime sulfonate compound represented by 105).
  • X 3 is an alkyl group, an alkoxyl group, or a halogen atom. If X 3 there are a plurality, each be the same or may be different. Alkyl group and an alkoxyl group represented by X 3 may have a substituent.
  • the halogen atom in the X 3, a chlorine atom or a fluorine atom is preferable.
  • m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X 3 may be the same or different.
  • R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl group of numbers 1 to 5, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W.
  • W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms.
  • oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-200969A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.
  • R s1 represents an alkyl group, an aryl group or a heteroaryl group
  • R s6 which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
  • Xs represents O or S.
  • ns represents 1 or 2
  • ms represents an integer from 0 to 6.
  • an alkyl group represented by R s1 preferably 1 to 30 carbon atoms
  • an aryl group preferably 6 to 30 carbon atoms
  • a heteroaryl group preferably numbers 4 to 30
  • R s1 preferably 1 to 30 carbon atoms
  • aryl group preferably 6 to 30 carbon atoms
  • heteroaryl group preferably numbers 4 to 30
  • T may have a substituent T.
  • R s2 is preferably a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms) or an aryl group (preferably 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable.
  • the Rs2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
  • the alkyl group or aryl group represented by R s2 may have a substituent T.
  • Xs represents O or S, and is preferably O.
  • the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
  • ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
  • the alkyl group represented by R s6 preferably having 1 to 30 carbon atoms
  • the alkyloxy group preferably having 1 to 30 carbon atoms
  • ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
  • the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111).
  • the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.
  • R t1 represents an alkyl group, an aryl group or a heteroaryl group
  • R t7 represents a hydrogen atom or a bromine atom
  • R t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups
  • R t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups
  • R t2 represents a hydrogen atom or a methyl group.
  • R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
  • R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, and a phenyl group.
  • it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.
  • R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
  • R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
  • the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
  • Specific examples of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692 and paragraphs of JP-A-2015-194674.
  • the compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
  • oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
  • Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, and the like. Represents an aryl group or a heteroaryl group.
  • R u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
  • Ru2a represents an alkyl group or an aryl group.
  • Xu is -O-, -S-, -NH- , -NR u5-, -CH 2- , -CR u6 H- or CR u6 R u7.
  • R u5 to R u7 independently represent an alkyl group or an aryl group, respectively.
  • Ru1 to Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. 2 in turn, each may be bonded to each other to form a ring of the R u1 ⁇ R u4. At this time, the ring may be condensed to form a fused ring together with the benzene ring.
  • R u1 ⁇ R u4 a hydrogen atom, preferably a halogen atom or an alkyl group, also aspects to form the at least two aryl groups bonded to each other of R u1 ⁇ R u4 preferred.
  • Ru1 to Ru4 are hydrogen atoms. Any of the above-mentioned substituents may further have a substituent.
  • the compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
  • the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
  • Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-20969 and paragraph numbers 0195 to 0207 of JP-A-2015-194674. And these contents are incorporated herein.
  • b-9, b-16, b-31, and b-33 are preferable.
  • 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-443, WPAG-469, WPAG-638, and WPAG-690 (any of which).
  • Fujifilm Wako Pure Chemical Industries, Ltd. Omnicat 250, Omnicat 270 (all manufactured by IGM Resins BV), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF), MBZ-101 (all manufactured by BASF). (Made by Midori Chemical Industries, Ltd.) and the like.
  • an organic halogenated compound can also be applied.
  • the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A. 48-36281, JP-A-55-3207, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62- 212401, JP-A-63-70243, JP-A-63-298339, M.D. P.
  • S-triazine compounds S-triazine compounds
  • an organic borate compound can also be applied.
  • the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, and JP-A-2000. -131837, JP-A-2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin "Rad Tech'98. Proceeding Compound 19-22, 1998, Chicago", etc.
  • Japanese Patent Laid-Open No. 6-175553 Organic Boron Iodonium Complex
  • Japanese Patent Application Laid-Open No. 9-188710 Organic Boron Phosphorium Complex
  • JP-A-7-128785 JP-A.
  • Specific examples thereof include organic boron transition metal coordination complexes of JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014.
  • a disulfone compound can also be applied as a photoacid generator.
  • examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.
  • onium salt compound examples include S. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.I. S. The diazonium salt described in Bal et al, Polymer, 21, 423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069, Phosphonium salts described in 055 and 4,069,056, European Patents 104 and 143, US Patents 339,049 and 410,201, JP-A-2. -150848, Iodonium salt described in JP-A-2-296514, European Patent Nos.
  • onium salts examples include onium salts represented by the following general formulas (RI-I) to (RI-III).
  • Ar11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 1 to 12 carbon atoms.
  • Z11 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, surface stability
  • Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion are preferable.
  • Ar21 and Ar22 each represent an aryl group having 20 or less carbon atoms which may independently have 1 to 6 substituents, and a preferable substituent is an alkyl group having 1 to 12 carbon atoms.
  • Alkylamino group with 1 to 12 carbon atoms dialkylamino group with 1 to 12 carbon atoms, alkylamide group or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, 1 to 12 carbon atoms
  • Examples thereof include a thioalkyl group of 1 to 12 and a thioaryl group having 1 to 12 carbon atoms.
  • Z21 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
  • R31, R32, and R33 each represent an aryl group or an alkyl group having 20 or less carbon atoms, an alkenyl group, and an alkynyl group, which may independently have 1 to 6 substituents, and are preferable. From the viewpoint of reactivity and stability, an aryl group is desirable.
  • Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.
  • Examples thereof include a group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms.
  • Z31 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
  • 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 composition of the present invention. It is more preferably 2 to 15% by mass. 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 photobase generator as a photosensitive agent.
  • the curable resin composition contains a photobase generator and a cross-linking agent described later, for example, the cross-linking reaction of the cross-linking agent is promoted by promoting the cyclization of the specific resin by the base generated in the exposed portion. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion due to such an action. According to such an aspect, a negative type relief pattern can be obtained.
  • the photobase generator is not particularly limited as long as it generates a base by exposure, and known ones can be used.
  • M. Shirai, and M. Tsunooka Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C.I. Kutal, Code. Chem. Rev. , 211,353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mother. , 11, 170 (1999); H. Tachi, M. et al. Shirai, and M. Tsunooka, J.M. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J.M.
  • Ionic compounds whose base components are neutralized by forming salts and nonionic compounds whose base components are latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds.
  • carbamate derivatives, amide derivatives, imide derivatives, ⁇ -cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives and the like are more preferable examples of the photobase generator.
  • the basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines. From the viewpoint of the imidization rate, it is preferable that the basic substance has a large pKa in DMSO (dimethyl sulfoxide) of the conjugate acid.
  • the pKa is preferably 1 or more, and more preferably 3 or more.
  • the upper limit of the above pKa is not particularly limited, but is preferably 20 or less.
  • pKa represents the logarithm of the reciprocal of the first dissociation constant of acid
  • pKa represents the logarithm of the reciprocal of the first dissociation constant of acid
  • the photobase generator is preferably a photobase generator that does not contain a salt in the structure, and the nitrogen atom of the base portion generated in the photobase generator is preferable. It is preferable that there is no charge on the top.
  • the photobase generator it is preferable that the generated base is latent using a covalent bond, and the mechanism of base generation is such that the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is cleaved. It is preferable that the base is generated.
  • the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is better and the pot life is improved.
  • the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
  • the photobase generator is preferably a photobase generator containing a salt in the structure.
  • the base generated as described above is latent using a covalent bond, and the generated base has an amide bond, a carbamate bond, and an oxime bond. It is preferably latent using.
  • the photobase generator according to the present invention include a photobase generator having a cinnamon acid amide structure as disclosed in JP-A-2009-080452 and International Publication No. 2009/123122, JP-A-2006-189591.
  • Examples thereof include a photobase generator having an oxime structure, but the present invention is not limited to these, and other known photobase generator structures can be used.
  • the photobase generator the compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746, and the compounds described in paragraphs 0022 to 0069 of JP2013-194205.
  • Examples thereof include the compounds described in paragraphs 0026 to 0074 of JP2013-204319A, and the compounds described in paragraph number 0052 of International Publication No. 2010/064631.
  • a commercially available product may be used as the photobase generator.
  • Commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-207, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG. -166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), A2502, B5085, N0528, N1052, O0396, O0447, O0448 ( (Made by Tokyo Chemical Industry 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 photobase generator may be contained, or two or more types may be contained. When two or more photobase generators are contained, the total is preferably in the above range.
  • the composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator.
  • the 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 resin and the polymerizable compound can be promoted in the heating step described later, so that the solvent resistance can be further improved.
  • thermal radical polymerization initiator examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
  • 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 composition of the present invention. More preferably, it is 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 composition of the present invention may contain a thermoacid generator.
  • the thermoacid generator generates an acid by heating and promotes a cross-linking reaction of 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. It has the effect of making it.
  • 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 the composition is applied to the substrate, and at the time of final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
  • the thermal decomposition start temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the thermal acid 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 thermal acid 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 JP2013-072935.
  • those that generate an alkyl sulfonic acid having 1 to 4 carbon atoms or a haloalkyl sulfonic acid having 1 to 4 carbon atoms are more preferable from the viewpoint that there is little residue in the organic film and it is difficult to deteriorate the physical properties of the organic 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, 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, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
  • the curable resin composition of the present invention may further contain an onium salt.
  • an onium salt when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain an onium salt.
  • the type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt or phosphonium salt are preferably mentioned.
  • an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and 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 the anion may or may not be bonded via a covalent bond. .. That is, the onium salt may be an intramolecular salt having a cation part and an anion part 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 thermal base generator described later.
  • the thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.
  • Examples of the onium salt include the onium salt described in paragraphs 0122 to 0138 of International Publication No. 2018/043262.
  • onium salts used in the field of polyimide precursors can be used without particular limitation.
  • 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 kinds are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention may further contain a thermosetting agent.
  • a 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.
  • the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators.
  • the nonionic thermal base 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 monocyclic ring or a condensed ring in which 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 a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and an alkenyl group (preferably 2 to 24 carbon atoms).
  • 2-18 is more preferred, 3-12 is more preferred
  • ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
  • 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 which 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.
  • 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.
  • cyclohexyl groups are more preferred.
  • Rb 3 examples include an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 18 carbon atoms). ⁇ 10 is more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms are more preferable).
  • 7 to 12 are more preferable), an arylalkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxyl group (preferably 1 to 24 carbon atoms, 2 to 2 to 24).
  • 18 is more preferred, 3 to 12 are more preferred), aryloxy groups (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 12 are even more preferred), or arylalkyloxy groups (7 to 12 carbon atoms are preferred).
  • 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
  • a cycloalkyl group (preferably 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 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), 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 effect of the present invention is exhibited.
  • 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 preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). , 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, still more 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, still more 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), and 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 thermal base 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.
  • thermo base generators or specific examples of thermal base generators other than the above-mentioned onium salts include the following compounds.
  • the content of the other 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, 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 thermal base generator one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a cross-linking agent.
  • the cross-linking agent include radical cross-linking agents and other cross-linking agents.
  • the curable resin composition of the present invention preferably further contains a radical cross-linking agent.
  • the radical cross-linking agent is a compound having a radically polymerizable group.
  • a group containing an ethylenically unsaturated bond is preferable.
  • the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group and a (meth) acryloyl group.
  • the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.
  • the radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more ethylenically unsaturated bonds.
  • the compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the ethylenically unsaturated bond.
  • the curable resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent.
  • the compound having 3 or more ethylenically unsaturated bonds a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable.
  • the compound having is more preferable.
  • the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds.
  • a compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
  • the curable resin composition of the present invention has a compound having two ethylenically unsaturated bonds and three or more ethylenically unsaturated bonds. It is also preferable to contain a compound.
  • the molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
  • radical cross-linking agent examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and are preferable.
  • 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 group or an epoxy group, 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 polyelectron substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a halogeno group.
  • Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
  • radical cross-linking agent 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-51-0379193.
  • Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof.
  • 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 radical cross-linking agent 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.
  • Compounds having two or more groups and cardo resins can also be used.
  • the compound described in JP-A No. 10-062986 together with specific examples as the formulas (1) and (2), which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also available. It can be used as a radical cross-linking agent.
  • dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol residues or propylene glycol residues. A structure that is bonded via the above
  • SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
  • SR-209 manufactured by Sartmer 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 are examples of the radical cross-linking agent.
  • 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 (Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.) And so on.
  • radical cross-linking agent examples include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-0322293, and Japanese Patent 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.
  • radical cross-linking agent compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do it.
  • the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
  • the radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
  • the radical cross-linking agent provided with the above is more preferable.
  • the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound.
  • 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 radical cross-linking agent 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 radical cross-linking agent is within the above range, it is excellent in manufacturable handling and further excellent in developability. Moreover, the polymerizability 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 bifunctional metal acrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
  • 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.
  • Glycoglycyl diacrylate polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol Dimethacrylate, dimethyrol-tricyclodecanediacrylate, dimethyrol-tricyclodecanedimethacrylate, EO adduct diacrylate of bisphenol A, EO adux glycol dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO of bisphenol A Additives dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having a ure
  • a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent.
  • the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth).
  • N-vinyl compounds such as acrylic acid derivatives, N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate and triallyl trimellitate are preferably used.
  • the monofunctional radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
  • the content thereof 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.
  • the radical cross-linking agent may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably in the above range.
  • the curable resin composition of the present invention contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
  • the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and a covalent bond is formed with another compound in the composition or a reaction product thereof by exposure to the above-mentioned photosensitizer.
  • the compound has a plurality of groups in the molecule that promote the formation reaction, and the reaction of forming a covalent bond with another compound in the composition or a reaction product thereof is the action of the acid or the base.
  • a compound having a plurality of groups promoted by the above in the molecule is preferable.
  • the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator which is a photosensitizer in the exposure step.
  • a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is a nitrogen atom.
  • a compound having a structure directly bonded to is more preferable.
  • an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to a methylol group or an alkoxymethyl group.
  • examples thereof include compounds having a substituted structure.
  • the method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
  • the cross-linking agent using melamine is a melamine-based cross-linking agent
  • the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent
  • the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent.
  • a cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
  • the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and preferably contains a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. It is more preferable to contain at least one compound selected from the group consisting of system cross-linking agents.
  • melamine-based cross-linking agent examples include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.
  • urea-based cross-linking agent examples include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl.
  • Glycol-uryl-based cross-linking agent such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea, Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propy
  • benzoguanamine-based cross-linking agent examples include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
  • Tetramethoxymethylated benzoguanamine Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Examples thereof include methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like.
  • a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
  • Compounds to which a group is directly bonded are also preferably used. Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylphenyl hydroxymethylbenzoate.
  • suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
  • the curable resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.
  • Epoxy compound (compound having an epoxy group)
  • 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; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether.
  • Examples include, but are not limited to, the contained silicone.
  • oxetane compound compound having an oxetanyl group
  • examples of 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. Alternatively, two or more types may be mixed.
  • Benzoxazine compound (compound having a benzoxazolyl group) Since the benzoxazine compound is a cross-linking reaction derived from the cycloaddition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
  • benzoxazine compound are BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (above, 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 other cross-linking agent 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 particularly preferably 1.0 to 10% by mass.
  • the other cross-linking agent may be contained in only one kind, or may be contained in two or more kinds. When two or more other cross-linking agents are contained, the total is preferably in the above range.
  • the curable 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.
  • 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. show.
  • 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 is preferably a compound having one sulfonamide structure.
  • 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 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 and a carboxy group.
  • 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, a naphthyl group and the like.
  • 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 isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a pyrimididin 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 bonded to form a ring structure, where R 4 is. * it is may form a ring structure and other structures that bind, R 5 may form a ring structure and other structures that bind *, * is independently other 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, a naphthyl group and the like.
  • 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 isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a pyrimididin 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-benzoylthiourea, 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-thiohydrantin.
  • 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 curable resin composition of the present invention. %, More preferably 0.2 to 3% by mass.
  • the curable 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 of them. When only one kind is contained, the content of the compound is preferably in the above range, and when two or more kinds are contained, the total amount thereof 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, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol (t-butylcatechol), 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso- N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4 -Methylphenol,
  • 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 even more preferably 0.05 to 2.5% by mass.
  • the polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total 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 adhesiveness improving agent include 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 and the like.
  • Aluminum-based adhesive aid examples include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), ethyl acetoacetate aluminum diisopropylate, and the like. Further, as the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can be used. ..
  • 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 kinds are used, it is preferable that the total is in the above range.
  • the curable resin composition of the present invention contains various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, and inorganic particles, if necessary, to the extent that the effects of the present invention can be obtained.
  • additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, and inorganic particles, if necessary, to the extent that the effects of the present invention can be obtained.
  • Curing agent, curing catalyst, filler, antioxidant, ultraviolet absorber, antiaggregating agent and the like can be 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 electronically excited state.
  • the sensitizer in the electronically excited state comes into contact with the thermal curing accelerator, the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur.
  • the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid, or a base.
  • sensitizer examples include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal).
  • a sensitizing dye may be used as the sensitizer.
  • the description in paragraphs 0161 to 0163 of JP-A-2016-027355 can be referred to, and the content thereof 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 Polymer Dictionary, Third Edition (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.
  • thiol compounds 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 is preferably in the above range.
  • a 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 a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the following surfactants are also preferable.
  • the parentheses indicating the repeating unit of the main chain indicate the content (mol%) of each repeating unit
  • the parentheses indicating the repeating unit of the side chain indicate the number of repetitions of each repeating unit.
  • the surfactant the compound described in paragraphs 0159 to 0165 of International Publication No.
  • 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 thereof include 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 in the thickness of the coating film and liquid saving, 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), KP341, KF6001, KF6002 (all 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 ethers, polyoxyethylene stearyl ethers, 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.
  • anion-type 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 based on 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 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 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 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 phenylsalicylate, 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- Hydroxyl-4-octoxybenzophenone and the like can be mentioned.
  • benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 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.
  • the triazine-based ultraviolet absorber 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin
  • the 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) diisopropoxiside, titanium di (n-butoxide) bis (2,4-pentanegenate, titanium diisopropoxiside bis (2,4-pentanegeonate)).
  • Titanium Alkoxy Titanium Compounds For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), 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.
  • Titanosen compounds for example, pentamethylcyclopentadienyl titanium trimethoxide, bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis ( ⁇ 5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
  • Monoalkoxytitanium compound For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
  • Titanium oxide compound For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide 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) titanosen compound has better chemical resistance. It is preferable from the viewpoint of playing.
  • -Pyrrole-1-yl) phenyl) titanium is preferred.
  • the blending amount thereof 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 a phenol compound, a phosphite ester compound, a thioether compound 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.
  • 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, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, the composition of the present invention may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound in which the 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. This includes compounds in which the protecting group is desorbed and functions as an antioxidant.
  • 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).
  • 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 interaction with a resin and metal adhesion due to 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.
  • the addition amount is less than 0.1 part by mass, it is difficult to obtain the effect of improving the elongation property after reliability and the adhesion to the metal material, and when the addition amount is more than 10 parts by mass, it is due to the interaction with the photosensitizer. , There is a risk of reducing the sensitivity of the resin composition.
  • Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more kinds 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, still 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, still 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, it is preferable that the total of these metals is in the above range.
  • a raw material having a low metal content is selected as the 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 are 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 by mass, 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 in which the inner wall of the container is composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in JP-A-2015-123351.
  • 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 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 hole diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still 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 for use.
  • 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. ..
  • the pressurizing pressure is preferably 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 cured film of the present invention is obtained by curing the curable resin composition of the present invention or the resin film of the present invention.
  • the film thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, and can be 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. It is preferable that the laminated body of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, 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.
  • both the first cured film and the second cured film are curable of the present invention.
  • An embodiment in which the resin composition is a cured film is preferable.
  • 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. It may be present or it may be a composition having a different composition.
  • the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
  • Examples of the applicable field 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 a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, and manufacturing a protective lacquer and a dielectric layer in electronics, particularly microelectronics.
  • the method for producing a cured film of the present invention is a film forming in which the curable resin composition of the present invention is applied to a substrate to form a film (resin film). It is preferable to include a step.
  • the method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film. Further, it is more preferable that the method for producing a cured film of the present invention includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C.
  • Development step for developing the developed film (d) Heating step for heating the developed film at 50 to 450 ° C. By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed, and sufficient curability is obtained.
  • 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 steps (a), the steps (a) to (c), or (a) are further performed.
  • )-(D) it is preferable to perform each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order.
  • a metal layer on the portion provided with the cured film, between the cured films, or both.
  • 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 substrate can be appropriately determined depending on the application, but semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin 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.
  • 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 thereof.
  • a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface thereof.
  • HMDS hexamethyldisilazane
  • the 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.
  • 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 becomes the 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. Further, the coating method can be appropriately selected depending on the shape of the substrate.
  • a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable.
  • 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 for about 10 seconds to 1 minute. Further, depending on the viscosity of the resin composition and the film thickness to be set, it is also preferable to apply the resin composition at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds.
  • the production method of the present invention may include a step of drying to remove the solvent after the film forming step (layer forming step).
  • 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 exposure amount 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 set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
  • the exposure wavelengths are as follows: (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. As a result, particularly high exposure sensitivity can be obtained. From the viewpoint of handling and productivity, a broad (three wavelengths of g, h, and i lines) 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 developing (developing the above-mentioned film) the exposed film (curable resin composition layer). By performing the development, the unexposed portion (non-exposed portion) is removed in the case of the negative type, and the exposed portion is removed in the case of the positive type.
  • 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 substrate, and the like, and ejection from a nozzle is preferably used.
  • the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, a process in which the developer is vibrated by ultrasonic waves, and a combination thereof. Processes can be adopted.
  • the developing solution is not particularly limited and a known one can be used, but a developing solution containing an organic solvent or an alkaline aqueous solution can be used.
  • 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.
  • the organic solvent may be, for example, as esters such as ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate.
  • alkyl alkyloxyacetate 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.) , 3-Methylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
  • the developer is a developer containing an organic solvent
  • cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable in the present invention.
  • the organic solvent may be used alone or in combination of two or more.
  • the developer is a developer containing an organic solvent
  • 50% by mass or more of the developer is preferably an organic solvent
  • 70% by mass or more is more preferably an organic solvent
  • 90% by mass or more is organic. It is more preferably a solvent.
  • the developer may be 100% by mass of an organic solvent.
  • the developer may further contain other components.
  • other components include known surfactants and known defoaming agents.
  • examples of the basic compound that the alkaline aqueous solution can contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate and the like, and TMAH is preferable. ..
  • TMAH tetramethylammonium hydroxide
  • KOH potassium hydroxide
  • sodium carbonate sodium carbonate
  • TMAH is preferable.
  • 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 method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and a method of immersing the base material in the developer, a method of supplying the developer on the base material using a nozzle and 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 developing solution, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable.
  • the method of supplying with a spray nozzle is more preferable. Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, or this step may be repeated a plurality of times.
  • the method of supplying the developer in the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate. 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 determined, but it can be usually 10 to 45 ° C, preferably 20 to 40 ° C.
  • rinsing After the treatment with the developer, further rinsing may be performed. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
  • the rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed using the solvent contained in the curable resin composition.
  • the rinse solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), and the like, preferably PGMEA.
  • water is preferable as the rinsing solution for development with a developing solution containing an alkaline aqueous solution.
  • 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 determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
  • the ethers include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate.
  • alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid). Eth
  • Ethyl propionate, etc. methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran.
  • Ethyl Glycol Monomethyl Ether Ethyl Glycol Monoethyl Ether, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Ethyl Glycol Monomethyl Ether (PGME), Ethyl Glycol Monomethyl Ether Acetate (PGMEA), Propylene glycol monoethyl ether acetate, propionate Lopyrene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons.
  • ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone,
  • toluene, xylene, anisole, limonene and the like dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene as alcohols.
  • Glycols and the like, and examples of the 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, PGME are particularly preferable, cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA, PGME are more preferable, and cyclohexanone and PGMEA are 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 defoaming agents.
  • the method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinsing liquid, the method of supplying the rinsing liquid on the base material by filling, and the method of supplying the rinsing liquid to the base material with a shower.
  • the method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc. there is a method of supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying the rinse liquid 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.
  • the rinsing step is preferably a step of supplying the rinsing liquid to the film after exposure by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
  • a method of supplying the rinse liquid in the rinsing step 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 a sonic 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 above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the precursor, which is a specific resin, proceeds.
  • the curable resin composition of the present invention may contain a radically polymerizable compound other than the precursor which is a specific resin, but may also cure a radically polymerizable compound other than the precursor which is an unreacted specific resin. It can be advanced in this step.
  • 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 even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable.
  • the upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
  • 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 in the case of an oven capable of rapid heating, it is preferable to carry out 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 the layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.
  • 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 the temperature is kept at 200 ° C. for 120 minutes. , Such as a pretreatment step 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 perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547.
  • the pretreatment step may be 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, for example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then 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 developed film (curable resin composition layer).
  • metal layer existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, and copper, aluminum, and these metals are exemplified.
  • the alloy containing the above is more preferable, and copper is further preferable.
  • 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 combination method thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.
  • the thickness of the metal layer is preferably 0.01 to 100 ⁇ m, more preferably 0.1 to 50 ⁇ m, still more preferably 1 to 10 ⁇ m in the thickest portion.
  • the production method of the present invention preferably further includes a laminating step.
  • 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.
  • 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 layer all at once.
  • the (c) developing step may include (e) a metal layer forming step, and even if the heating is performed each time (d), the (d) is collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, 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.
  • Plasma treatment is exemplified as the surface activation treatment.
  • the laminating step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even 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.
  • a structure such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferable, and the resin layer is preferably 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less.
  • a cured film (resin layer) of the curable resin composition so as to cover the metal layer after the metal layer is provided.
  • a film forming step in which (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are repeated in this order, or (a) film forming.
  • Examples thereof include an embodiment in which (b) an exposure step, (c) a development step, and (e) a metal layer forming step are repeated in this order, and (d) a heating step is collectively provided at the end or in the middle.
  • the method for producing a laminate 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 activation treatment step is usually performed after the metal layer forming step, but after the exposure development step, the photosensitive resin composition layer may be subjected to the surface activation treatment step and then 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 that forms the photosensitive resin composition layer on the surface. ..
  • the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure. As described above, by performing the surface activating treatment on the surface of the photosensitive resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activating treatment.
  • the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF 4 / O 2.
  • Etching treatment with NF 3 / O 2 , SF 6 , NF 3 , NF 3 / O 2 surface treatment with ultraviolet (UV) ozone method, soaking in a hydrochloric acid aqueous solution to remove the oxide film, and then removing amino and thiol groups.
  • UV ultraviolet
  • 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.
  • the present invention also discloses a semiconductor device including 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 of JP-A-2016-0273557 and the description in FIG. 1 are referred to. Yes, these contents are incorporated herein.
  • MP-1 The structure of MP-1 is presumed to be the structure represented by the following formula (MP-1).
  • the filtrate was transferred to a separating funnel, washed twice with 50 mL of water and twice with 150 mL of saturated brine, and dried over sodium sulfate. This was transferred to a 1-necked flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 20 g of MP-2.
  • the structure of MP-2 is presumed to be the structure represented by the following formula (MP-2).
  • MC-1 The structure of MC-1 is presumed to be the structure represented by the following formula (MC-1).
  • flask 2 In another flask (flask 2), 23.2 g (80 mmol) of 3- (triethoxysilyl) propyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1 .72 g (20 mmol) and 0.46 g of the polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were added, dissolved in 38.1 g of propylene glycol monomethyl ether, and added dropwise to flask 1 over 3 hours. ..
  • PC-1 The structure of PC-1 is presumed to be the structure represented by the following formula (PC-1).
  • the parenthesized subscripts represent the content ratio (molar ratio) of each repeating unit.
  • the weight average molecular weight (Mw) was measured and found to be 23,100.
  • PB-1 PB-1 solution.
  • PB-1 The structure of PB-1 is presumed to be the structure represented by the following formula (PB-1).
  • the parenthesized subscripts represent the content ratio (molar ratio) of each repeating unit.
  • the weight average molecular weight (Mw) was measured and found to be 1,6900.
  • the polybenzoxazole precursor resin was filtered off, stirred again in 6 liters of water for 30 minutes and filtered again. Then, the obtained polybenzoxazole precursor resin was dried under reduced pressure at 45 ° C. for 3 days to obtain a polybenzoxazole precursor A-1.
  • the structure of the polybenzoxazole precursor A-1 is presumed to be the structure represented by the following formula (A-1).
  • polyimide precursor A-2 was obtained.
  • the weight average molecular weight of this polyimide precursor A-2 was 21,000.
  • the content of the carboxy group in A-2 was 0.35 mmol / g.
  • the structure of the polyimide precursor A-2 is presumed to be the structure represented by the following formula (A-2).
  • the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days to obtain a polyimide precursor A-5.
  • the obtained polyimide precursor A-5 had a weight average molecular weight of 23,800 and a number average molecular weight of 10,400.
  • the content of the carboxy group in A-5 was 0.19 mmol / g.
  • the structure of the polyimide precursor A-5 is presumed to be the structure represented by the following formula (A-5).
  • the obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate consisting of a crude polymer.
  • the produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
  • the obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polyimide precursor A-6.
  • the weight average molecular weight (Mw) of this polyimide precursor A-6 was measured and found to be 24,000.
  • the content of the carboxy group in A-6 was 0.11 mmol / g.
  • ⁇ Synthesis Example A-7 Synthesis of polyimide precursor A-7 from 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate> Synthesis Example 6 except that 147.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride. Polymer A-7 was obtained by carrying out the reaction in the same manner as described in 6. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 22,900. The content of the carboxy group in A-7 was 0.15 mmol / g.
  • 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 300 mL of saturated brine in that order. After liquid separation washing, drying with 30 g of magnesium sulfate, concentration using an evaporator, and vacuum drying were performed to obtain 61.0 g of a dinitro compound (A-1).
  • CH 3 COOEt ethyl acetate
  • Examples and comparative examples> In each example, the components listed in the table below were mixed to obtain each curable resin composition. Further, in each comparative example, the components listed in the following table were mixed to obtain each comparative composition. Specifically, the content of the components other than the solvent described in the table is the amount (parts by mass) described in each "addition amount" column of the table.
  • the obtained curable resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 ⁇ m. Further, in the table, the description of "-" indicates that the composition does not contain the corresponding component.
  • B-1 to B-6 Compounds having the following structures, B-1, B-2, B-4 and B-5, are manufactured by Tokyo Chemical Industry Co., Ltd., and B-3 and B-6 are manufactured by Aldrich. Made of. PB-1 to PB-3, PB-5 to PB-6: PB-1 to PB-3 and PB-5 to PB-6 synthesized in the above synthesis example.
  • PB-4 Epocross RPS-1005 (manufactured by Nippon Shokubai Co., Ltd.)
  • PB-1 to PB-6 are resins having a repeating unit containing an oxazoline group.
  • C-1 to C-6 C-1 to C-6 synthesized in the above synthesis example.
  • -PC-1 to PC-5 PC-1 to PC-5 synthesized in the above synthesis example.
  • PC-1 to PC-5 are resins having a repeating unit containing an acid group and a repeating unit containing an alkoxysilyl group.
  • the structures of C-1 to C-6 are presumed to be the structures represented by the following formulas (C-1) to (C-6). Further, in the formulas (PC-1) to (PC-5), the subscripts in parentheses represent the content ratio (molar ratio) of the repeating unit to be written.
  • G-1 1,4-benzoquinone
  • G-2 4-methoxyphenol
  • G-3 1,4-dihydroxybenzene
  • G-4 a compound having the following structure
  • DMSO / GBL is a mixture of DMSO and GBL at a mixing ratio (mass ratio) of 80:20. It is shown that.
  • the temperature is raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching the temperature described in the column of "curing temperature (° C.)" in the table, this temperature is maintained for 3 hours to form a resin film.
  • I got 2.
  • the pattern was heated at an exposure amount of 500 mJ / cm 2 while heating for 3 hours. The entire surface was exposed to i-line. Shear force was measured on a 100 ⁇ m square resin film 2 on a copper substrate in an environment of 25 ° C.
  • B Shear force exceeds 35 gf and 40 gf or less
  • C Shear force exceeds 30 gf and 35 gf or less
  • D Shear force exceeds 25 gf and 30 gf or less
  • E Shear force exceeds 25 gf 1 gf Is 9.80665 ⁇ 10 -3 N.
  • a curable resin composition or a comparative composition was applied onto 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 exposed to i-line with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed curable resin composition layer (resin layer) was subjected to i-line exposure.
  • the film thicknesses were compared and the dissolution rate (nm / min) was calculated.
  • the film thickness was measured at 10 points on the coated surface with an ellipsometer (KT-22 manufactured by Foothill), and the film thickness was determined as the arithmetic mean value.
  • the evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Chemical resistance" column of the table. It can be said that the smaller the value of the dissolution rate, the better the chemical resistance of the obtained cured film (resin layer).
  • C The dissolution rate was 300 nm / min or more and less than 400 nm / min.
  • D The dissolution rate was 400 nm / min or more.
  • Example 101 The curable resin composition used in Example 1 was applied in a layered manner on the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 4 minutes. After forming a curable resin composition layer having a thickness of 20 ⁇ m, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes.
  • NSR1505 i6 a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m
  • the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to form an interlayer insulating film for the rewiring layer.
  • the interlayer insulating film for the rewiring layer was excellent in insulating property. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Abstract

Provided are: a curable resin composition containing a compound having an oxazoline group, a compound containing an acid group and an alkoxysilyl group, and at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimides, and polybenzoxazoles; a cured film formed by curing the curable resin composition; a laminate including the cured film; a method for producing the cured film; and a semiconductor device including the cured film or the laminate.

Description

硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイスCurable resin composition, cured film, laminate, method for manufacturing cured film, and semiconductor device
 本発明は、硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイスに関する。 The present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.
 ポリイミド又はポリベンゾオキサゾールは、耐熱性及び絶縁性等に優れるため、様々な用途に適用されている。上記用途としては特に限定されないが、実装用の半導体デバイスを例に挙げると、絶縁膜や封止材の材料、又は、保護膜としての利用が挙げられる。また、フレキシブル基板のベースフィルムやカバーレイなどとしても用いられている。 Polyimide or polybenzoxazole is applied to various applications because it has excellent heat resistance and insulating properties. The application is not particularly limited, and examples thereof include a semiconductor device for mounting as a material for an insulating film or a sealing material, or a protective film. It is also used as a base film and coverlay for flexible substrates.
 例えば上述した用途において、ポリイミド又はポリベンゾオキサゾールは、ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、及び、ポリベンゾオキサゾール前駆体よりなる群から選ばれた少なくとも一種の樹脂を含む硬化性樹脂組成物の形態で用いられる。
 このような硬化性樹脂組成物を、例えば塗布等により基材に適用して樹脂膜を形成し、その後、必要に応じて露光、現像、加熱等を行うことにより、硬化膜を基材上に形成することができる。
 上記ポリイミド前駆体、上記ポリベンゾオキサゾール前駆体は、例えば加熱により環化され、硬化膜中でそれぞれポリイミド、ポリベンゾオキサゾールとなる。
 硬化性樹脂組成物は、公知の塗布方法等により適用可能であるため、例えば、適用される硬化性樹脂組成物の適用時の形状、大きさ、適用位置等の設計の自由度が高いなど、製造上の適応性に優れるといえる。ポリイミド、ポリベンゾオキサゾール等が有する高い性能に加え、このような製造上の適応性に優れる観点から、上述の硬化性樹脂組成物の産業上の応用展開がますます期待されている。
For example, in the above-mentioned applications, the polyimide or polybenzoxazole is a form of a curable resin composition containing at least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor. Used in.
Such a curable resin composition is applied to a base material by, for example, coating to form a resin film, and then exposed, developed, heated or the like as necessary to form a cured film on the base material. Can be formed.
The polyimide precursor and the polybenzoxazole precursor are cyclized by heating, for example, and become polyimide and polybenzoxazole in the cured membrane, respectively.
Since the curable resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied curable resin composition at the time of application. It can be said that it has excellent manufacturing adaptability. In addition to the high performance of polyimide, polybenzoxazole, etc., from the viewpoint of excellent manufacturing adaptability, the above-mentioned curable resin composition is expected to be increasingly applied in industry.
 例えば、特許文献1には、半導体素子を支持部材に接着するための接着剤組成物であって、(A)カルボキシル基及び/又は水酸基を有する熱可塑性樹脂と、(B)分子内にオキサゾリン基を有する化合物と、(C)熱硬化性樹脂と、を含有する接着剤組成物が記載されている。
 例えば、特許文献2には、特定の構造を有するポリイミドが記載されている。
For example, Patent Document 1 describes an adhesive composition for adhering a semiconductor element to a support member, wherein (A) a thermoplastic resin having a carboxyl group and / or a hydroxyl group, and (B) an oxazoline group in the molecule. An adhesive composition containing (C) a thermosetting resin and a compound having the above is described.
For example, Patent Document 2 describes a polyimide having a specific structure.
特開2008-260907号公報Japanese Unexamined Patent Publication No. 2008-260907 特開2016-113498号公報Japanese Unexamined Patent Publication No. 2016-113498
 硬化性樹脂組成物からなる硬化膜であって、金属と接する硬化膜の製造において、上記硬化膜と金属との密着性の向上が求められている。
 上記金属としては、例えば、導電層等の金属層として含まれる金属が挙げられ、銅、アルミニウム、ニッケル、バナジウム、チタン、クロム、コバルト、金及びタングステンが例示され、銅、アルミニウム、及び、これらの金属を含む合金が好ましく、銅又は銅を含む合金がより好ましく、銅が更に好ましい。
 例えば、金属層及び金属層と接する硬化膜を含む積層体において、上記金属層と上記硬化膜との密着性の向上が求められている。
In the production of a cured film made of a curable resin composition and in contact with a metal, it is required to improve the adhesion between the cured film and the metal.
Examples of the metal include metals contained as a metal layer such as a conductive layer, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten, and copper, aluminum and these. Alloys containing metals are preferred, copper or alloys containing copper are more preferred, and copper is even more preferred.
For example, in a laminated body including a metal layer and a cured film in contact with the metal layer, improvement in adhesion between the metal layer and the cured film is required.
 本発明は、金属との密着性に優れた硬化膜が得られる硬化性樹脂組成物、上記硬化性樹脂組成物を硬化してなる硬化膜、上記硬化膜を含む積層体、上記硬化膜の製造方法、及び、上記硬化膜又は上記積層体を含む半導体デバイスを提供することを目的とする。 INDUSTRIAL APPLICABILITY The present invention provides a curable resin composition capable of obtaining a cured film having excellent adhesion to a metal, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and production of the cured film. It is an object of the present invention to provide a method and a semiconductor device including the cured film or the laminate.
 本発明の代表的な実施態様の例を以下に示す。
<1> ポリイミド前駆体、ポリベンゾオキサゾール前駆体、ポリイミド及びポリベンゾオキサゾールよりなる群から選ばれた少なくとも1種の樹脂、
 オキサゾリン基を有する化合物、並びに、
 酸基及びアルコキシシリル基を含む化合物を含む、
 硬化性樹脂組成物。
<2> 上記樹脂におけるカルボキシ基の含有量が、1.0mmol/g以下である、<1>に記載の硬化性樹脂組成物。
<3> 上記オキサゾリン基を有する化合物が、構造中にオキサゾリン基を2個以上含む化合物である、<1>又は<2>に記載の硬化性樹脂組成物。
<4> 上記オキサゾリン基を有する化合物が、アルコキシシリル基、ラジカル重合性基及びアゾール基よりなる群から選ばれた少なくとも1種を含む、<1>~<3>のいずれか1つに記載の硬化性樹脂組成物。
<5> 上記オキサゾリン基を有する化合物が樹脂である、<1>~<4>のいずれか1つに記載の硬化性樹脂組成物。
<6> 上記酸基及びアルコキシシリル基を含む化合物が、樹脂である、<1>~<5>のいずれか1つに記載の硬化性樹脂組成物。
<7> 上記酸基及びアルコキシシリル基を含む化合物が、ラジカル重合性基及びアゾール基よりなる群から選ばれた少なくとも1種の基を含む、<1>~<6>のいずれか1つに記載の硬化性樹脂組成物。
<8> 熱塩基発生剤、光塩基発生剤、及び、オニウム塩よりなる群から選ばれた少なくとも1種の化合物を含む、<1>~<7>のいずれか1つに記載の硬化性樹脂組成物。
<9> 再配線層用層間絶縁膜の形成に用いられる、<1>~<8>のいずれか1つに記載の硬化性樹脂組成物。
<10> <1>~<9>のいずれか1つに記載の硬化性樹脂組成物を硬化してなる硬化膜。
<11> <10>に記載の硬化膜を2層以上含み、上記硬化膜同士のいずれかの間に金属層を含む積層体。
<12> <1>~<9>のいずれか1つに記載の硬化性樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
<13> 上記膜を露光する露光工程及び上記膜を現像する現像工程を含む、<12>に記載の硬化膜の製造方法。
<14> 上記膜を、50~450℃で加熱する加熱工程を含む、<12>又は<13>に記載の硬化膜の製造方法。
<15> <10>に記載の硬化膜又は<11>に記載の積層体を含む、半導体デバイス。
Examples of typical embodiments of the present invention are shown below.
<1> At least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide and a polybenzoxazole.
Compounds having an oxazoline group, as well as
Includes compounds containing acid and alkoxysilyl groups,
Curable resin composition.
<2> The curable resin composition according to <1>, wherein the content of the carboxy group in the resin is 1.0 mmol / g or less.
<3> The curable resin composition according to <1> or <2>, wherein the compound having an oxazoline group is a compound containing two or more oxazoline groups in its structure.
<4> The compound according to any one of <1> to <3>, wherein the compound having an oxazoline group contains at least one selected from the group consisting of an alkoxysilyl group, a radically polymerizable group and an azole group. Curable resin composition.
<5> The curable resin composition according to any one of <1> to <4>, wherein the compound having an oxazoline group is a resin.
<6> The curable resin composition according to any one of <1> to <5>, wherein the compound containing the acid group and the alkoxysilyl group is a resin.
<7> The compound containing the acid group and the alkoxysilyl group comprises at least one group selected from the group consisting of a radically polymerizable group and an azole group, and is selected from any one of <1> to <6>. The curable resin composition according to the above.
<8> The curable resin according to any one of <1> to <7>, which comprises at least one compound selected from the group consisting of a thermosetting agent, a photobase generating agent, and an onium salt. Composition.
<9> The curable resin composition according to any one of <1> to <8>, which is used for forming an interlayer insulating film for a rewiring layer.
<10> A cured film obtained by curing the curable resin composition according to any one of <1> to <9>.
<11> A laminate containing two or more layers of the cured film according to <10> and containing a metal layer between any of the cured films.
<12> 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 <9> to a substrate to form a film.
<13> The method for producing a cured film according to <12>, which comprises an exposure step for exposing the film and a developing step for developing the film.
<14> The method for producing a cured film according to <12> or <13>, which comprises a heating step of heating the film at 50 to 450 ° C.
<15> A semiconductor device comprising the cured film according to <10> or the laminate according to <11>.
 本発明によれば、金属との密着性に優れた硬化膜が得られる硬化性樹脂組成物、上記硬化性樹脂組成物を硬化してなる硬化膜、上記硬化膜を含む積層体、上記硬化膜の製造方法、及び、上記硬化膜又は上記積層体を含む半導体デバイスが提供される。 According to the present invention, a curable resin composition capable of obtaining a cured film having excellent adhesion to a metal, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the cured film. And a semiconductor device including the cured film or the laminate.
 以下、本発明の主要な実施形態について説明する。しかしながら、本発明は、明示した実施形態に限られるものではない。
 本明細書において「~」という記号を用いて表される数値範囲は、「~」の前後に記載される数値をそれぞれ下限値及び上限値として含む範囲を意味する。
 本明細書において「工程」との語は、独立した工程だけではなく、その工程の所期の作用が達成できる限りにおいて、他の工程と明確に区別できない工程も含む意味である。
 本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有しない基(原子団)と共に置換基を有する基(原子団)をも包含する。例えば、「アルキル基」とは、置換基を有しないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
 本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた露光も含む。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線又は放射線が挙げられる。
 本明細書において、「(メタ)アクリレート」は、「アクリレート」及び「メタクリレート」の両方、又は、いずれかを意味し、「(メタ)アクリル」は、「アクリル」及び「メタクリル」の両方、又は、いずれかを意味し、「(メタ)アクリロイル」は、「アクリロイル」及び「メタクリロイル」の両方、又は、いずれかを意味する。
 本明細書において、構造式中のMeはメチル基を表し、Etはエチル基を表し、Buはブチル基を表し、Phはフェニル基を表す。
 本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。また本明細書において、固形分濃度とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。
 本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、特に述べない限り、ゲル浸透クロマトグラフィ(GPC測定)に従い、ポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、例えば、HLC-8220GPC(東ソー(株)製)を用い、カラムとしてガードカラムHZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、TSKgel Super HZ2000(東ソー(株)製)を用いることによって求めることができる。それらの分子量は特に述べない限り、溶離液としてTHF(テトラヒドロフラン)を用いて測定したものとする。また、GPC測定における検出は特に述べない限り、UV線(紫外線)の波長254nm検出器を使用したものとする。
 本明細書において、積層体を構成する各層の位置関係について、「上」又は「下」と記載したときには、注目している複数の層のうち基準となる層の上側又は下側に他の層があればよい。すなわち、基準となる層と上記他の層の間に、更に第3の層や要素が介在していてもよく、基準となる層と上記他の層は接している必要はない。また、特に断らない限り、基材に対し層が積み重なっていく方向を「上」と称し、又は、感光層がある場合には、基材から感光層へ向かう方向を「上」と称し、その反対方向を「下」と称する。なお、このような上下方向の設定は、本明細書中における便宜のためであり、実際の態様においては、本明細書における「上」方向は、鉛直上向きと異なることもありうる。
 本明細書において、特段の記載がない限り、組成物は、組成物に含まれる各成分として、その成分に該当する2種以上の化合物を含んでもよい。また、特段の記載がない限り、組成物における各成分の含有量とは、その成分に該当する全ての化合物の合計含有量を意味する。
 本明細書において、特に述べない限り、温度は23℃、気圧は101,325Pa(1気圧)、相対湿度は50%RHである。
 本明細書において、好ましい態様の組み合わせは、より好ましい態様である。
Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, 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.
As used herein, 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 intended action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, 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).
As used herein, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. 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.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. , Any, and "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, 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. In the present specification, for 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). Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "up" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Further, unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101,325 Pa (1 atmospheric pressure), and the relative humidity is 50% RH.
As used herein, a combination of preferred embodiments is a more preferred embodiment.
(硬化性樹脂組成物)
 本発明の硬化性樹脂組成物は、ポリイミド前駆体、ポリベンゾオキサゾール前駆体、ポリイミド及びポリベンゾオキサゾールよりなる群から選ばれた少なくとも1種の樹脂(以下、「特定樹脂」ともいう。)、オキサゾリン基を有する化合物、並びに、酸基及びアルコキシシリル基を含む化合物を含む。
(Curable resin composition)
The curable resin composition of the present invention is at least one resin (hereinafter, also referred to as "specific resin") selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, polyimide and polybenzoxazole, and oxazoline. It contains a compound having a group and a compound containing an acid group and an alkoxysilyl group.
 本発明の硬化性樹脂組成物は、ネガ型の硬化性樹脂組成物であってもポジ型の硬化性樹脂組成物であってもよいが、ネガ型の硬化性樹脂組成物であることが好ましい。
 ネガ型の硬化性樹脂組成物とは、硬化性樹脂組成物から形成された層を露光した場合に、露光されていない部分(非露光部)が現像液により除去される組成物をいう。
 ポジ型の硬化性樹脂組成物とは、硬化性樹脂組成物から形成された層を露光した場合に、露光された部分(露光部)が現像液により除去される組成物をいう。
The curable resin composition of the present invention may be a negative type curable resin composition or a positive type curable resin composition, but 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 developer when a layer formed from the curable resin composition is exposed.
The positive type curable resin composition refers to a composition in which an exposed portion (exposed portion) is removed by a developing solution when a layer formed from the curable resin composition is exposed.
 また、本発明の硬化性樹脂組成物は、得られる硬化膜の膜強度の観点から、後述する熱塩基発生剤、光塩基発生剤、及び、オニウム塩よりなる群から選ばれた少なくとも1種の化合物を含むことが好ましい。 Further, the curable resin composition of the present invention is at least one selected from the group consisting of a thermosetting agent, a photobase generating agent and an onium salt, which will be described later, from the viewpoint of the film strength of the obtained cured film. It preferably contains a compound.
 本発明の硬化性樹脂組成物によれば、金属との密着性に優れた硬化膜が得られる。
 上記効果が得られるメカニズムは不明であるが、下記のように推測される。
According to the curable resin composition of the present invention, a cured film having excellent adhesion to a metal can be obtained.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
 本発明の硬化性樹脂組成物は、オキサゾリン基を有する化合物、並びに、酸基及びアルコキシシリル基を含む化合物を含むことにより、得られる硬化膜の金属との密着性に優れる。
 硬化膜の形成において、上記酸基と上記オキサゾリン基とが反応することにより得られる硬化膜に含まれるアルコキシシリル基の結合により形成されるシロキサン結合を有する樹脂にはオキサゾリン基由来の構造が含まれることとなる。このオキサゾリン基由来の構造と特定樹脂との相互作用により、密着性に優れた硬化膜が得られると推測される。
 特に、オキサゾリン基が2官能以上である場合、酸基及びアルコキシシリル基を有する化合物における酸基同士、又は、酸基及びアルコキシシリル基を有する化合物における酸基と、特定樹脂における酸基との間に架橋構造を形成することができ、密着性に更に優れると考えられる。
 オキサゾリン基を有する化合物が、オキサゾリン基以外の重合性基を有する場合、オキサゾリン基を有する化合物同士の重合、または、例えば架橋剤(重合性化合物ともいう。)又は重合性基を有する特定樹脂とオキサゾリン基を有する化合物との重合により、特定樹脂又は重合性化合物の重合により形成される樹脂にオキサゾリン基由来の構造が含まれるため、密着性に更に優れると考えられる。
 オキサゾリン基を有する化合物がアゾール基を含む場合、上記アゾール基が金属に配位する等の理由から、金属との密着性に更に優れると考えられる。
 また、オキサゾリン基は特定樹脂における酸基とも架橋することにより、耐薬品性も向上すると考えられる。
The curable resin composition of the present invention contains a compound having an oxazoline group and a compound containing an acid group and an alkoxysilyl group, so that the obtained cured film has excellent adhesion to a metal.
In the formation of the cured film, the resin having a siloxane bond formed by the bond of the alkoxysilyl group contained in the cured film obtained by the reaction of the acid group and the oxazoline group includes a structure derived from the oxazoline group. It will be. It is presumed that a cured film having excellent adhesion can be obtained by the interaction between the structure derived from the oxazoline group and the specific resin.
In particular, when the oxazoline group is bifunctional or higher, between the acid groups in the compound having an acid group and an alkoxysilyl group, or between the acid group in the compound having an acid group and an alkoxysilyl group and the acid group in the specific resin. It is considered that a crosslinked structure can be formed and the adhesion is further excellent.
When the compound having an oxazoline group has a polymerizable group other than the oxazoline group, the polymerization of the compounds having the oxazoline group, or, for example, a cross-linking agent (also referred to as a polymerizable compound) or a specific resin having a polymerizable group and oxazoline. Since the specific resin or the resin formed by the polymerization of the polymerizable compound contains a structure derived from an oxazoline group by polymerization with a compound having a group, it is considered that the adhesion is further excellent.
When the compound having an oxazoline group contains an azole group, it is considered that the adhesion to the metal is further excellent because the azole group is coordinated to the metal.
Further, it is considered that the chemical resistance is also improved by cross-linking the oxazoline group with the acid group in the specific resin.
 ここで、特許文献1及び2には、オキサゾリン基を有する化合物、並びに、酸基及びアルコキシシリル基を含む化合物を含む硬化性樹脂組成物については記載も示唆もない。 Here, Patent Documents 1 and 2 do not describe or suggest a curable resin composition containing a compound having an oxazoline group and a compound containing an acid group and an alkoxysilyl group.
 以下、本発明の硬化性樹脂組成物に含まれる成分について詳細に説明する。 Hereinafter, the components contained in the curable resin composition of the present invention will be described in detail.
<特定樹脂>
 本発明の硬化性樹脂組成物は、ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール及びポリベンゾオキサゾール前駆体よりなる群から選ばれた少なくとも1種の樹脂(特定樹脂)を含む。
 本発明の硬化性樹脂組成物は、特定樹脂として、ポリイミド又はポリイミド前駆体を含むことが好ましく、ポリイミド前駆体を含むことがより好ましい。
<Specific resin>
The curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor.
The curable resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.
 また、特定樹脂は重合性基を有することが好ましい。
 特定樹脂における重合性基としては、ラジカル重合性基、エポキシ基、オキセタニル基、メチロール基、アルコキシメチル基等の公知の重合性基が挙げられる。
 上記ラジカル重合性基としては、エチレン性不飽和結合を有する基が好ましい。
 エチレン性不飽和結合を有する基としては、ビニル基、アリル基、ビニルフェニル基等の芳香環に直接結合した、置換されていてもよいビニル基を有する基、(メタ)アクリルアミド基、(メタ)アクリロイルオキシ基等が挙げられ、(メタ)アクリロイルオキシ基が好ましい。
 オキサゾリン基を有する化合物が重合性基を含む場合、特定樹脂はオキサゾリン基を有する化合物と重合可能な重合性基を有することが好ましい。
 重合可能な重合性基の組み合わせとしては、特定樹脂がラジカル重合性基を有し、かつ、オキサゾリン基を有する化合物がラジカル重合性基を有する、又は、特定樹脂がエポキシ基を有し、かつ、オキサゾリン基を有する化合物がエポキシ基を有する等の組み合わせが挙げられる。
 上記態様によれば、硬化膜中で特定樹脂における重合性基と、オキサゾリン基を有する化合物における重合性基とが重合することにより、得られる硬化膜の金属との密着性がより向上すると考えられる。
Moreover, it is preferable that the specific resin has a polymerizable group.
Examples of the polymerizable group in the specific resin include known polymerizable groups such as a radical polymerizable group, an epoxy group, an oxetanyl group, a methylol group and an alkoxymethyl group.
As the radically polymerizable group, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group. Examples thereof include an acryloyloxy group, and a (meth) acryloyloxy group is preferable.
When the compound having an oxazoline group contains a polymerizable group, it is preferable that the specific resin has a polymerizable group that can be polymerized with the compound having an oxazoline group.
As a combination of polymerizable groups, the specific resin has a radical polymerizable group and the compound having an oxazoline group has a radical polymerizable group, or the specific resin has an epoxy group and the specific resin has an epoxy group. Examples thereof include a combination in which a compound having an oxazoline group has an epoxy group.
According to the above aspect, it is considered that the polymerization of the polymerizable group in the specific resin and the polymerizable group in the compound having an oxazoline group in the cured film further improves the adhesion of the obtained cured film to the metal. ..
 また、酸基及びアルコキシシリル基を含む化合物が重合性基を有する場合、特定樹脂は、酸基及びアルコキシシリル基を含む化合物における重合性基と重合可能な重合性基を有することが好ましい。
 重合可能な重合性基の組み合わせとしては、特定樹脂がラジカル重合性基を有し、かつ、酸基及びアルコキシシリル基を含む化合物がラジカル重合性基を有する、又は、特定樹脂がエポキシ基を有し、かつ、酸基及びアルコキシシリル基を含む化合物がエポキシ基を有する等の組み合わせが挙げられる。
 上記態様によれば、硬化膜中で特定樹脂における重合性基と、酸基及びアルコキシシリル基を含む化合物における重合性基とが重合し、更に、酸基及びアルコキシシリル基を含む化合物における酸基と、オキサゾリン基を有する化合物におけるオキサゾリン基とが結合するため、得られる硬化膜の金属との密着性がより向上すると考えられる。
 更に、上記態様において、オキサゾリン基を有する化合物はアルコキシシリル基を有することが好ましい。
 上記態様によれば、硬化膜中で特定樹脂における重合性基と、酸基及びアルコキシシリル基を含む化合物における重合性基とが重合し、酸基及びアルコキシシリル基を含む化合物におけるアルコキシシリル基と、オキサゾリン基を有する化合物におけるアルコキシシリル基とが縮合するため、各化合物間での結合が強固となり、得られる硬化膜の金属との密着性がより向上すると考えられる。
When the compound containing an acid group and an alkoxysilyl group has a polymerizable group, the specific resin preferably has a polymerizable group that can be polymerized with the polymerizable group in the compound containing the acid group and the alkoxysilyl group.
As a combination of polymerizable groups, the specific resin has a radically polymerizable group, the compound containing an acid group and an alkoxysilyl group has a radically polymerizable group, or the specific resin has an epoxy group. In addition, a combination in which a compound containing an acid group and an alkoxysilyl group has an epoxy group and the like can be mentioned.
According to the above aspect, the polymerizable group in the specific resin and the polymerizable group in the compound containing the acid group and the alkoxysilyl group are polymerized in the cured film, and further, the acid group in the compound containing the acid group and the alkoxysilyl group. And the oxazoline group in the compound having an oxazoline group are bonded to each other, so that it is considered that the adhesion of the obtained cured film to the metal is further improved.
Further, in the above embodiment, the compound having an oxazoline group preferably has an alkoxysilyl group.
According to the above aspect, the polymerizable group in the specific resin and the polymerizable group in the compound containing the acid group and the alkoxysilyl group are polymerized in the cured film, and the alkoxysilyl group in the compound containing the acid group and the alkoxysilyl group is used. Since the alkoxysilyl group in the compound having an oxazoline group is condensed, the bond between each compound is strengthened, and it is considered that the adhesion of the obtained cured film to the metal is further improved.
 また、特定樹脂はラジカル重合性基を含むことが好ましい。
 特定樹脂がラジカル重合性基を有する場合、硬化性樹脂組成物は、感光剤として後述の光ラジカル重合開始剤を含むことが好ましく、感光剤として後述の光ラジカル重合開始剤を含み、かつ、後述のラジカル架橋剤を含むことがより好ましく、感光剤として後述の光ラジカル重合開始剤を含み、後述のラジカル架橋剤を含み、かつ、後述の増感剤を含むことが更に好ましい。このような硬化性樹脂組成物からは、例えば、ネガ型感光層が形成される。
 また、特定樹脂は、酸分解性基等の極性変換基を有していてもよい。
 特定樹脂が酸分解性基を有する場合、硬化性樹脂組成物は、感光剤として後述の光酸発生剤を含むことが好ましい。このような硬化性樹脂組成物からは、例えば、化学増幅型であるポジ型感光層又はネガ型感光層が形成される。
Further, the specific resin preferably contains a radically polymerizable group.
When the specific resin has a radically polymerizable group, the curable resin composition preferably contains a photoradical polymerization initiator described later as a photosensitizer, contains a photoradical polymerization initiator described later as a photosensitizer, and is described later. It is more preferable to contain the radical cross-linking agent described below, and it is further preferable to contain the photoradical polymerization initiator described below as the photosensitizer, the radical cross-linking agent described below, and the sensitizer described below. From such a curable resin composition, for example, a negative photosensitive layer is formed.
Further, the specific resin may have a polar conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the curable resin composition preferably contains a photoacid generator described later as a photosensitive agent. From such a curable resin composition, for example, a chemically amplified positive type photosensitive layer or a negative type photosensitive layer is formed.
 特定樹脂におけるカルボキシ基の含有量は、1.0mmol/g以下であることも好ましい。
 上記態様によれば、現像液として有機溶剤を含む現像液を用いた場合の現像性が向上する。
 また、特定樹脂におけるカルボキシ基の含有量は、0.001~1.0mmol/gであることが好ましく、0.01~0.8mmol/gであることがより好ましい。
 上記態様によれば、現像液として有機溶剤を含む現像液を用いた場合の現像性が向上し、かつ、オキサゾリン基を有する化合物と特定樹脂とが結合を形成することが可能となるため、得られる硬化膜の金属との密着性にも優れると考えられる。
The content of the carboxy group in the specific resin is also preferably 1.0 mmol / g or less.
According to the above aspect, the developability is improved when a developer containing an organic solvent is used as the developer.
The content of the carboxy group in the specific resin is preferably 0.001 to 1.0 mmol / g, more preferably 0.01 to 0.8 mmol / g.
According to the above aspect, the developability when a developer containing an organic solvent is used as the developer is improved, and the compound having an oxazoline group and the specific resin can form a bond. It is considered that the cured film is also excellent in adhesion to metal.
〔ポリイミド前駆体〕
 本発明で用いるポリイミド前駆体は、その種類等特に定めるものではないが、下記式(2)で表される繰り返し単位を含むことが好ましい。
式(2)
Figure JPOXMLDOC01-appb-C000001

 式(2)中、A及びAは、それぞれ独立に、酸素原子又はNHを表し、R111は、2価の有機基を表し、R115は、4価の有機基を表し、R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表す。
[Polyimide precursor]
The polyimide precursor used in the present invention is not particularly specified, such as its type, but preferably contains a repeating unit represented by the following formula (2).
Equation (2)
Figure JPOXMLDOC01-appb-C000001

In formula (2), A 1 and A 2 independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, and R 113. And R 114 independently represent a hydrogen atom or a monovalent organic group.
 式(2)におけるA及びAは、それぞれ独立に、酸素原子又はNHを表し、酸素原子が好ましい。
 式(2)におけるR111は、2価の有機基を表す。2価の有機基としては、直鎖又は分岐の脂肪族基、環状の脂肪族基及び芳香族基を含む基が例示され、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数6~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、これらの組み合わせからなる基が好ましく、炭素数6~20の芳香族基を含む基がより好ましい。本発明の特に好ましい実施形態として、-Ar-L-Ar-で表される基であることが例示される。但し、Arは、それぞれ独立に、芳香族基であり、Lは、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO-又はNHCO-、あるいは、上記の2つ以上の組み合わせからなる基である。これらの好ましい範囲は、上述のとおりである。
A 1 and A 2 in the formula (2) independently represent an oxygen atom or NH, and an oxygen atom is preferable.
R 111 in the formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms are exemplified. A cyclic aliphatic group having 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. As a particularly preferable embodiment of the present invention, a group represented by —L—Ar— is exemplified. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO 2- or NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.
 R111は、ジアミンから誘導されることが好ましい。ポリイミド前駆体の製造に用いられるジアミンとしては、直鎖又は分岐の脂肪族、環状の脂肪族又は芳香族ジアミンなどが挙げられる。ジアミンは、1種のみ用いてもよいし、2種以上用いてもよい。
具体的には、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数6~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、これらの組み合わせからなる基を含むジアミンであることが好ましく、炭素数6~20の芳香族基からなる基を含むジアミンであることがより好ましい。芳香族基の例としては、下記が挙げられる。
R 111 is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. The diamine containing the above is preferable, and the diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of aromatic groups include:
Figure JPOXMLDOC01-appb-C000002
 式中、Aは、単結合、又は、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-C(=O)-、-S-、-SO-、NHCO-、又は、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数1~3のアルキレン基、-O-、-C(=O)-、-S-、又は、-SO-から選択される基であることがより好ましく、-CH-、-O-、-S-、-SO-、-C(CF-、又は、-C(CH-であることが更に好ましい。
 式中、*は他の構造との結合部位を表す。
Figure JPOXMLDOC01-appb-C000002
In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or substituted with a fluorine atom, —O—, —C (= O) −, —S—, —SO. 2 -, NHCO-, or is preferably a group selected from these combinations, a single bond, an alkylene group which ~ 1 carbon atoms which may be 3-substituted by fluorine atoms, -O -, - C ( = O) -, - S-, or, -SO 2 -, more preferably a group selected from, -CH 2 -, - O - , - S -, - SO 2 -, - C (CF 3 ) 2- or -C (CH 3 ) 2- is more preferable.
In the formula, * represents a binding site with another structure.
 ジアミンとしては、具体的には、1,2-ジアミノエタン、1,2-ジアミノプロパン、1,3-ジアミノプロパン、1,4-ジアミノブタン及び1,6-ジアミノヘキサン;1,2-又は1,3-ジアミノシクロペンタン、1,2-、1,3-又は1,4-ジアミノシクロヘキサン、1,2-、1,3-又は1,4-ビス(アミノメチル)シクロヘキサン、ビス-(4-アミノシクロヘキシル)メタン、ビス-(3-アミノシクロヘキシル)メタン、4,4’-ジアミノ-3,3’-ジメチルシクロヘキシルメタン及びイソホロンジアミン;m-又はp-フェニレンジアミン、ジアミノトルエン、4,4’-又は3,3’-ジアミノビフェニル、4,4’-ジアミノジフェニルエーテル、3,3-ジアミノジフェニルエーテル、4,4’-及び3,3’-ジアミノジフェニルメタン、4,4’-及び3,3’-ジアミノジフェニルスルホン、4,4’-及び3,3’-ジアミノジフェニルスルフィド、4,4’-又は3,3’-ジアミノベンゾフェノン、3,3’-ジメチル-4,4’-ジアミノビフェニル、2,2’-ジメチル-4,4’-ジアミノビフェニル、3,3’-ジメトキシ-4,4’-ジアミノビフェニル、2,2-ビス(4-アミノフェニル)プロパン、2,2-ビス(4-アミノフェニル)ヘキサフルオロプロパン、2,2-ビス(3-ヒドロキシ-4-アミノフェニル)プロパン、2,2-ビス(3-ヒドロキシ-4-アミノフェニル)ヘキサフルオロプロパン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン、ビス(3-アミノ-4-ヒドロキシフェニル)スルホン、ビス(4-アミノ-3-ヒドロキシフェニル)スルホン、4,4’-ジアミノパラテルフェニル、4,4’-ビス(4-アミノフェノキシ)ビフェニル、ビス[4-(4-アミノフェノキシ)フェニル]スルホン、ビス[4-(3-アミノフェノキシ)フェニル]スルホン、ビス[4-(2-アミノフェノキシ)フェニル]スルホン、1,4-ビス(4-アミノフェノキシ)ベンゼン、9,10-ビス(4-アミノフェニル)アントラセン、3,3’-ジメチル-4,4’-ジアミノジフェニルスルホン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(3-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェニル)ベンゼン、3,3’-ジエチル-4,4’-ジアミノジフェニルメタン、3,3’-ジメチル-4,4’-ジアミノジフェニルメタン、4,4’-ジアミノオクタフルオロビフェニル、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、9,9-ビス(4-アミノフェニル)-10-ヒドロアントラセン、3,3’,4,4’-テトラアミノビフェニル、3,3’,4,4’-テトラアミノジフェニルエーテル、1,4-ジアミノアントラキノン、1,5-ジアミノアントラキノン、3,3-ジヒドロキシ-4,4’-ジアミノビフェニル、9,9’-ビス(4-アミノフェニル)フルオレン、4,4’-ジメチル-3,3’-ジアミノジフェニルスルホン、3,3’,5,5’-テトラメチル-4,4’-ジアミノジフェニルメタン、2,4-及び2,5-ジアミノクメン、2,5-ジメチル-p-フェニレンジアミン、アセトグアナミン、2,3,5,6-テトラメチル-p-フェニレンジアミン、2,4,6-トリメチル-m-フェニレンジアミン、ビス(3-アミノプロピル)テトラメチルジシロキサン、2,7-ジアミノフルオレン、2,5-ジアミノピリジン、1,2-ビス(4-アミノフェニル)エタン、ジアミノベンズアニリド、ジアミノ安息香酸のエステル、1,5-ジアミノナフタレン、ジアミノベンゾトリフルオライド、1,3-ビス(4-アミノフェニル)ヘキサフルオロプロパン、1,4-ビス(4-アミノフェニル)オクタフルオロブタン、1,5-ビス(4-アミノフェニル)デカフルオロペンタン、1,7-ビス(4-アミノフェニル)テトラデカフルオロヘプタン、2,2-ビス[4-(3-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2-ビス[4-(2-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、2,2-ビス[4-(4-アミノフェノキシ)-3,5-ジメチルフェニル]ヘキサフルオロプロパン、2,2-ビス[4-(4-アミノフェノキシ)-3,5-ビス(トリフルオロメチル)フェニル]ヘキサフルオロプロパン、p-ビス(4-アミノ-2-トリフルオロメチルフェノキシ)ベンゼン、4,4’-ビス(4-アミノ-2-トリフルオロメチルフェノキシ)ビフェニル、4,4’-ビス(4-アミノ-3-トリフルオロメチルフェノキシ)ビフェニル、4,4’-ビス(4-アミノ-2-トリフルオロメチルフェノキシ)ジフェニルスルホン、4,4’-ビス(3-アミノ-5-トリフルオロメチルフェノキシ)ジフェニルスルホン、2,2-ビス[4-(4-アミノ-3-トリフルオロメチルフェノキシ)フェニル]ヘキサフルオロプロパン、3,3’,5,5’-テトラメチル-4,4’-ジアミノビフェニル、4,4’-ジアミノ-2,2’-ビス(トリフルオロメチル)ビフェニル、2,2’,5,5’,6,6’-ヘキサフルオロトリジン及び4,4’-ジアミノクアテルフェニルから選ばれる少なくとも1種のジアミンが挙げられる。 Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-,1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diamino Diphenyl sulfone, 4,4'-and 3,3'-diaminodiphenyl sulfide, 4,4'-or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino) -4-Hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) ) Sulfone, 4,4'-diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'- Dimethyl-4,4'-diaminodiphenyl sulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-) Aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4, 4'-Diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-tetramethyl-4 , 4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2, , 4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane , Diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octa Fluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-Bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4, 4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluo) Lomethylphenoxy) Biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenyl sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, 2, 2-Bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'- At least one selected from diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl. Diamine can be mentioned.
 また、国際公開第2017/038598号の段落0030~0031に記載のジアミン(DA-1)~(DA-18)も好ましい。 Further, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferable.
その他に以下のジアミンも好適に使用できる。
Figure JPOXMLDOC01-appb-C000003
In addition, the following diamines can also be preferably used.
Figure JPOXMLDOC01-appb-C000003
 また、国際公開第2017/038598号の段落0032~0034に記載の2つ以上のアルキレングリコール単位を主鎖にもつジアミンも好ましく用いられる。 Further, a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 is also preferably used.
 R111は、得られる有機膜の柔軟性の観点から、-Ar-L-Ar-で表されることが好ましい。但し、Arは、それぞれ独立に、芳香族基であり、Lは、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO-又はNHCO-、あるいは、上記の2つ以上の組み合わせからなる基である。Arは、フェニレン基が好ましく、Lは、フッ素原子で置換されていてもよい炭素数1又は2の脂肪族炭化水素基、-O-、-CO-、-S-又はSO-が好ましい。ここでの脂肪族炭化水素基は、アルキレン基が好ましい。 R 111 is preferably represented by −Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—. , -SO 2- or NHCO-, or a group consisting of a combination of two or more of the above. Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group having a fluorine atom are carbon atoms and optionally 1 or substituted by 2, -O -, - CO - , - S- or SO 2 - are preferred. The aliphatic hydrocarbon group here is preferably an alkylene group.
 また、R111は、i線透過率の観点から、下記式(51)又は式(61)で表される2価の有機基であることが好ましい。特に、i線透過率、入手のし易さの観点から、式(61)で表される2価の有機基であることがより好ましい。
 式(51)
Figure JPOXMLDOC01-appb-C000004

 式(51)中、R50~R57は、それぞれ独立に、水素原子、フッ素原子又は1価の有機基であり、R50~R57の少なくとも1つは、フッ素原子、メチル基又はトリフルオロメチル基である。
 R50~R57の1価の有機基としては、炭素数1~10(好ましくは炭素数1~6)の無置換のアルキル基、炭素数1~10(好ましくは炭素数1~6)のフッ化アルキル基等が挙げられる。
Figure JPOXMLDOC01-appb-C000005

 式(61)中、R58及びR59は、それぞれ独立に、フッ素原子又はトリフルオロメチル基である。
 式(51)又は(61)の構造を与えるジアミン化合物としては、2,2’-ジメチルベンジジン、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル、2,2’-ビス(フルオロ)-4,4’-ジアミノビフェニル、4,4’-ジアミノオクタフルオロビフェニル等が挙げられる。これらは1種で又は2種以上を組み合わせて用いてもよい。
Further, from the viewpoint of i-ray transmittance, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable.
Equation (51)
Figure JPOXMLDOC01-appb-C000004

In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoro. It is a methyl group.
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.
Figure JPOXMLDOC01-appb-C000005

In formula (61), R 58 and R 59 are independently fluorine atoms or trifluoromethyl groups, respectively.
Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.
 また、R111は重合性基を含む構造であってもよい。
 例えば、R111は重合性基を有するジアミン化合物に由来する構造とすることもできる。
 重合性基を有するジアミン化合物は、特に限定されないが、芳香環構造を含む化合物であることが好ましく、芳香環構造に、アミノ基及び重合性基を含む構造が直結した構造を有する化合物であることがより好ましい。
 重合性基としては、エチレン性不飽和基、環状エーテル基、メチロール基又はアルコキシメチル基を含む基が好ましく、ビニル基、(メタ)アリル基、(メタ)アクリルアミド基、(メタ)アクリロキシ基、マレイミド基、ビニルフェニル基、エポキシ基、オキセタニル基、メチロール基又はアルコキシメチル基がより好ましく、(メタ)アクリロキシ基、(メタ)アクリルアミド基、エポキシ基、メチロール基又はアルコキシメチル基が更に好ましい。
Further, R 111 may have a structure containing a polymerizable group.
For example, R 111 may have a structure derived from a diamine compound having a polymerizable group.
The diamine compound having a polymerizable group is not particularly limited, but is preferably a compound containing an aromatic ring structure, and is a compound having a structure in which a structure containing an amino group and a polymerizable group is directly linked to the aromatic ring structure. Is more preferable.
As the polymerizable group, an ethylenically unsaturated group, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group and a maleimide are preferable. A group, a vinylphenyl 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.
 また、R111が重合性基を含む構造である場合、R111は下記式(1-1)で表される構造であることが好ましい。
Figure JPOXMLDOC01-appb-C000006

 式(1-1)中、Yは、芳香族炭化水素基を含むn+2価の基を表し、Pは重合性基を含む基を表し、nは1以上の整数を表し、*はそれぞれ、式(2)中のR111が結合する窒素原子との結合部位を表す。
When R 111 has a structure containing a polymerizable group, it is preferable that R 111 has a structure represented by the following formula (1-1).
Figure JPOXMLDOC01-appb-C000006

In formula (1-1), Y 1 represents an n + divalent group containing an aromatic hydrocarbon group, P 1 represents a group containing a polymerizable group, n represents an integer of 1 or more, and * represents each. , Represents the bonding site with the nitrogen atom to which R 111 in the formula (2) is bonded.
-Y
 式(1-1)中、Yは芳香族炭化水素基を含むn+2価の基を表す。
 Yにおける芳香族炭化水素基は、炭素数6~30の芳香族炭化水素基であることが好ましく、炭素数6~20の芳香族炭化水素基であることがより好ましく、ベンゼン環から2以上の水素原子を除いた基であることが更に好ましく、ベンゼン環から3以上の水素原子を除いた基であることが特に好ましい。
 式(1-1)中、Yにおける、式(1-1)に記載の2つの*との結合部位は、いずれも芳香族炭化水素基であることが好ましい。すなわち、式(1-1)に記載の2つの*は、Yに含まれる芳香族炭化水素環構造と、直接結合することが好ましい。
 また、式(1-1)中、Yにおける、Pとの結合部位は、いずれも芳香族炭化水素基であることが好ましい。すなわち、Pは、Yに含まれる芳香族炭化水素環構造と、直接結合することが好ましい。
-Y 1-
In formula (1-1), Y 1 represents an n + divalent group containing an aromatic hydrocarbon group.
Aromatic hydrocarbon group for Y 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.
In the formula (1-1), in Y 1, binding site of two * and according to equation (1-1) is preferably either an aromatic hydrocarbon group. That is, the two * is described in equation (1-1), an aromatic hydrocarbon ring structure contained in Y 1, it is preferable to directly bond.
In the formula (1-1), in Y 1, binding site of the P 1 is preferably either an aromatic hydrocarbon group. That is, it is preferable that P 1 is directly bonded to the aromatic hydrocarbon ring structure contained in Y 1.
 Yは、下記式(A2-1)~式(A2-5)で表される構造よりなる群から選ばれた少なくとも1種の構造を含むことが好ましく、上述の式(A2-1)~式(A2-5)で表される構造よりなる群から選ばれた少なくとも1種の構造であることがより好ましい。
Figure JPOXMLDOC01-appb-C000007
 式(A2-1)~(A2-5)中、RA211~RA214、RA221~RA224、RA231~RA238、RA241~RA248及びRA251~RA258はそれぞれ独立に、水素原子、アルキル基、環状アルキル基、アルコキシ基、ヒドロキシ基、シアノ基、ハロゲン化アルキル基、又は、ハロゲン原子を表し、LA231及びLA241はそれぞれ独立に、単結合、カルボニル基、スルホニル基、2価の飽和炭化水素基、2価の不飽和炭化水素基、ヘテロ原子、ヘテロ環基、又は、ハロゲン化アルキレン基を表し、RA211~RA214のうち少なくとも1つ、RA221~RA224のうち少なくとも1つ、RA231~RA238のうち少なくとも1つ、RA241~RA248のうち少なくとも1つ、及び、RA251~RA258のうち少なくとも1つが上記式(1-1)中のPとの結合部位であってもよく、*はそれぞれ独立に、他の構造との結合部位を表す。
Y 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-mentioned formulas (A2-1) to Y1. 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).
Figure JPOXMLDOC01-appb-C000007
Wherein (A2-1) ~ (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. saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or, a halogenated alkylene group, at least one of 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 P 1 in the formula (1-1) It may be a binding site, and * independently represents a binding site with another structure.
 これらの中でも、溶剤溶解性の観点から、Yは式(A2-1)~式(A2-4)のいずれかで表される構造を含むことが好ましく、式(A2-2)又は式(A2-4)のいずれかで表される構造を含むことがより好ましい。 Among these, from the viewpoint of solvent solubility, Y 1 preferably contains a structure represented by any of the formulas (A2-1) to (A2-4), and is preferably the formula (A2-2) or the formula (A2-2). It is more preferable to include the structure represented by any one of A2-4).
 式(A2-1)~(A2-5)中、RA211~RA214、RA221~RA224、RA231~RA238、RA241~RA248及びRA251~RA258は、上記式(1-1)中のカルボニル基との結合部位を含まず、RA211~RA214のうち少なくとも1つ、RA221~RA224のうち少なくとも1つ、RA231~RA238のうち少なくとも1つ、RA241~RA248のうち少なくとも1つ、及び、RA251~RA258のうち少なくとも1つが上記式(1-1)中のPとの結合部位であってもよい。
 式(A2-1)中、RA211~RA214がPとの結合部位でない場合、RA211~RA214はそれぞれ独立に、水素原子、炭素数1~6のアルキル基、炭素数3~12の環状アルキル基、炭素数1~6のアルコキシ基、ヒドロキシ基、シアノ基、炭素数1~3のハロゲン化アルキル基、又は、ハロゲン原子を表すことが好ましく、溶剤溶解性の観点からは、水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、炭素数1~3のハロゲン化アルキル基がより好ましく、水素原子又は炭素数1~6のアルキル基がより好ましい。
 上記RA211~RA214における上記ハロゲン化アルキル基におけるハロゲン原子、又は、上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、塩素原子又は臭素原子が好ましい。
 式(A2-2)中、RA221~RA224は式(A2-1)におけるRA211~RA214とそれぞれ同義であり、好ましい態様も同様である。
 式(A2-3)中、RA231~RA238はそれぞれ独立に、水素原子、炭素数1~6のアルキル基、炭素数3~12の環状アルキル基、炭素数1~6のアルコキシ基、ヒドロキシ基、シアノ基、炭素数1~3のハロゲン化アルキル基、又は、ハロゲン原子を表すことが好ましく、溶剤溶解性の観点からは、水素原子、炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、又は、炭素数1~3のハロゲン化アルキル基がより好ましく、水素原子又は炭素数1~6のアルキル基がより好ましい。
 上記RA231~RA238における上記ハロゲン化アルキル基におけるハロゲン原子、又は、上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、塩素原子又は臭素原子が好ましい。
 式(A2-3)中、LA231は、単結合、炭素数1~6の2価の飽和炭化水素基、炭素数5~24の2価の不飽和炭化水素基、-O-、-S-、-NR-、ヘテロ環基、又は、炭素数1~6のハロゲン化アルキレン基を表すことが好ましく、単結合、炭素数1~6の飽和炭化水素基、-O-又はヘテロ環基を表すことが好ましく、単結合又は-O-を表すことが更に好ましい。
 上記Rは水素原子又は炭化水素基を表し、水素原子、アルキル基又はアリール基がより好ましく、水素原子又はアルキル基が更に好ましく、水素原子が特に好ましい。
 上記2価の不飽和炭化水素基は、2価の脂肪族不飽和炭化水素基であってもよいし、2価の芳香族炭化水素基であってもよいが、2価の芳香族炭化水素基であることが好ましい。
 上記ヘテロ環基としては、例えば、脂肪族又は芳香族ヘテロ環から2つの水素原子を除いた基が好ましく、脂肪族又は芳香族ヘテロ環から2つの水素原子を除いた基が好ましく、ピロリジン環、テトラヒドロフラン環、テトラヒドロチオフェン環、ピロール環、フラン環、チオフェン環、ピペリジン環、テトラヒドロピラン環、ピリジン環、モルホリン環等の環構造から2つの水素原子を除いた基がより好ましい。これらのヘテロ環は、更に他のヘテロ環又は炭化水素環と縮合環を形成していてもよい。
 上記ヘテロ環の環員数は、5~10であることが好ましく、5又は6であることがより好ましい。
 また、上記ヘテロ環基におけるヘテロ原子としては、酸素原子、窒素原子、又は、硫黄原子であることが好ましい。
 上記ハロゲン化アルキレン基におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、塩素原子又は臭素原子が好ましい。
 式(A2-4)中、RA241~RA248、LA241は式(A2-3)におけるRA231~RA238、LA231とそれぞれ同義であり、好ましい態様も同様である。
 式(A2-5)中、RA251~RA258は式(A2-1)におけるRA211~RA214とそれぞれ同義であり、好ましい態様も同様である。
Wherein (A2-1) ~ (A2-5), R A211 ~ R A214, R A221 ~ R A224, R A231 ~ R A238, R A241 ~ R A248 and R A251 ~ R A258, the above equation (1 1) free of attachment to the carbonyl group in at least one of R A211 ~ R A214, at least one of R a 221 ~ R A224, at least one of R A231 ~ R A238, R A241 ~ at least one of R A248, and, at least one of R A251 ~ R A258 may be binding sites for P 1 in formula (1-1).
Wherein (A2-1), if R A211 ~ R A214 is not binding site of P 1, R A211 ~ R A214 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, 3 to 12 carbon atoms It is preferable to represent a cyclic alkyl group, an alkoxy group having 1 to 6 carbon atoms, a hydroxy group, a cyano group, an alkyl halide group having 1 to 3 carbon atoms, or a halogen atom. From the viewpoint of solvent solubility, hydrogen is used. Atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and alkyl halide groups having 1 to 3 carbon atoms are more preferable, and hydrogen atoms or alkyl groups having 1 to 6 carbon atoms are more preferable.
Halogen atom in the halogenated alkyl group in the R A211 ~ R A214, or, as the halogen atom, fluorine atom, chlorine atom, bromine atom, and an iodine atom, a chlorine atom or a bromine atom.
Wherein (A2-2), R A221 ~ R A224 have the same meanings as R A211 ~ R A214 in formula (A2-1), preferable embodiments thereof are also the same.
Wherein (A2-3), R A231 ~ R A238 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, a halogenated alkyl 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, and 1 to 6 carbon atoms. An alkoxy group of 6 or an alkyl halide group having 1 to 3 carbon atoms is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable.
Halogen atom in the halogenated alkyl group in the R A231 ~ R A238, or, as the halogen atom, fluorine atom, chlorine atom, bromine atom, and an iodine atom, a chlorine atom or a bromine atom.
In the formula (A2-3), 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. Is preferable, and it is more preferable to represent a single bond or —O—.
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 divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, but may be a divalent aromatic hydrocarbon. It is preferably a group.
As the heterocyclic group, for example, a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable, and a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable, and a pyrrolidine ring, More preferably, a group obtained by removing two hydrogen atoms from a ring structure such as a tetrahydrofuran ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, a piperidine ring, a tetrahydropyran ring, a pyridine ring, or a morpholin ring. These heterocycles may further form a fused ring with another heterocycle or a hydrocarbon ring.
The number of ring members of the heterocycle is preferably 5 to 10, and more preferably 5 or 6.
The heteroatom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
Examples of 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 chlorine atom or a bromine atom is preferable.
Wherein (A2-4), R A241 ~ R A248, L A241 have the same meanings as R A231 ~ R A238, L A231 in formula (A2-3), preferable embodiments thereof are also the same.
Wherein (A2-5), R A251 ~ R A258 have the same meanings as R A211 ~ R A214 in formula (A2-1), preferable embodiments thereof are also the same.
 式(A2-1)中、RA211~RA214のうち少なくとも1つが、式(1-1)中のPとの結合部位であることが好ましく、RA211~RA214のうち1つが上記Pとの結合部位であることがより好ましく、RA213が上記Pとの結合部位であることが好ましい。
 式(A2-2)中、RA221~RA224のうち少なくとも1つが、式(1-1)中のPとの結合部位であることが好ましく、RA221~RA224のうち1つが上記Pとの結合部位であることがより好ましく、RA223が上記Pとの結合部位であることが好ましい。
 式(A2-3)中、RA231~RA238のうち少なくとも1つが、式(1-1)中のPとの結合部位であることが好ましく、RA231~RA238のうち2つが、上記Pとの結合部位であることがより好ましく、RA231~RA234のうち1つと、RA235~RA238のうち1つの計2つが上記Pとの結合部位であることが更に好ましく、RA231及びRA238の2つが、上記Pとの結合部位であることが特に好ましい。
 式(A2-4)中、RA241~RA248のうち少なくとも1つが、式(1-1)中のPとの結合部位であることが好ましく、RA241~RA248のうち2つが、上記Pとの結合部位であることがより好ましく、RA241~RA244のうち1つと、RA245~RA248のうち1つの計2つが上記Pとの結合部位であることが更に好ましく、RA241及びRA248の2つが、上記Pとの結合部位であることが特に好ましい。
 式(A2-5)中、RA251~RA258のうち少なくとも1つが、式(1-1)中のPとの結合部位であることが好ましく、RA251~RA258のうち2つが、上記Pとの結合部位であることがより好ましく、RA251~RA254のうち1つと、RA255~RA258のうち1つの計2つが上記Pとの結合部位であることが更に好ましく、RA253及びRA257の2つが、上記Pとの結合部位であることが特に好ましい。
In formula (A2-1), at least one of R A211 ~ R A214, is preferably a binding site for P 1 in formula (1-1), one of the P of the R A211 ~ R A214 more preferably a binding site with 1, it is preferred that R A213 is a bond site to the P 1.
In formula (A2-2), at least one of R A 221 ~ R A224, is preferably a binding site for P 1 in formula (1-1), one of the P of the R A221 ~ R A224 more preferably a binding site with 1, it is preferred that R a 223 is a binding site between the P 1.
In formula (A2-3), at least one of R A231 ~ R A238, is preferably a binding site for P 1 in formula (1-1), two of R A231 ~ R A238, the more preferably a binding site of the P 1, bract one of R A231 ~ R A234, more preferably two one meter of the R A235 ~ R A238 is a binding site of the P 1, R A231 and two of R A238, it is particularly preferred that the binding site of the P 1.
In formula (A2-4), at least one of R A 241 ~ R A248, is preferably a binding site for P 1 in formula (1-1), two of R A241 ~ R A248, the more preferably a binding site of the P 1, bract one of R A241 ~ R A244, more preferably two one meter of the R A245 ~ R A248 is a binding site of the P 1, R A241 and two of R A248, it is particularly preferred that the binding site of the P 1.
In formula (A2-5), at least one of R A251 ~ R A258, is preferably a binding site for P 1 in formula (1-1), two of R A251 ~ R A258, the more preferably a binding site of the P 1, bract one of R A251 ~ R A254, more preferably two one meter of the R A255 ~ R A258 is a binding site of the P 1, R A253 and two of R A257, it is particularly preferred that the binding site of the P 1.
 式(A2-1)~式(A2-5)中、2つの*はそれぞれ、式(1-1)中の*であることが好ましい。すなわち、式(2)中のR111が結合する2つの窒素原子は、式(A2-1)~式(A2-5)中の2つの*で表される位置と直接結合することが好ましい。 In the formulas (A2-1) to (A2-5), it is preferable that the two * are the * in the formula (1-1), respectively. That is, it is preferable that the two nitrogen atoms to which R 111 in the formula (2) is bonded are directly bonded to the positions represented by the two * in the formulas (A2-1) to (A2-5).
 これらの中でも、Yは、下記式(Y-1)又は(Y-2)で表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000008

 式(Y-1)中、RY11、RY12、RY13はそれぞれ、式(A2-1)におけるRA211、RA212及びRA214と同義であり、好ましい態様も同様である。
 式(Y-2)中、RY21~RY26はそれぞれ、式(A2-4)におけるRA242~RA247と同義であり、好ましい態様も同様である。
 式(Y-1)又は式(Y-2)中、*はそれぞれ、式(2)中のR111が結合する2つの窒素原子との結合部位を、#はそれぞれ、式(1-1)中のPとの結合部位を、それぞれ示している。
Among these, Y 1 is preferably a group represented by the following formula (Y-1) or (Y-2).
Figure JPOXMLDOC01-appb-C000008

Wherein (Y-1), R Y11 , R Y12, R Y13 each has the same meaning as R A211, R A212 and R A214 in formula (A2-1), preferable embodiments thereof are also the same.
Wherein (Y-2), each of R Y21 ~ R Y26, have the same meanings as R A242 ~ R A247 in formula (A2-4), preferable embodiments thereof are also the same.
In the formula (Y-1) or the formula (Y-2), * is the binding site with the two nitrogen atoms to which R 111 in the formula (2) is bonded, and # is the formula (1-1), respectively. the binding site of P 1 in, respectively.
-P
 式(1-1)中、Pは重合性基を含む基を表す。
 重合性基としては、エチレン性不飽和基、環状エーテル基、メチロール基又はアルコキシメチル基を含む基が好ましく、ビニル基、(メタ)アリル基、(メタ)アクリルアミド基、(メタ)アクリロキシ基、マレイミド基、ビニルフェニル基、エポキシ基、オキセタニル基、メチロール基又はアルコキシメチル基がより好ましく、(メタ)アクリロキシ基、(メタ)アクリルアミド基、エポキシ基、メチロール基又はアルコキシメチル基が更に好ましい。
 Pに含まれる重合性基の数は、1個以上であり、1~15個であることが好ましく、1~10個であることがより好ましく、1~5個であることが更に好ましく、1又は2個であることが特に好ましく、1個であることが最も好ましい。
-P 1-
In formula (1-1), P 1 represents a group containing a polymerizable group.
As the polymerizable group, an ethylenically unsaturated group, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group and a maleimide are preferable. A group, a vinylphenyl 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 number of polymerizable groups contained in P 1 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.
 また、Pは下記式(P-1)で表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000009

 式(P-1)中、Lは単結合又はm+1価の連結基を表し、Aは重合性基を表し、mは1以上の整数を表し、*はYとの結合部位を表す。
 式(P-1)中、Lは単結合、又は、炭化水素基、エーテル結合、カルボニル基、チオエーテル結合、スルホニル基、-NR-、若しくは、これらが2以上結合した基が好ましく、単結合、又は、炭化水素基、エーテル結合、カルボニル基、-NR-、若しくは、これらが2以上結合した基がより好ましい。
 上記Rは水素原子又は炭化水素基を表し、水素原子、アルキル基又はアリール基がより好ましく、水素原子又はアルキル基が更に好ましく、水素原子が特に好ましい。
 上記Lにおける炭化水素基としては、炭素数1~30の飽和脂肪族炭化水素基、炭素数6~30の芳香族炭化水素基、又は、これらの組み合わせにより表される基が好ましく、炭素数1~10の飽和脂肪族炭化水素基、ベンゼン環から2以上の水素原子を除いた基、又は、これらの結合により表される基であることがより好ましい。
Further, P 1 is preferably a group represented by the following formula (P-1).
Figure JPOXMLDOC01-appb-C000009

In formula (P-1), L 1 represents a single bond or m + 1 valent linking group, A 2 represents a polymerizable group, m represents an integer of 1 or more, and * represents a binding site with Y 1. ..
In the formula (P-1), L 1 is preferably a single bond, a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N- , or a group in which two or more of these are bonded, preferably a single bond. A bond, or a hydrocarbon group, an ether bond, a carbonyl group, -NR N- , or a group in which two or more of these are bonded is more preferable.
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 these combinations Preferably, 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.
 式(P-1)中、Aはビニル基、(メタ)アリル基、(メタ)アクリルアミド基、(メタ)アクリロキシ基、マレイミド基、ビニルフェニル基、エポキシ基、オキセタニル基、メチロール基又はアルコキシメチル基が好ましく、(メタ)アクリロキシ基、(メタ)アクリルアミド基、エポキシ基、メチロール基又はアルコキシメチル基がより好ましい。 In formula (P-1), 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.
 式(P-1)中、mは1~15の整数であることが好ましく、1~10の整数であることがより好ましく、1~5の整数であることが更に好ましく、1又は2であることが特に好ましく、1であることが最も好ましい。 In the formula (P-1), m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, further preferably an integer of 1 to 5, and 1 or 2. It is particularly preferable, and 1 is most preferable.
 また、Pは下記式(P-2)又は式(P-3)で表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000010

 式(P-2)中、Aは重合性基を表し、*はYとの結合部位を表す。
 式(P-2)中、Aは式(P-1)におけるAと同義であり、好ましい態様も同様である。
 式(P-3)中、Aは重合性基を表し、Lは炭化水素基、又は、炭化水素基と、エーテル結合、カルボニル基、チオエーテル結合、スルホニル基、-NR-、若しくは、これらが2以上結合した基を表し、Zはエーテル結合、エステル結合、ウレタン結合、ウレア結合、アミド結合、又は、カーボネート結合を表し、*はYとの結合部位を表す。Rは上述の通りである。
 式(P-3)中、Aは式(P-1)におけるAと同義であり、好ましい態様も同様である。
 式(P-3)中、Lは炭化水素基、(ポリ)アルキレンオキシ基、又は、これらの組み合わせにより表される基が好ましい。上記炭化水素基としては、アルキレン基、2価の芳香族炭化水素基、又はこれらの組み合わせにより表される基であることが好ましく、アルキレン基であることがより好ましい。
 本明細書において、(ポリ)アルキレンオキシ基とは、アルキレンオキシ基又はポリアルキレンオキシ基を意味する。また、本発明において、ポリアルキレンオキシ基とは、アルキレンオキシ基が2以上直接結合した基をいう。ポリアルキレンオキシ基に含まれる複数のアルキレンオキシ基におけるアルキレン基は、それぞれ同一であっても異なっていてもよい。ポリアルキレンオキシ基が、アルキレン基が異なる複数種のアルキレンオキシ基を含む場合、ポリアルキレンオキシ基におけるアルキレンオキシ基の配列は、ランダムな配列であってもよいし、ブロックを有する配列であってもよいし、交互等のパターンを有する配列であってもよい。
 上記アルキレン基としては、炭素数1~30のアルキレン基が好ましく、炭素数1~20のアルキレン基がより好ましく、炭素数1~10のアルキレン基が更に好ましい。
 上記芳香族炭化水素基としては、炭素数6~30の芳香族炭化水素基が好ましく、炭素数6~20の芳香族炭化水素基がより好ましく、フェニレン基又はナフチレン基が更に好ましく、フェニレン基が特に好ましい。
 上記(ポリ)アルキレンオキシ基におけるアルキレン基としては、炭素数2~10のアルキレン基が好ましく、炭素数2~4のアルキレン基がより好ましく、エチレン基又はプロピレン基がより好ましく、エチレン基が更に好ましい。
 また、ポリアルキレンオキシ基に含まれるアルキレンオキシ基の数(ポリアルキレンオキシ基の繰り返し数)は、2~20が好ましく、2~10がより好ましく、2~5が更に好ましく、2~4が特に好ましい。
 式(P-3)中、Zはエーテル結合、エステル結合、ウレタン結合、ウレア結合、アミド結合、又は、カーボネート結合を表し、エステル結合、ウレタン結合、ウレア結合、又は、アミド結合がより好ましい。
 本発明において、単に「エステル結合」、「ウレタン結合」、「アミド結合」等と記載した場合、これらの結合の向きは限定されないものとする。例えば、上記Zがエステル結合である場合、ZにおけるLとの結合部位は、エステル結合における炭素原子であってもよいし、酸素原子であってもよい。
Further, P 1 is preferably a group represented by the following formula (P-2) or formula (P-3).
Figure JPOXMLDOC01-appb-C000010

In formula (P-2), A 2 represents a polymerizable group, and * represents a binding site with Y 1.
Wherein (P-2), A 2 has the same meaning as A 2 in Formula (P-1), a preferable embodiment thereof is also the same.
In the formula (P-3), A 2 represents a polymerizable group, and L 2 is a hydrocarbon group or a hydrocarbon group and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N- , or. These represent a group in which two or more are bonded, Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and * represents a binding site with Y 1. RN is as described above.
Wherein (P-3), A 2 has the same meaning as A 2 in Formula (P-1), a preferable embodiment thereof is also the same.
In the formula (P-3), L 2 is preferably a hydrocarbon group, a (poly) alkyleneoxy group, or a group represented by a combination thereof. 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.
As used herein, the (poly) alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group. Further, in the present invention, the polyalkyleneoxy group means a group in which two or more alkyleneoxy groups are directly bonded. The alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the sequence 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.
As the 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.
As the 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, a phenylene group or a naphthylene group is more preferable, and a phenylene group is preferable. Especially preferable.
As the 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 (the number of repetitions of 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.
In the formula (P-3), Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and an ester bond, a urethane bond, a urea bond, or an amide bond is more preferable.
In the present invention, when the description is simply "ester bond", "urethane bond", "amide bond" or the like, the direction of these bonds is not limited. For example, when Z 1 is an ester bond, the binding site with L 2 in Z 1 may be a carbon atom or an oxygen atom in the ester bond.
 式(2)におけるR115は、4価の有機基を表す。4価の有機基としては、芳香環を含む4価の有機基が好ましく、下記式(5)又は式(6)で表される基がより好ましい。
式(5)又は式(6)中、*はそれぞれ独立に、他の構造との結合部位を表す。
Figure JPOXMLDOC01-appb-C000011

 式(5)中、R112は、単結合、又は、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO-、及びNHCO-、ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数1~3のアルキレン基、-O-、-CO-、-S-及びSO-から選択される基であることがより好ましく、-CH-、-C(CF-、-C(CH-、-O-、-CO-、-S-及びSO-からなる群から選択される2価の基であることが更に好ましい。
R 115 in the formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
In formula (5) or formula (6), * independently represents a binding site with another structure.
Figure JPOXMLDOC01-appb-C000011

In formula (5), R 112 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be single-bonded or substituted with a fluorine atom, —O—, —CO—, —S—, —SO. 2- , And NHCO-, and preferably a group selected from a combination thereof, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO. More preferably, it is a group selected from-, -S- and SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2-, -O-, -CO. -, - and more preferably a divalent radical selected from the group consisting of - S-, and SO 2.
 R115は、具体的には、テトラカルボン酸二無水物から無水物基の除去後に残存するテトラカルボン酸残基などが挙げられる。テトラカルボン酸二無水物は、1種のみ用いてもよいし、2種以上用いてもよい。
 テトラカルボン酸二無水物は、下記式(O)で表されることが好ましい。
Figure JPOXMLDOC01-appb-C000012

 式(O)中、R115は、4価の有機基を表す。R115の好ましい範囲は式(2)におけるR115と同義であり、好ましい範囲も同様である。
Specific examples of R 115 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).
Figure JPOXMLDOC01-appb-C000012

In formula (O), R 115 represents a tetravalent organic group. A preferred range of R 115 has the same meaning as R 115 in formula (2), and preferred ranges are also the same.
 テトラカルボン酸二無水物の具体例としては、ピロメリット酸二無水物(PMDA)、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、3,3’,4,4’-ジフェニルスルフィドテトラカルボン酸二無水物、3,3’,4,4’-ジフェニルスルホンテトラカルボン酸二無水物、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’-ジフェニルメタンテトラカルボン酸二無水物、2,2’,3,3’-ジフェニルメタンテトラカルボン酸二無水物、2,3,3’,4’-ビフェニルテトラカルボン酸二無水物、2,3,3’,4’-ベンゾフェノンテトラカルボン酸二無水物、4,4’-オキシジフタル酸二無水物、2,3,6,7-ナフタレンテトラカルボン酸二無水物、1,4,5,7-ナフタレンテトラカルボン酸二無水物、2,2-ビス(3,4-ジカルボキシフェニル)プロパン二無水物、2,2-ビス(2,3-ジカルボキシフェニル)プロパン二無水物、2,2-ビス(3,4-ジカルボキシフェニル)ヘキサフルオロプロパン二無水物、1,3-ジフェニルヘキサフルオロプロパン-3,3,4,4-テトラカルボン酸二無水物、1,4,5,6-ナフタレンテトラカルボン酸二無水物、2,2’,3,3’-ジフェニルテトラカルボン酸二無水物、3,4,9,10-ペリレンテトラカルボン酸二無水物、1,2,4,5-ナフタレンテトラカルボン酸二無水物、1,4,5,8-ナフタレンテトラカルボン酸二無水物、1,8,9,10-フェナントレンテトラカルボン酸二無水物、1,1-ビス(2,3-ジカルボキシフェニル)エタン二無水物、1,1-ビス(3,4-ジカルボキシフェニル)エタン二無水物、1,2,3,4-ベンゼンテトラカルボン酸二無水物、ならびに、これらの炭素数1~6のアルキル及び炭素数1~6のアルコキシ誘導体が挙げられる。 Specific examples of tetracarboxylic acid dianhydride include pyromellitic acid dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-. Diphenylsulfide tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3'. , 4,4'-Diphenylmethanetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5 , 7-Naphthalenetetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenyl hexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5, 6-naphthalenetetracarboxylic acid dianhydride, 2,2', 3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4 5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrentetracarboxylic acid dianhydride, 1,1-bis (2, 3-Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and these. Examples thereof include an alkyl having 1 to 6 carbon atoms and an alkoxy derivative having 1 to 6 carbon atoms.
また、国際公開第2017/038598号の段落0038に記載のテトラカルボン酸二無水物(DAA-1)~(DAA-5)も好ましい例として挙げられる。 Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.
 R111とR115の少なくとも一方がOH基を有することも好ましい。より具体的には、R111として、ビスアミノフェノール誘導体の残基が挙げられる。 It is also preferable that at least one of R 111 and R 115 has an OH group. More specifically, as R 111 , a residue of a bisaminophenol derivative can be mentioned.
 R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表し、R113及びR114の少なくとも一方が重合性基を含むことが好ましく、両方が重合性基を含むことがより好ましい。重合性基としては、熱、ラジカル等の作用により、架橋反応することが可能な基であって、ラジカル重合性基が好ましい。特定樹脂における重合性基の具体例としては、エチレン性不飽和結合を有する基、アルコキシメチル基、ヒドロキシメチル基、アシルオキシメチル基、エポキシ基、オキセタニル基、ベンゾオキサゾリル基、ブロックイソシアネート基、メチロール基、アミノ基が挙げられる。ポリイミド前駆体等が有するラジカル重合性基としては、エチレン性不飽和結合を有する基が好ましい。
 エチレン性不飽和結合を有する基としては、ビニル基、(メタ)アリル基、下記式(III)で表される基などが挙げられ、下記式(III)で表される基が好ましい。
R 113 and R 114 independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and both contain a polymerizable group. preferable. As the polymerizable group, a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like. Specific examples of the polymerizable group in the specific resin include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and a methylol. Examples include a group and an amino group. As the radically polymerizable group of the polyimide precursor or the like, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III) and the like, and a group represented by the following formula (III) is preferable.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
 式(III)において、R200は、水素原子又はメチル基を表し、水素原子が好ましい。
 式(III)において、*は他の構造との結合部位を表す。
 式(III)において、R201は、炭素数2~12のアルキレン基、-CHCH(OH)CH-又はポリアルキレンオキシ基を表す。
 好適なR201の例は、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、1,2-ブタンジイル基、1,3-ブタンジイル基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基、-CHCH(OH)CH-、ポリアルキレンオキシ基が挙げられ、エチレン基、プロピレン基、トリメチレン基、-CHCH(OH)CH-、ポリアルキレンオキシ基がより好ましく、ポリアルキレンオキシ基が更に好ましい。
 本発明において、ポリアルキレンオキシ基とは、アルキレンオキシ基が2以上直接結合した基をいう。ポリアルキレンオキシ基に含まれる複数のアルキレンオキシ基におけるアルキレン基は、それぞれ同一であっても異なっていてもよい。
 ポリアルキレンオキシ基が、アルキレン基が異なる複数種のアルキレンオキシ基を含む場合、ポリアルキレンオキシ基におけるアルキレンオキシ基の配列は、ランダムな配列であってもよいし、ブロックを有する配列であってもよいし、交互等のパターンを有する配列であってもよい。
 上記アルキレン基の炭素数(アルキレン基が置換基を有する場合、置換基の炭素数を含む)は、2以上であることが好ましく、2~10であることがより好ましく、2~6であることがより好ましく、2~5であることが更に好ましく、2~4であることが一層好ましく、2又は3であることが特に好ましく、2であることが最も好ましい。
 また、上記アルキレン基は、置換基を有していてもよい。好ましい置換基としては、アルキル基、アリール基、ハロゲン原子等が挙げられる。
 また、ポリアルキレンオキシ基に含まれるアルキレンオキシ基の数(ポリアルキレンオキシ基の繰り返し数)は、2~20が好ましく、2~10がより好ましく、2~6が更に好ましい。
 ポリアルキレンオキシ基としては、溶剤溶解性及び耐溶剤性の観点からは、ポリエチレンオキシ基、ポリプロピレンオキシ基、ポリトリメチレンオキシ基、ポリテトラメチレンオキシ基、又は、複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基が好ましく、ポリエチレンオキシ基又はポリプロピレンオキシ基がより好ましく、ポリエチレンオキシ基が更に好ましい。上記複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基において、エチレンオキシ基とプロピレンオキシ基とはランダムに配列していてもよいし、ブロックを形成して配列していてもよいし、交互等のパターン状に配列していてもよい。これらの基におけるエチレンオキシ基等の繰り返し数の好ましい態様は上述の通りである。
In formula (III), R200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
In formula (III), * represents a binding site with another structure.
In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a polyalkyleneoxy group.
Examples of suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butanjiyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH 2 CH (OH) CH 2- , polyalkyleneoxy group, and ethylene group, propylene group, trimethylene group, -CH 2 CH (OH) CH 2- , polyalkyleneoxy group are more preferable, and polyalkylene group. Oxy groups are more preferred.
In the present invention, the polyalkyleneoxy group means a group in which two or more alkyleneoxy groups are directly bonded. The alkylene group in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the sequence 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. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
Further, the 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 (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
The polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance. A group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, 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.
 R113及びR114は、それぞれ独立に、水素原子又は1価の有機基である。1価の有機基としては、アリール基を構成する炭素の1つ、2つ又は3つに、好ましくは1つに酸性基を結合している、芳香族基及びアラルキル基などが挙げられる。具体的には、酸性基を有する炭素数6~20の芳香族基、酸性基を有する炭素数7~25のアラルキル基が挙げられる。より具体的には、酸性基を有するフェニル基及び酸性基を有するベンジル基が挙げられる。酸性基は、OH基が好ましい。
 R113又はR114が、水素原子、2-ヒドロキシベンジル、3-ヒドロキシベンジル及び4-ヒドロキシベンジルであることもより好ましい。
R 113 and R 114 are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one. Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.
It is also more preferable that R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.
 有機溶剤への溶解度の観点からは、R113又はR114は、1価の有機基であることが好ましい。1価の有機基としては、直鎖又は分岐のアルキル基、環状アルキル基、芳香族基を含むことが好ましく、芳香族基で置換されたアルキル基がより好ましい。
 アルキル基の炭素数は1~30が好ましい。アルキル基は直鎖、分岐、環状のいずれであってもよい。直鎖又は分岐のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、オクタデシル基、イソプロピル基、イソブチル基、sec-ブチル基、t-ブチル基、1-エチルペンチル基、2-エチルヘキシル基2-(2-(2-メトキシエトキシ)エトキシ)エトキシ基、2-(2-(2-エトキシエトキシ)エトキシ)エトキシ)エトキシ基、2-(2-(2-(2-メトキシエトキシ)エトキシ)エトキシ)エトキシ基、及び2-(2-(2-(2-エトキシエトキシ)エトキシ)エトキシ)エトキシ基が挙げられる。環状のアルキル基は、単環の環状のアルキル基であってもよく、多環の環状のアルキル基であってもよい。単環の環状のアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基及びシクロオクチル基が挙げられる。多環の環状のアルキル基としては、例えば、アダマンチル基、ノルボルニル基、ボルニル基、カンフェニル基、デカヒドロナフチル基、トリシクロデカニル基、テトラシクロデカニル基、カンホロイル基、ジシクロヘキシル基及びピネニル基が挙げられる。中でも、高感度化との両立の観点から、シクロヘキシル基が最も好ましい。また、芳香族基で置換されたアルキル基としては、後述する芳香族基で置換された直鎖アルキル基が好ましい。
 芳香族基としては、具体的には、置換又は無置換のベンゼン環、ナフタレン環、ペンタレン環、インデン環、アズレン環、ヘプタレン環、インダセン環、ペリレン環、ペンタセン環、アセナフテン環、フェナントレン環、アントラセン環、ナフタセン環、クリセン環、トリフェニレン環、フルオレン環、ビフェニル環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、インドリジン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、イソベンゾフラン環、キノリジン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キノキサゾリン環、イソキノリン環、カルバゾール環、フェナントリジン環、アクリジン環、フェナントロリン環、チアントレン環、クロメン環、キサンテン環、フェノキサチイン環、フェノチアジン環又はフェナジン環である。ベンゼン環が最も好ましい。
From the viewpoint of solubility in an organic solvent, R 113 or R 114 is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group. , Isobutyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ) Ethoxy group is mentioned. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the cyclic alkyl group of the monocycle include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene. Ring, naphthalene ring, chrysen ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring. , Indol ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, aclysine ring, phenanthrene ring, It is a thianthrene ring, a chromen ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring or a phenazine ring. The benzene ring is most preferred.
 式(2)において、R113が水素原子である場合、又は、R114が水素原子である場合、ポリイミド前駆体はエチレン性不飽和結合を有する3級アミン化合物と対塩を形成していてもよい。このようなエチレン性不飽和結合を有する3級アミン化合物の例としては、N,N-ジメチルアミノプロピルメタクリレートが挙げられる。 In formula (2), when R 113 is a hydrogen atom or R 114 is a hydrogen atom, even if the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond. good. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
 R113及びR114の少なくとも一方が、酸分解性基等の極性変換基であってもよい。酸分解性基としては、酸の作用で分解して、フェノール性ヒドロキシ基、カルボキシ基等のアルカリ可溶性基を生じるものであれば特に限定されないが、アセタール基、ケタール基、シリル基、シリルエーテル基、第三級アルキルエステル基等が好ましく、露光感度の観点からは、アセタール基がより好ましい。
 酸分解性基の具体例としては、tert-ブトキシカルボニル基、イソプロポキシカルボニル基、テトラヒドロピラニル基、テトラヒドロフラニル基、エトキシエチル基、メトキシエチル基、エトキシメチル基、トリメチルシリル基、tert-ブトキシカルボニルメチル基、トリメチルシリルエーテル基などが挙げられる。露光感度の観点からは、エトキシエチル基、又は、テトラヒドロフラニル基が好ましい。
At least one of R 113 and R 114 may be a polar conversion group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it is decomposed by the action of an acid to form an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group or a silyl ether group. , A tertiary alkyl ester group or the like is preferable, and an acetal group is more preferable from the viewpoint of exposure sensitivity.
Specific examples of the acid-degradable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl. Examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
 また、ポリイミド前駆体は、構造単位中にフッ素原子を有することも好ましい。ポリイミド前駆体中のフッ素原子含有量は、10質量%以上が好ましく、また、20質量%以下が好ましい。 It is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
 また、基板との密着性を向上させる目的で、ポリイミド前駆体は、シロキサン構造を有する脂肪族基と共重合していてもよい。具体的には、ジアミン成分として、ビス(3-アミノプロピル)テトラメチルジシロキサン、ビス(p-アミノフェニル)オクタメチルペンタシロキサンなどが挙げられる。 Further, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
 式(2)で表される繰り返し単位は、式(2-A)で表される繰り返し単位であることが好ましい。すなわち、本発明で用いるポリイミド前駆体等の少なくとも1種が、式(2-A)で表される繰り返し単位を有する前駆体であることが好ましい。このような構造とすることにより、露光ラチチュードの幅をより広げることが可能になる。
式(2-A)
Figure JPOXMLDOC01-appb-C000014

 式(2-A)中、A及びAは、酸素原子を表し、R111及びR112は、それぞれ独立に、2価の有機基を表し、R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表し、R113及びR114の少なくとも一方は、重合性基を含む基であり、両方が重合性基であることが好ましい。
The repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors and the like used in the present invention is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further widened.
Equation (2-A)
Figure JPOXMLDOC01-appb-C000014

In formula (2-A), A 1 and A 2 represent oxygen atoms, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently. Representing a hydrogen atom or a monovalent organic group , at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are polymerizable groups.
 A、A、R111、R113及びR114は、それぞれ独立に、式(2)におけるA、A、R111、R113及びR114と同義であり、好ましい範囲も同様である。
112は、式(5)におけるR112と同義であり、好ましい範囲も同様である。
A 1, A 2, R 111 , R 113 and R 114 each independently have the same meaning as A 1, A 2, R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same ..
R 112 has the same meaning as R 112 in formula (5), and preferred ranges are also the same.
 ポリイミド前駆体は、式(2)で表される繰り返し構造単位を1種含んでいてもよいが、2種以上で含んでいてもよい。また、式(2)で表される繰り返し単位の構造異性体を含んでいてもよい。また、ポリイミド前駆体は、上記式(2)の繰り返し単位のほかに、他の種類の繰り返し構造単位をも含んでよいことはいうまでもない。 The polyimide precursor may contain one kind of repeating structural unit represented by the formula (2), but may also contain two or more kinds. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).
 本発明におけるポリイミド前駆体の一実施形態として、全繰り返し単位の50モル%以上、更には70モル%以上、特に90モル%以上が式(2)で表される繰り返し単位であるポリイミド前駆体が例示される。 As one embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all repeating units is a repeating unit represented by the formula (2) is used. Illustrated.
 ポリイミド前駆体の重量平均分子量(Mw)は、好ましくは18,000~30,000であり、より好ましくは20,000~27,000であり、更に好ましくは22,000~25,000である。また、数平均分子量(Mn)は、好ましくは7,200~14,000であり、より好ましくは8,000~12,000であり、更に好ましくは9,200~11,200である。
 上記ポリイミド前駆体の分子量の分散度は、2.5以上が好ましく、2.7以上がより好ましく、2.8以上であることが更に好ましい。ポリイミド前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、4.5以下が好ましく、4.0以下がより好ましく、3.8以下が更に好ましく、3.2以下が一層好ましく、3.1以下がより一層好ましく、3.0以下が更に一層好ましく、2.95以下が特に好ましい。
 本明細書において、分子量の分散度とは、重量平均分子量/数平均分子量により算出される値である。
The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
In the present specification, the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
〔ポリイミド〕
 本発明に用いられるポリイミドは、アルカリ可溶性ポリイミドであってもよく、有機溶剤を主成分とする現像液に対して可溶なポリイミドであってもよい。
 本明細書において、アルカリ可溶性ポリイミドとは、100gの2.38質量%テトラメチルアンモニウム水溶液に対し、23℃で0.1g以上溶解するポリイミドをいい、パターン形成性の観点からは、0.5g以上溶解するポリイミドであることが好ましく、1.0g以上溶解するポリイミドであることが更に好ましい。上記溶解量の上限は特に限定されないが、100g以下であることが好ましい。
 また、ポリイミドは、得られる有機膜の膜強度及び絶縁性の観点からは、複数個のイミド構造を主鎖に有するポリイミドであることが好ましい。
 本明細書において、「主鎖」とは、樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖をいい、「側鎖」とはそれ以外の結合鎖をいう。
[Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide that is soluble in a developing solution containing an organic solvent as a main component.
In the present specification, the alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and 0.5 g or more from the viewpoint of pattern formability. A polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable. The upper limit of the dissolved amount is not particularly limited, but is preferably 100 g or less.
Further, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain from the viewpoint of the film strength and the insulating property of the obtained organic film.
As used herein, the "main chain" refers to the relatively longest bound chain among the molecules of the polymer compound constituting the resin, and the "side chain" refers to other bound chains.
-フッ素原子-
 得られる有機膜の膜強度の観点からは、ポリイミドは、フッ素原子を有することが好ましい。
 フッ素原子は、例えば、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131にフッ化アルキル基として含まれることがより好ましい。
 ポリイミドの全質量に対するフッ素原子の量は、1~50mol/gであることが好ましく、5~30mol/gであることがより好ましい。
-Fluorine atom-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a fluorine atom.
The fluorine atom is preferably contained in, for example, R 132 in the repeating unit represented by the formula (4) described later, or R 131 in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula (4) described later. It is more preferable that it is contained as an alkyl fluoride group in R 132 in the repeating unit represented by 4) or in R 131 in the repeating unit represented by the formula (4) described later.
The amount of fluorine atoms with respect to the total mass of the polyimide is preferably 1 to 50 mol / g, more preferably 5 to 30 mol / g.
-ケイ素原子-
 得られる有機膜の膜強度の観点からは、ポリイミドは、ケイ素原子を有することが好ましい。
 ケイ素原子は、例えば、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR131に後述する有機変性(ポリ)シロキサン構造として含まれることがより好ましい。
 また、上記ケイ素原子又は上記有機変性(ポリ)シロキサン構造はポリイミドの側鎖に含まれていてもよいが、ポリイミドの主鎖に含まれることが好ましい。
 ポリイミドの全質量に対するケイ素原子の量は、0.01~5mol/gであることが好ましく、0.05~1mol/gであることがより好ましい。
-Silicon atom-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a silicon atom.
The silicon atom is preferably contained in R 131 in the repeating unit represented by the formula (4) described later, and is organically modified (poly ) in R 131 in the repeating unit represented by the formula (4) described later. ) It is more preferable that it is contained as a siloxane structure.
Further, the silicon atom or the organically modified (poly) siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms with respect to the total mass of the polyimide is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.
-エチレン性不飽和結合-
 得られる有機膜の膜強度の観点からは、ポリイミドは、エチレン性不飽和結合を有することが好ましい。
 ポリイミドは、エチレン性不飽和結合を主鎖末端に有していてもよいし、側鎖に有していてもよいが、側鎖に有することが好ましい。
 上記エチレン性不飽和結合は、ラジカル重合性を有することが好ましい。
 エチレン性不飽和結合は、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131にエチレン性不飽和結合を有する基として含まれることがより好ましい。
 これらの中でも、エチレン性不飽和結合は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR131にエチレン性不飽和結合を有する基として含まれることがより好ましい。
 エチレン性不飽和結合を有する基としては、ビニル基、アリル基、ビニルフェニル基等の芳香環に直接結合した、置換されていてもよいビニル基を有する基、(メタ)アクリルアミド基、(メタ)アクリロイルオキシ基、下記式(IV)で表される基などが挙げられる。
-Ethylene unsaturated bond-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the end of the main chain or may have it in the side chain, but it is preferable to have it in the side chain.
The ethylenically unsaturated bond is preferably radically polymerizable.
The ethylenically unsaturated bond is preferably contained in R 132 in the repeating unit represented by the formula (4) described later or R 131 in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula described later. It is more preferable that R 132 in the repeating unit represented by (4) or R 131 in the repeating unit represented by the formula (4) described later is contained as a group having an ethylenically unsaturated bond.
Of these, ethylenically unsaturated bond, ethylene R 131 in the repeating unit represented by the preferably contained in R 131 in the repeating unit represented by the formula (4) described later, which will be described later Equation (4) It is more preferably contained as a group having a sex unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group. Examples thereof include an acryloyloxy group and a group represented by the following formula (IV).
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
 式(IV)中、R20は、水素原子又はメチル基を表し、メチル基が好ましい。 Wherein (IV), R 20 represents a hydrogen atom or a methyl group, a methyl group is preferable.
 式(IV)中、R21は、炭素数2~12のアルキレン基、-O-CHCH(OH)CH-、-C(=O)O-、-O(C=O)NH-、炭素数2~30の(ポリ)アルキレンオキシ基(アルキレン基の炭素数は2~12が好ましく、2~6がより好ましく、2又は3が特に好ましい;繰り返し数は1~12が好ましく、1~6がより好ましく、1~3が特に好ましい)、又はこれらを2以上組み合わせた基を表す。 In formula (IV), R 21 is an alkylene group having 2 to 12 carbon atoms, —O—CH 2 CH (OH) CH 2- , −C (= O) O−, —O (C = O) NH−. , (Poly) alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12 and 1). ~ 6 is more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined is represented.
 これらの中でも、R21は下記式(R1)~式(R3)のいずれかで表される基であることが好ましく、式(R1)で表される基であることがより好ましい。
Figure JPOXMLDOC01-appb-C000016

 式(R1)~(R3)中、Lは単結合、又は、炭素数2~12のアルキレン基、炭素数2~30の(ポリ)アルキレンオキシ基若しくはこれらを2以上結合した基を表し、Xは酸素原子又は硫黄原子を表し、*は他の構造との結合部位を表し、●は式(III)中のR201が結合する酸素原子との結合部位を表す。
 式(R1)~(R3)中、Lにおける炭素数2~12のアルキレン基、又は、炭素数2~30の(ポリ)アルキレンオキシ基の好ましい態様は、上述のR21における、炭素数2~12のアルキレン基、又は、炭素数2~30の(ポリ)アルキレンオキシ基の好ましい態様と同様である。
 式(R1)中、Xは酸素原子であることが好ましい。
 式(R1)~(R3)中、*は式(IV)中の*と同義であり、好ましい態様も同様である。
 式(R1)で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、イソシアナト基及びエチレン性不飽和結合を有する化合物(例えば、2-イソシアナトエチルメタクリレート等)とを反応することにより得られる。
 式(R2)で表される構造は、例えば、カルボキシ基を有するポリイミドと、ヒドロキシ基及びエチレン性不飽和結合を有する化合物(例えば、2-ヒドロキシエチルメタクリレート等)とを反応することにより得られる。
 式(R3)で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、グリシジル基及びエチレン性不飽和結合を有する化合物(例えば、グリシジルメタクリレート等)とを反応することにより得られる。
 ポリアルキレンオキシ基としては、溶剤溶解性及び耐溶剤性の観点からは、ポリエチレンオキシ基、ポリプロピレンオキシ基、ポリトリメチレンオキシ基、ポリテトラメチレンオキシ基、又は、複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基が好ましく、ポリエチレンオキシ基又はポリプロピレンオキシ基がより好ましく、ポリエチレンオキシ基が更に好ましい。上記複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基において、エチレンオキシ基とプロピレンオキシ基とはランダムに配列していてもよいし、ブロックを形成して配列していてもよいし、交互等のパターン状に配列していてもよい。これらの基におけるエチレンオキシ基等の繰り返し数の好ましい態様は上述の通りである。
Among these, R 21 is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1).
Figure JPOXMLDOC01-appb-C000016

In the formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) alkyleneoxy group having 2 to 30 carbon atoms, or a group having two or more bonds thereof, and is X. Indicates an oxygen atom or a sulfur atom, * represents a bond site with another structure, and ● represents a bond site with an oxygen atom to which R 201 in the formula (III) is bonded.
In the formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms in L or the (poly) alkyleneoxy group having 2 to 30 carbon atoms is the above-mentioned R 21 having 2 to 12 carbon atoms. This is the same as the preferred embodiment of the alkylene group of 12 or the (poly) alkyleneoxy group having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In the formulas (R1) to (R3), * is synonymous with * in the formula (IV), and the preferred embodiment is also the same.
The structure represented by the formula (R1) comprises, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reacting.
The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
The structure represented by the formula (R3) is obtained by reacting, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate). can get.
The polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethylethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance. A group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, 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.
 式(IV)中、*は他の構造との結合部位を表し、ポリイミドの主鎖との結合部位であることが好ましい。 In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the main chain of polyimide.
 ポリイミドの全質量に対するエチレン性不飽和結合の量は、0.05~10mol/gであることが好ましく、0.1~5mol/gであることがより好ましい。
 また、製造適性の観点では、ポリイミドの全質量に対するエチレン性不飽和結合の量は、0.0001~0.1mol/gであることが好ましく、0.0005~0.05mol/gであることがより好ましい。
The amount of the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
From the viewpoint of production suitability, the amount of ethylenically unsaturated bonds with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and preferably 0.0005 to 0.05 mol / g. More preferred.
-エチレン性不飽和結合以外の架橋性基-
 ポリイミドは、エチレン性不飽和結合以外の架橋性基を有していてもよい。
 エチレン性不飽和結合以外の架橋性基としては、エポキシ基、オキセタニル基等の環状エーテル基、メトキシメチル基等のアルコキシメチル基、メチロール基等が挙げられる。
 エチレン性不飽和結合以外の架橋性基は、例えば、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましい。
 ポリイミドの全質量に対するエチレン性不飽和結合以外の架橋性基の量は、0.05~10mol/gであることが好ましく、0.1~5mol/gであることがより好ましい。
 また、製造適性の観点では、ポリイミドの全質量に対するエチレン性不飽和結合以外の架橋性基の量は、0.0001~0.1mol/gであることが好ましく、0.001~0.05mol/gであることがより好ましい。
-Crosslinkable groups other than ethylenically unsaturated bonds-
The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
Examples of the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
The crosslinkable group other than the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by the formula (4) described later, for example.
The amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
From the viewpoint of production suitability, the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. It is more preferably g.
-極性変換基-
 ポリイミドは、酸分解性基等の極性変換基を有していてもよい。ポリイミドにおける酸分解性基は、上述の式(2)におけるR113及びR114において説明した酸分解性基と同様であり、好ましい態様も同様である。
-Polar conversion group-
The polyimide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R 113 and R 114 in the above formula (2), and the preferred embodiment is also the same.
-酸価-
 ポリイミドがアルカリ現像に供される場合、現像性を向上する観点からは、ポリイミドの酸価は、30mgKOH/g以上であることが好ましく、50mgKOH/g以上であることがより好ましく、70mgKOH/g以上であることが更に好ましい。
 また、上記酸価は500mgKOH/g以下であることが好ましく、400mgKOH/g以下であることがより好ましく、200mgKOH/g以下であることが更に好ましい。
 また、ポリイミドが有機溶剤を主成分とする現像液を用いた現像(例えば、後述する「溶剤現像」)に供される場合、ポリイミドの酸価は、2~35mgKOH/gが好ましく、3~30mgKOH/gがより好ましく、5~20mgKOH/gが更に好ましい。
 上記酸価は、公知の方法により測定され、例えば、JIS K 0070:1992に記載の方法により測定される。
 また、ポリイミドに含まれる酸基としては、保存安定性及び現像性の両立の観点から、pKaが0~10である酸基が好ましく、3~8である酸基がより好ましい。
 pKaとは、酸から水素イオンが放出される解離反応を考え、その平衡定数Kaをその負の常用対数pKaによって表したものである。本明細書において、pKaは、特に断らない限り、ACD/ChemSketch(登録商標)による計算値とする。又は、日本化学会編「改定5版 化学便覧 基礎編」に掲載の値を参照してもよい。
 また、酸基が例えばリン酸等の多価の酸である場合、上記pKaは第一解離定数である。
 このような酸基として、ポリイミドは、カルボキシ基、及び、フェノール性ヒドロキシ基よりなる群から選ばれた少なくとも1種を含むことが好ましく、フェノール性ヒドロキシ基を含むことがより好ましい。
-Acid value-
When the polyimide is subjected to alkaline development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more from the viewpoint of improving developability. Is more preferable.
The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
When the polyimide is subjected to development using a developing solution containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 2 to 35 mgKOH / g, and 3 to 30 mgKOH. / G is more preferable, and 5 to 20 mgKOH / g is even more preferable.
The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
Further, as the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of achieving both storage stability and developability.
The pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa. In the present specification, pKa is a value calculated by ACD / ChemSketch (registered trademark) unless otherwise specified. Alternatively, the values published in "Revised 5th Edition Chemistry Handbook Basics" edited by the Chemical Society of Japan may be referred to.
Further, when the acid group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.
-フェノール性ヒドロキシ基-
 アルカリ現像液による現像速度を適切なものとする観点からは、ポリイミドは、フェノール性ヒドロキシ基を有することが好ましい。
 ポリイミドは、フェノール性ヒドロキシ基を主鎖末端に有してもよいし、側鎖に有してもよい。
 フェノール性ヒドロキシ基は、例えば、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましい。
 ポリイミドの全質量に対するフェノール性ヒドロキシ基の量は、0.1~30mol/gであることが好ましく、1~20mol/gであることがより好ましい。
-Phenolic hydroxy group-
From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxy group.
The polyimide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
The phenolic hydroxy group is preferably contained in, for example, R 132 in the repeating unit represented by the formula (4) described later or R 131 in the repeating unit represented by the formula (4) described later.
The amount of the phenolic hydroxy group with respect to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.
 本発明で用いるポリイミドとしては、イミド環を有する高分子化合物であれば、特に限定はないが、下記式(4)で表される繰り返し単位を含むことが好ましく、式(4)で表される繰り返し単位を含み、重合性基を有する化合物であることがより好ましい。
式(4)
Figure JPOXMLDOC01-appb-C000017

 式(4)中、R131は、2価の有機基を表し、R132は、4価の有機基を表す。
 重合性基を有する場合、重合性基は、R131及びR132の少なくとも一方に位置していてもよいし、下記式(4-1)又は式(4-2)に示すようにポリイミドの末端に位置していてもよい。
式(4-1)
Figure JPOXMLDOC01-appb-C000018

式(4-1)中、R133は重合性基であり、他の基は式(4)と同義である。
式(4-2)
Figure JPOXMLDOC01-appb-C000019

 R134及びR135の少なくとも一方は重合性基であり、重合性基でない場合は有機基であり、他の基は式(4)と同義である。
The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably contains a repeating unit represented by the following formula (4), and is represented by the formula (4). It is more preferable that the compound contains a repeating unit and has a polymerizable group.
Equation (4)
Figure JPOXMLDOC01-appb-C000017

In formula (4), R 131 represents a divalent organic group and R 132 represents a tetravalent organic group.
When having a polymerizable group, the polymerizable group may be located at at least one of R 131 and R 132 , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be located in.
Equation (4-1)
Figure JPOXMLDOC01-appb-C000018

In formula (4-1), R 133 is a polymerizable group, and the other groups are synonymous with formula (4).
Equation (4-2)
Figure JPOXMLDOC01-appb-C000019

At least one of R 134 and R 135 is a polymerizable group, when it is not a polymerizable group, it is an organic group, and the other group is synonymous with the formula (4).
 重合性基は、上記のポリイミド前駆体等が有している重合性基で述べた重合性基と同義である。
 R131は、2価の有機基を表す。2価の有機基としては、式(2)におけるR111と同様のものが例示され、好ましい範囲も同様である。
 また、R131としては、ジアミンのアミノ基の除去後に残存するジアミン残基が挙げられる。ジアミンとしては、脂肪族、環式脂肪族又は芳香族ジアミンなどが挙げられる。具体的な例としては、ポリイミド前駆体の式(2)中のR111の例が挙げられる。
The polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.
R 131 represents a divalent organic group. As the divalent organic group, the same group as R 111 in the formula (2) is exemplified, and the preferred range is also the same.
In addition, examples of R 131 include diamine residues remaining after removal of the amino group of diamine. Examples of the diamine include aliphatic, cyclic aliphatic or aromatic diamines. Specific examples include the example of R 111 in the formula (2) of the polyimide precursor.
 R131は、少なくとも2つのアルキレングリコール単位を主鎖にもつジアミン残基であることが、焼成時における反りの発生をより効果的に抑制する点で好ましい。より好ましくは、エチレングリコール鎖、プロピレングリコール鎖のいずれか又は両方を一分子中にあわせて2つ以上含むジアミン残基であり、更に好ましくは芳香環を含まないジアミン残基である。 It is preferable that R 131 is a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the generation of warpage during firing. A diamine residue containing two or more of an ethylene glycol chain and / or a propylene glycol chain in one molecule is more preferable, and a diamine residue containing no aromatic ring is more preferable.
 エチレングリコール鎖、プロピレングリコール鎖のいずれか又は両方を一分子中にあわせて2つ以上含むジアミンとしては、ジェファーミン(登録商標)KH-511、ED-600、ED-900、ED-2003、EDR-148、EDR-176、D-200、D-400、D-2000、D-4000(以上商品名、HUNTSMAN(株)製)、1-(2-(2-(2-アミノプロポキシ)エトキシ)プロポキシ)プロパン-2-アミン、1-(1-(1-(2-アミノプロポキシ)プロパン-2-イル)オキシ)プロパン-2-アミンなどが挙げられるが、これらに限定されない。 Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine® KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) Examples thereof include, but are not limited to, propoxy) propane-2-amine and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propane-2-amine.
 R132は、4価の有機基を表す。4価の有機基としては、式(2)におけるR115と同様のものが例示され、好ましい範囲も同様である。
 例えば、R115として例示される4価の有機基の4つの結合子が、上記式(4)中の4つの-C(=O)-の部分と結合して縮合環を形成する。
R 132 represents a tetravalent organic group. As the tetravalent organic group, the same group as R 115 in the formula (2) is exemplified, and the preferable range is also the same.
For example, four conjugates of a tetravalent organic group exemplified as R 115 combine with four —C (= O) − moieties in the above formula (4) to form a fused ring.
 また、R132は、テトラカルボン酸二無水物から無水物基の除去後に残存するテトラカルボン酸残基などが挙げられる。具体的な例としては、ポリイミド前駆体の式(2)中のR115の例が挙げられる。有機膜の強度の観点から、R132は1~4つの芳香環を有する芳香族ジアミン残基であることが好ましい。 In addition, examples of R 132 include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Specific examples include the example of R 115 in the formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
 R131とR132の少なくとも一方にOH基を有することも好ましい。より具体的には、R131として、2,2-ビス(3-ヒドロキシ-4-アミノフェニル)プロパン、2,2-ビス(3-ヒドロキシ-4-アミノフェニル)ヘキサフルオロプロパン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン、上記の(DA-1)~(DA-18)が好ましい例として挙げられ、R132として、上記の(DAA-1)~(DAA-5)がより好ましい例として挙げられる。 It is also preferable to have an OH group in at least one of R 131 and R 132. More specifically, as R 131 , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the above (DA-1) to (DA-18) are preferable examples. As R 132 , the above-mentioned (DAA-1) to (DAA-5) are more preferable examples.
 また、ポリイミドは、構造単位中にフッ素原子を有することも好ましい。ポリイミド中のフッ素原子の含有量は10質量%以上が好ましく、また、20質量%以下が好ましい。 It is also preferable that the polyimide has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.
 また、基板との密着性を向上させる目的で、ポリイミドは、シロキサン構造を有する脂肪族の基を共重合してもよい。具体的には、ジアミン成分として、ビス(3-アミノプロピル)テトラメチルジシロキサン、ビス(p-アミノフェニル)オクタメチルペンタシロキサンなどが挙げられる。 Further, for the purpose of improving the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
 また、組成物の保存安定性を向上させるため、ポリイミドは主鎖末端をモノアミン、酸無水物、モノカルボン酸、モノ酸クロリド化合物、モノ活性エステル化合物などの末端封止剤で封止することが好ましい。これらのうち、モノアミンを用いることがより好ましく、モノアミンの好ましい化合物としては、アニリン、2-エチニルアニリン、3-エチニルアニリン、4-エチニルアニリン、5-アミノ-8-ヒドロキシキノリン、1-ヒドロキシ-7-アミノナフタレン、1-ヒドロキシ-6-アミノナフタレン、1-ヒドロキシ-5-アミノナフタレン、1-ヒドロキシ-4-アミノナフタレン、2-ヒドロキシ-7-アミノナフタレン、2-ヒドロキシ-6-アミノナフタレン、2-ヒドロキシ-5-アミノナフタレン、1-カルボキシ-7-アミノナフタレン、1-カルボキシ-6-アミノナフタレン、1-カルボキシ-5-アミノナフタレン、2-カルボキシ-7-アミノナフタレン、2-カルボキシ-6-アミノナフタレン、2-カルボキシ-5-アミノナフタレン、2-アミノ安息香酸、3-アミノ安息香酸、4-アミノ安息香酸、4-アミノサリチル酸、5-アミノサリチル酸、6-アミノサリチル酸、2-アミノベンゼンスルホン酸、3-アミノベンゼンスルホン酸、4-アミノベンゼンスルホン酸、3-アミノ-4,6-ジヒドロキシピリミジン、2-アミノフェノール、3-アミノフェノール、4-アミノフェノール、2-アミノチオフェノール、3-アミノチオフェノール、4-アミノチオフェノールなどが挙げられる。これらを2種以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。 Further, in order to improve the storage stability of the composition, the main chain end of the polyimide may be sealed with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound. preferable. Of these, it is more preferable to use monoamine, and preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7. -Aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfone Acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Examples thereof include aminothiophenol and 4-aminothiophenol. Two or more of these may be used, or a plurality of different end groups may be introduced by reacting a plurality of terminal encapsulants.
-イミド化率(閉環率)-
 ポリイミドのイミド化率(「閉環率」ともいう)は、得られる有機膜の膜強度、絶縁性等の観点からは、70%以上であることが好ましく、80%以上であることがより好ましく、90%以上であることがより好ましい。
 上記イミド化率の上限は特に限定されず、100%以下であればよい。
 上記イミド化率は、例えば下記方法により測定される。
 ポリイミドの赤外吸収スペクトルを測定し、イミド構造由来の吸収ピークである1377cm-1付近のピーク強度P1を求める。次に、そのポリイミドを350℃で1時間熱処理した後、再度、赤外吸収スペクトルを測定し、1377cm-1付近のピーク強度P2を求める。得られたピーク強度P1、P2を用い、下記式に基づいて、ポリイミドのイミド化率を求めることができる。
 イミド化率(%)=(ピーク強度P1/ピーク強度P2)×100
-Imidization rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, the insulating property, etc. of the obtained organic film. More preferably, it is 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, for example, by the following method.
The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm -1, which is the absorption peak derived from the imide structure. Next, the polyimide 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. Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula.
Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100
 ポリイミドは、すべてが1種のR131又はR132を含む上記式(4)の繰り返し構造単位を含んでいてもよく、2つ以上の異なる種類のR131又はR132を含む上記式(4)の繰り返し単位を含んでいてもよい。また、ポリイミドは、上記式(4)の繰り返し単位のほかに、他の種類の繰り返し構造単位をも含んでいてもよい。 The polyimide may include the repeating structural unit of the above formula (4), all comprising one type of R 131 or R 132, and the above formula (4) containing two or more different types of R 131 or R 132. May include repeating units of. Further, the polyimide may contain other types of repeating structural units in addition to the repeating unit of the above formula (4).
 ポリイミドは、例えば、低温中でテトラカルボン酸二無水物とジアミン化合物(一部をモノアミンである末端封止剤に置換)を反応させる方法、低温中でテトラカルボン酸二無水物(一部を酸無水物又はモノ酸クロリド化合物又はモノ活性エステル化合物である末端封止剤に置換)とジアミン化合物を反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後ジアミン(一部をモノアミンである末端封止剤に置換)と縮合剤の存在下で反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸を酸クロリド化し、ジアミン(一部をモノアミンである末端封止剤に置換)と反応させる方法などの方法を利用して、ポリイミド前駆体を得、これを、既知のイミド化反応法を用いて完全イミド化させる方法、又は、途中でイミド化反応を停止し、一部イミド構造を導入する方法、更には、完全イミド化したポリマーと、そのポリイミド前駆体をブレンドする事によって、一部イミド構造を導入する方法を利用して合成することができる。
 ポリイミドの市販品としては、Durimide(登録商標)284(富士フイルム(株)製)、Matrimide5218(HUNTSMAN(株)製)が例示される。
The polyimide is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound (partially replaced with a terminal encapsulant which is a monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partly an acid) at a low temperature. A method of reacting a diamine compound with an anhydride or a monoacid chloride compound or a terminal encapsulant which is a monoactive ester compound) to obtain a diester with a tetracarboxylic acid dianhydride and an alcohol, and then diamine (partly monoamine). A method of reacting in the presence of a condensing agent (replaced with an end-capping agent), a diester is obtained by tetracarboxylic acid dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid chlorided to diamine (partly monoamine). A polyimide precursor is obtained by using a method such as a method of reacting with a terminal encapsulant (replacement with an end-capping agent), which is completely imidized by a known imidization reaction method, or an imide in the middle. Synthesis using a method of stopping the conversion reaction and introducing a partially imidized structure, and further, a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor. Can be done.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrix5218 (manufactured by HUNTSMAN Co., Ltd.).
 ポリイミドの重量平均分子量(Mw)は、4,000~100,000が挙げられ、5,000~70,000が好ましく、8,000~50,000がより好ましく、10,000~30,000が更に好ましい。重量平均分子量を5,000以上とすることにより、硬化後の膜の耐折れ性を向上させることができる。機械特性に優れた有機膜を得るため、重量平均分子量は、20,000以上が特に好ましい。また、ポリイミドを2種以上含有する場合、少なくとも1種のポリイミドの重量平均分子量が上記範囲であることが好ましい。 The weight average molecular weight (Mw) of the polyimide is 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and 10,000 to 30,000. More preferred. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polyimides are contained, it is preferable that the weight average molecular weight of at least one kind of polyimide is in the above range.
〔ポリベンゾオキサゾール前駆体〕
 本発明で用いるポリベンゾオキサゾール前駆体は、その構造等について特に定めるものではないが、好ましくは下記式(3)で表される繰り返し単位を含む。
式(3)
Figure JPOXMLDOC01-appb-C000020

 式(3)中、R121は、2価の有機基を表し、R122は、4価の有機基を表し、R123及びR124は、それぞれ独立に、水素原子又は1価の有機基を表す。
[Polybenzoxazole precursor]
The polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but preferably contains a repeating unit represented by the following formula (3).
Equation (3)
Figure JPOXMLDOC01-appb-C000020

In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. show.
 式(3)において、R123及びR124は、それぞれ、式(2)におけるR113と同義であり、好ましい範囲も同様である。すなわち、少なくとも一方は、重合性基であることが好ましい。
 式(3)において、R121は、2価の有機基を表す。2価の有機基としては、脂肪族基及び芳香族基の少なくとも一方を含む基が好ましい。脂肪族基としては、直鎖の脂肪族基が好ましい。R121は、ジカルボン酸残基が好ましい。ジカルボン酸残基は、1種のみ用いてもよいし、2種以上用いてもよい。
In the formula (3), R 123 and R 124 are synonymous with R 113 in the formula (2), respectively, and the preferable range is also the same. That is, at least one is preferably a polymerizable group.
In formula (3), R 121 represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a linear aliphatic group is preferable. R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
 ジカルボン酸残基としては、脂肪族基を含むジカルボン酸及び芳香族基を含むジカルボン酸残基が好ましく、芳香族基を含むジカルボン酸残基がより好ましい。
 脂肪族基を含むジカルボン酸としては、直鎖又は分岐(好ましくは直鎖)の脂肪族基を含むジカルボン酸が好ましく、直鎖又は分岐(好ましくは直鎖)の脂肪族基と2つの-COOHからなるジカルボン酸がより好ましい。直鎖又は分岐(好ましくは直鎖)の脂肪族基の炭素数は、2~30であることが好ましく、2~25であることがより好ましく、3~20であることが更に好ましく、4~15であることが一層好ましく、5~10であることが特に好ましい。直鎖の脂肪族基はアルキレン基であることが好ましい。
 直鎖の脂肪族基を含むジカルボン酸としては、マロン酸、ジメチルマロン酸、エチルマロン酸、イソプロピルマロン酸、ジ-n-ブチルマロン酸、スクシン酸、テトラフルオロスクシン酸、メチルスクシン酸、2,2-ジメチルスクシン酸、2,3-ジメチルスクシン酸、ジメチルメチルスクシン酸、グルタル酸、ヘキサフルオログルタル酸、2-メチルグルタル酸、3-メチルグルタル酸、2,2-ジメチルグルタル酸、3,3-ジメチルグルタル酸、3-エチル-3-メチルグルタル酸、アジピン酸、オクタフルオロアジピン酸、3-メチルアジピン酸、ピメリン酸、2,2,6,6-テトラメチルピメリン酸、スベリン酸、ドデカフルオロスベリン酸、アゼライン酸、セバシン酸、ヘキサデカフルオロセバシン酸、1,9-ノナン二酸、ドデカン二酸、トリデカン二酸、テトラデカン二酸、ペンタデカン二酸、ヘキサデカン二酸、ヘプタデカン二酸、オクタデカン二酸、ノナデカン二酸、エイコサン二酸、ヘンエイコサン二酸、ドコサン二酸、トリコサン二酸、テトラコサン二酸、ペンタコサン二酸、ヘキサコサン二酸、ヘプタコサン二酸、オクタコサン二酸、ノナコサン二酸、トリアコンタン二酸、ヘントリアコンタン二酸、ドトリアコンタン二酸、ジグリコール酸、更に下記式で表されるジカルボン酸等が挙げられる。
As the dicarboxylic acid residue, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two -COOH are preferable. A dicarboxylic acid consisting of is more preferable. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, and 4 to 20. It is more preferably 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Didimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimeric acid, sverin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid , Octadecandioic acid, Nonadecandioic acid, Eikosandioic acid, Heneikosandioic acid, Docosandioic acid, Tricosanedioic acid, Tetracosandioic acid, Pentacosandioic acid, Hexacosandioic acid, Heptakosandioic acid, Octakosandioic acid, Nonakosandioic acid, Tria Examples thereof include contandioic acid, hentoria-contandioic acid, dotoria-contanedioic acid, diglycolic acid, and dicarboxylic acid represented by the following formula.
Figure JPOXMLDOC01-appb-C000021

(式中、Zは炭素数1~6の炭化水素基であり、nは1~6の整数である。)
Figure JPOXMLDOC01-appb-C000021

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).
 芳香族基を含むジカルボン酸としては、以下の芳香族基を有するジカルボン酸が好ましく、以下の芳香族基と2つの-COOHのみからなるジカルボン酸がより好ましい。 As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic groups is preferable, and a dicarboxylic acid consisting of only the following aromatic groups and two -COOH is more preferable.
Figure JPOXMLDOC01-appb-C000022

 式中、Aは-CH-、-O-、-S-、-SO-、-CO-、-NHCO-、-C(CF-、及び、-C(CH-からなる群から選択される2価の基を表し、*はそれぞれ独立に、他の構造との結合部位を表す。
Figure JPOXMLDOC01-appb-C000022

In the formula, A is -CH 2- , -O-, -S-, -SO 2- , -CO-, -NHCO-, -C (CF 3 ) 2- , and -C (CH 3 ) 2- Represents a divalent group selected from the group consisting of, and * represents a binding site with another structure independently.
 芳香族基を含むジカルボン酸の具体例としては、4,4’-カルボニル二安息香酸及び4,4’-ジカルボキシジフェニルエーテル、テレフタル酸が挙げられる。 Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
 式(3)において、R122は、4価の有機基を表す。4価の有機基としては、上記式(2)におけるR115と同義であり、好ましい範囲も同様である。
 R122は、また、ビスアミノフェノール誘導体由来の基であることが好ましく、ビスアミノフェノール誘導体由来の基としては、例えば、3,3’-ジアミノ-4,4’-ジヒドロキシビフェニル、4,4’-ジアミノ-3,3’-ジヒドロキシビフェニル、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルスルホン、4,4’-ジアミノ-3,3’-ジヒドロキシジフェニルスルホン、ビス-(3-アミノ-4-ヒドロキシフェニル)メタン、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)プロパン、2,2-ビス-(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン、2,2-ビス-(4-アミノ-3-ヒドロキシフェニル)ヘキサフルオロプロパン、ビス-(4-アミノ-3-ヒドロキシフェニル)メタン、2,2-ビス-(4-アミノ-3-ヒドロキシフェニル)プロパン、4,4’-ジアミノ-3,3’-ジヒドロキシベンゾフェノン、3,3’-ジアミノ-4,4’-ジヒドロキシベンゾフェノン、4,4’-ジアミノ-3,3’-ジヒドロキシジフェニルエーテル、3,3’-ジアミノ-4,4’-ジヒドロキシジフェニルエーテル、1,4-ジアミノ-2,5-ジヒドロキシベンゼン、1,3-ジアミノ-2,4-ジヒドロキシベンゼン、1,3-ジアミノ-4,6-ジヒドロキシベンゼンなどが挙げられる。これらのビスアミノフェノールは、単独にて、あるいは混合して使用してもよい。
In formula (3), R 122 represents a tetravalent organic group. The tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferable range is also the same.
R 122 is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from a bisaminophenol derivative include, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-Hydroxyphenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-Amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-Diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4, Examples thereof include 4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.
 ビスアミノフェノール誘導体のうち、下記芳香族基を有するビスアミノフェノール誘導体が好ましい。 Of the bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferable.
Figure JPOXMLDOC01-appb-C000023

 式中、Xは、-O-、-S-、-C(CF-、-CH-、-SO-、-NHCO-を表し、*及び#はそれぞれ、他の構造との結合部位を表す。Rは水素原子又は1価の置換基を表し、水素原子又は炭化水素基が好ましく、水素原子又はアルキル基がより好ましい。また、R122は、上記式により表される構造であることも好ましい。R122が、上記式により表される構造である場合、計4つの*及び#のうち、いずれか2つが式(3)中のR122が結合する窒素原子との結合部位であり、かつ、別の2つが式(3)中のR122が結合する酸素原子との結合部位であることが好ましく、2つの*が式(3)中のR122が結合する酸素原子との結合部位であり、かつ、2つの#が式(3)中のR122が結合する窒素原子との結合部位であるか、又は、2つの*が式(3)中のR122が結合する窒素原子との結合部位であり、かつ、2つの#が式(3)中のR122が結合する酸素原子との結合部位であることがより好ましく、2つの*が式(3)中のR122が結合する酸素原子との結合部位であり、かつ、2つの#が式(3)中のR122が結合する窒素原子との結合部位であることが更に好ましい。
Figure JPOXMLDOC01-appb-C000023

In the formula, X 1 represents -O-, -S-, -C (CF 3 ) 2- , -CH 2- , -SO 2- , -NHCO-, and * and # represent other structures, respectively. Represents the binding site of. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Further, it is also preferable that R 122 has a structure represented by the above formula. When R 122 has a structure represented by the above formula, any two of the four * and # in total are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, and preferably R 122 in another 2 Exemplary ethynylphenylbiadamantane derivatives (3) is a binding site to the oxygen atom bonding, two * is a bond sites with an oxygen atom R 122 are attached in the formula (3) , And two # are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded, or two * are the bonding sites with the nitrogen atom to which R 122 in the formula (3) is bonded. It is more preferable that the site is a site and the two #s are the bonding sites with the oxygen atom to which the R 122 in the formula (3) is bonded, and the two * are the oxygen to which the R 122 in the formula (3) is bonded. It is more preferable that it is a bond site with an atom and the two #s are bond sites with a nitrogen atom to which R 122 in the formula (3) is bonded.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
 式(A-s)中、Rは、水素原子、アルキレン、置換アルキレン、-O-、-S-、-SO-、-CO-、-NHCO-、単結合、又は下記式(A-sc)の群から選ばれる有機基である。Rは、水素原子、アルキル基、アルコキシ基、アシルオキシ基、環状のアルキル基のいずれかであり、同一でも異なってもよい。Rは水素原子、直鎖又は分岐のアルキル基、アルコキシ基、アシルオキシ基、環状のアルキル基のいずれかであり、同一でも異なってもよい。 In the formula (As), R 1 is a hydrogen atom, an alkylene, a substituted alkylene, -O-, -S-, -SO 2- , -CO-, -NHCO-, a single bond, or the following formula (A-). It is an organic group selected from the group of sc). R 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R 3 is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
Figure JPOXMLDOC01-appb-C000025
(式(A-sc)中、*は上記式(A-s)で示されるビスアミノフェノール誘導体のアミノフェノール基の芳香環に結合することを示す。)
Figure JPOXMLDOC01-appb-C000025
(In the formula (A-sc), * indicates that it binds to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)
 上記式(A-s)中、フェノール性ヒドロキシ基基のオルソ位、すなわち、Rにも置換基を有することが、アミド結合のカルボニル炭素とヒドロキシ基基の距離をより接近させると考えられ、低温で硬化した際に高環化率になる効果が更に高まる点で、特に好ましい。 In the above formula (A-s), phenolic hydroxy original ortho, i.e., to have also substituent R 3 is believed to closer the distance of the carbonyl carbon and hydroxy original amide bond, It is particularly preferable in that the effect of increasing the cyclization rate when cured at a low temperature is further enhanced.
 また、上記式(A-s)中、Rがアルキル基であり、かつRがアルキル基であることが、i線に対する高透明性と低温で硬化した際に高環化率であるという効果を維持することができ、好ましい。 Further, in the above formula (As), it is said that the fact that R 2 is an alkyl group and R 3 is an alkyl group has high transparency to i-rays and a high cyclization rate when cured at a low temperature. The effect can be maintained, which is preferable.
 また、上記式(A-s)中、Rがアルキレン又は置換アルキレンであることが、更に好ましい。Rに係るアルキレン及び置換アルキレンの具体的な例としては、炭素数1~8の直鎖状又は分岐鎖状のアルキル基が挙げられるが、その中でも-CH-、-CH(CH)-、-C(CH-が、i線に対する高透明性と低温で硬化した際の高環化率であるという効果を維持しながら、溶剤に対して十分な溶解性を持つ、バランスに優れるポリベンゾオキサゾール前駆体を得ることができる点で、より好ましい。 Further, in the above formula (As), it is more preferable that R 1 is an alkylene or a substituted alkylene. Specific examples of the alkylene and the substituted alkylene according to R 1 include linear or branched alkyl groups having 1 to 8 carbon atoms, among which -CH 2- and -CH (CH 3 ). -, -C (CH 3 ) 2 -has sufficient solubility in a solvent while maintaining the effects of high transparency to i-rays and high cyclization rate when cured at low temperature. It is more preferable in that an excellent polybenzoxazole precursor can be obtained.
 上記式(A-s)で示されるビスアミノフェノール誘導体の製造方法としては、例えば、特開2013-256506号公報の段落番号0085~0094及び実施例1(段落番号0189~0190)を参考にすることができ、これらの内容は本明細書に組み込まれる。 As a method for producing the bisaminophenol derivative represented by the above formula (As), for example, paragraph numbers 805 to 0094 and Example 1 (paragraph numbers 0189 to 0190) of JP2013-256506A are referred to. These contents can be incorporated herein by reference.
 上記式(A-s)で示されるビスアミノフェノール誘導体の構造の具体例としては、特開2013-256506号公報の段落番号0070~0080に記載のものが挙げられ、これらの内容は本明細書に組み込まれる。もちろん、これらに限定されるものではないことは言うまでもない。 Specific examples of the structure of the bis-aminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP2013-256506, and these contents are described in the present specification. Will be incorporated into. Of course, it goes without saying that it is not limited to these.
 ポリベンゾオキサゾール前駆体は上記式(3)の繰り返し単位のほかに、他の種類の繰り返し構造単位も含んでよい。
 閉環に伴う反りの発生を抑制できる点で、下記式(SL)で表されるジアミン残基を他の種類の繰り返し構造単位として含むことが好ましい。
The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3).
It is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the occurrence of warpage due to ring closure can be suppressed.
Figure JPOXMLDOC01-appb-C000026

 式(SL)中、Zは、a構造とb構造を有し、R1sは、水素原子又は炭素数1~10の炭化水素基であり、R2sは炭素数1~10の炭化水素基であり、R3s、R4s、R5s、R6sのうち少なくとも1つは芳香族基で、残りは水素原子又は炭素数1~30の有機基で、それぞれ同一でも異なっていてもよい。a構造及びb構造の重合は、ブロック重合でもランダム重合でもよい。Z部分のモル%は、a構造は5~95モル%、b構造は95~5モル%であり、a+bは100モル%である。
Figure JPOXMLDOC01-appb-C000026

In formula (SL), Z has an a structure and a b structure, R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R 2s is a hydrocarbon group having 1 to 10 carbon atoms. Yes , at least one of R 3s, R 4s , R 5s , and R 6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.
 式(SL)において、好ましいZとしては、b構造中のR5s及びR6sがフェニル基であるものが挙げられる。また、式(SL)で示される構造の分子量は、400~4,000であることが好ましく、500~3,000がより好ましい。上記分子量を上記範囲とすることで、より効果的に、ポリベンゾオキサゾール前駆体の脱水閉環後の弾性率を下げ、反りを抑制できる効果と溶剤溶解性を向上させる効果を両立することができる。 In the formula (SL), preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight in the above range, it is possible to more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure, and to achieve both the effect of suppressing warpage and the effect of improving solvent solubility.
 他の種類の繰り返し構造単位として式(SL)で表されるジアミン残基を含む場合、更に、テトラカルボン酸二無水物から無水物基の除去後に残存するテトラカルボン酸残基を繰り返し構造単位として含むことも好ましい。このようなテトラカルボン酸残基の例としては、式(2)中のR115の例が挙げられる。 When a diamine residue represented by the formula (SL) is contained as another type of repeating structural unit, the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is used as the repeating structural unit. It is also preferable to include it. Examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (2).
 ポリベンゾオキサゾール前駆体の重量平均分子量(Mw)は、例えば、後述する組成物に用いる場合、好ましくは18,000~30,000であり、より好ましくは20,000~29,000であり、更に好ましくは22,000~28,000である。また、数平均分子量(Mn)は、好ましくは7,200~14,000であり、より好ましくは8,000~12,000であり、更に好ましくは9,200~11,200である。
 上記ポリベンゾオキサゾール前駆体の分子量の分散度は、1.4以上であることが好ましく、1.5以上がより好ましく、1.6以上であることが更に好ましい。ポリベンゾオキサゾール前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、2.6以下が好ましく、2.5以下がより好ましく、2.4以下が更に好ましく、2.3以下が一層好ましく、2.2以下がより一層好ましい。
The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further, when used in a composition described later, for example. It is preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, still more preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, 2.6 or less is preferable, 2.5 or less is more preferable, 2.4 or less is further preferable, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.
〔ポリベンゾオキサゾール〕
 ポリベンゾオキサゾールとしては、ベンゾオキサゾール環を有する高分子化合物であれば、特に限定はないが、下記式(X)で表される化合物であることが好ましく、下記式(X)で表される化合物であって、重合性基を有する化合物であることがより好ましい。上記重合性基としては、ラジカル重合性基が好ましい。また、下記式(X)で表される化合物であって、酸分解性基等の極性変換基を有する化合物であってもよい。
Figure JPOXMLDOC01-appb-C000027

 式(X)中、R133は、2価の有機基を表し、R134は、4価の有機基を表す。
 重合性基又は酸分解性基等の極性変換基を有する場合、重合性基又は酸分解性基等の極性変換基は、R133及びR134の少なくとも一方に位置していてもよいし、下記式(X-1)又は式(X-2)に示すようにポリベンゾオキサゾールの末端に位置していてもよい。
式(X-1)
Figure JPOXMLDOC01-appb-C000028

 式(X-1)中、R135及びR136の少なくとも一方は、重合性基又は酸分解性基等の極性変換基であり、重合性基又は酸分解性基等の極性変換基でない場合は有機基であり、他の基は式(X)と同義である。
式(X-2)
Figure JPOXMLDOC01-appb-C000029

 式(X-2)中、R137は重合性基又は酸分解性基等の極性変換基であり、他は置換基であり、他の基は式(X)と同義である。
[Polybenzoxazole]
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X). It is more preferable that the compound has a polymerizable group. As the polymerizable group, a radically polymerizable group is preferable. Further, it may be a compound represented by the following formula (X) and having a polar conversion group such as an acid-degradable group.
Figure JPOXMLDOC01-appb-C000027

In formula (X), R 133 represents a divalent organic group and R 134 represents a tetravalent organic group.
When having a polar converting group such as a polymerizable group or an acid-degradable group, the polar converting group such as a polymerizable group or an acid-degradable group may be located at at least one of R 133 and R 134 , and may be located at least one of the following. It may be located at the terminal of polybenzoxazole as shown in the formula (X-1) or the formula (X-2).
Equation (X-1)
Figure JPOXMLDOC01-appb-C000028

In formula (X-1), at least one of R 135 and R 136 is a polar converting group such as a polymerizable group or an acid-degradable group, and is not a polar converting group such as a polymerizable group or an acid-degradable group. It is an organic group, and the other groups are synonymous with the formula (X).
Equation (X-2)
Figure JPOXMLDOC01-appb-C000029

In the formula (X-2), R 137 is a polar converting group such as a polymerizable group or an acid-degradable group, the other is a substituent, and the other group is synonymous with the formula (X).
 重合性基又は酸分解性基等の極性変換基は、上記のポリイミド前駆体等が有している重合性基で述べた重合性基と同義である。 A polar converting group such as a polymerizable group or an acid-degradable group has the same meaning as the polymerizable group described in the polymerizable group possessed by the above-mentioned polyimide precursor or the like.
 R133は、2価の有機基を表す。2価の有機基としては、脂肪族又は芳香族基が挙げられる。具体的な例としては、ポリベンゾオキサゾール前駆体の式(3)中のR121の例が挙げられる。また、その好ましい例はR121と同様である。 R 133 represents a divalent organic group. Examples of the divalent organic group include aliphatic or aromatic groups. Specific examples include the example of R 121 in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that of R 121.
 R134は、4価の有機基を表す。4価の有機基としては、ポリベンゾオキサゾール前駆体の式(3)中のR122の例が挙げられる。また、その好ましい例はR122と同様である。
 例えば、R122として例示される4価の有機基の4つの結合子が、上記式(X)中の窒素原子、酸素原子と結合して縮合環を形成する。例えば、R134が、下記有機基である場合、下記構造を形成する。
Figure JPOXMLDOC01-appb-C000030
R 134 represents a tetravalent organic group. Examples of the tetravalent organic group include R 122 in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that of R 122.
For example, four conjugates of a tetravalent organic group exemplified as R 122 combine with a nitrogen atom and an oxygen atom in the above formula (X) to form a fused ring. For example, when R 134 is the following organic group, it forms the following structure.
Figure JPOXMLDOC01-appb-C000030
 ポリベンゾオキサゾールはオキサゾール化率が85%以上であることが好ましく、90%以上であることがより好ましい。オキサゾール化率が85%以上であることにより、加熱によりオキサゾール化される時に起こる閉環に基づく膜収縮が小さくなり、反りの発生をより効果的に抑えることができる。 Polybenzoxazole preferably has an oxazole formation rate of 85% or more, more preferably 90% or more. When the oxazole formation rate is 85% or more, the membrane shrinkage due to ring closure that occurs when oxazoled by heating is reduced, and the occurrence of warpage can be suppressed more effectively.
 ポリベンゾオキサゾールは、すべてが1種のR131又はR132を含む上記式(X)の繰り返し構造単位を含んでいてもよく、2つ以上の異なる種類のR131又はR132を含む上記式(X)の繰り返し単位を含んでいてもよい。また、ポリベンゾオキサゾールは、上記式(X)の繰り返し単位のほかに、他の種類の繰り返し構造単位も含んでいてもよい。 The polybenzoxazole may comprise a repeating structural unit of formula (X), all comprising one R 131 or R 132 , comprising two or more different types of R 131 or R 132. It may include the repeating unit of X). Further, the polybenzoxazole may contain other types of repeating structural units in addition to the repeating unit of the above formula (X).
 ポリベンゾオキサゾールは、例えば、ビスアミノフェノール誘導体と、R133を含むジカルボン酸又は上記ジカルボン酸の、ジカルボン酸ジクロライド及びジカルボン酸誘導体等から選ばれる化合物とを反応させて、ポリベンゾオキサゾール前駆体を得、これを既知のオキサゾール化反応法を用いてオキサゾール化させることで得られる。
 なお、ジカルボン酸の場合には反応収率等を高めるため、1-ヒドロキシ-1,2,3-ベンゾトリアゾール等を予め反応させた活性エステル型のジカルボン酸誘導体を用いてもよい。
The resulting polybenzoxazole, for example, a bis-aminophenol derivative, a dicarboxylic acid or the dicarboxylic acid containing R 133, is reacted with a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives, the polybenzoxazole precursor , This can be obtained by oxazole using a known oxazole reaction method.
In the case of a dicarboxylic acid, an active ester-type dicarboxylic acid derivative that has been previously reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield or the like.
 ポリベンゾオキサゾールの重量平均分子量(Mw)は、5,000~70,000が好ましく、8,000~50,000がより好ましく、10,000~30,000が更に好ましい。重量平均分子量を5,000以上とすることにより、硬化後の膜の耐折れ性を向上させることができる。機械特性に優れた有機膜を得るため、重量平均分子量は、20,000以上が特に好ましい。また、ポリベンゾオキサゾールを2種以上含有する場合、少なくとも1種のポリベンゾオキサゾールの重量平均分子量が上記範囲であることが好ましい。 The weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is in the above range.
〔ポリイミド前駆体等の製造方法〕
 ポリイミド前駆体等は、ジカルボン酸又はジカルボン酸誘導体とジアミンとを反応させて得られる。好ましくは、ジカルボン酸又はジカルボン酸誘導体を、ハロゲン化剤を用いてハロゲン化させた後、ジアミンと反応させて得られる。
 ポリイミド前駆体等の製造方法では、反応に際し、有機溶剤を用いることが好ましい。有機溶剤は1種でもよいし、2種以上でもよい。
 有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル(ジグリム)、N-メチルピロリドン及びN-エチルピロリドンが例示される。
 ポリイミドは、ポリイミド前駆体を合成してから、熱イミド化、化学イミド化(例えば、触媒を作用させることによる環化反応の促進)等の方法により環化させて製造してもよいし、直接、ポリイミドを合成してもよい。
[Manufacturing method of polyimide precursor, etc.]
A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. 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 may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, promotion of cyclization reaction by acting a catalyst), or directly. , Polyimide may be synthesized.
 また、上記ハロゲン化剤を用いず、非ハロゲン系触媒を用いて合成することも好ましい。上記非ハロゲン系触媒としては、ハロゲン原子を含まない公知のアミド化触媒を特に制限なく使用することが可能であるが、例えば、ボロキシン化合物、N-ヒドロキシ化合物、3級アミン、リン酸エステル、アミン塩、ウレア化合物等、カルボジイミド化合物が挙げられる。上記カルボジイミド化合物としては、N,N’-ジイソプロピルカルボジイミド、N,N’-ジシクロへキシルカルボジイミド等が挙げられる。 It is also preferable to synthesize using a non-halogen catalyst without using the above-mentioned halogenating agent. As the non-halogen catalyst, a known amidation catalyst containing no halogen atom can be used without particular limitation. For example, a boroxin compound, an N-hydroxy compound, a tertiary amine, a phosphoric acid ester, or an amine can be used. Examples thereof include carbodiimide compounds such as salts and urea compounds. Examples of the carbodiimide compound include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide and the like.
-末端封止剤-
 ポリイミド前駆体等の製造方法に際し、組成物の保存安定性をより向上させるため、酸無水物、モノカルボン酸、モノ酸クロリド化合物、モノ活性エステル化合物などの末端封止剤で、ポリイミド前駆体等の末端を封止することが好ましい。末端封止剤としては、モノアミンを用いることがより好ましく、モノアミンの好ましい化合物としては、アニリン、2-エチニルアニリン、3-エチニルアニリン、4-エチニルアニリン、5-アミノ-8-ヒドロキシキノリン、1-ヒドロキシ-7-アミノナフタレン、1-ヒドロキシ-6-アミノナフタレン、1-ヒドロキシ-5-アミノナフタレン、1-ヒドロキシ-4-アミノナフタレン、2-ヒドロキシ-7-アミノナフタレン、2-ヒドロキシ-6-アミノナフタレン、2-ヒドロキシ-5-アミノナフタレン、1-カルボキシ-7-アミノナフタレン、1-カルボキシ-6-アミノナフタレン、1-カルボキシ-5-アミノナフタレン、2-カルボキシ-7-アミノナフタレン、2-カルボキシ-6-アミノナフタレン、2-カルボキシ-5-アミノナフタレン、2-アミノ安息香酸、3-アミノ安息香酸、4-アミノ安息香酸、4-アミノサリチル酸、5-アミノサリチル酸、6-アミノサリチル酸、2-アミノベンゼンスルホン酸、3-アミノベンゼンスルホン酸、4-アミノベンゼンスルホン酸、3-アミノ-4,6-ジヒドロキシピリミジン、2-アミノフェノール、3-アミノフェノール、4-アミノフェノール、2-アミノチオフェノール、3-アミノチオフェノール、4-アミノチオフェノール、4-アミノスチレンなどが挙げられる。これらを2種以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。
-End sealant-
In order to further improve the storage stability of the composition in the method for producing a polyimide precursor, etc., a polyimide precursor or the like is used as an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. It is preferable to seal the end of the resin. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-. Hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy -6-Aminonaphthalene, 2-carboxy-5-Aminonaphthalene, 2-Aminobenzoic acid, 3-Aminobenzoic acid, 4-Aminobenzoic acid, 4-Aminosalicylic acid, 5-Aminosalicylic acid, 6-Aminosalicylic acid, 2- Aminobenzene sulfonic acid, 3-aminobenzene sulfonic acid, 4-aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol , 3-Aminothiophenol, 4-Aminothiophenol, 4-Aminostyrene and the like. Two or more of these may be used, or a plurality of different end groups may be introduced by reacting a plurality of terminal encapsulants.
-固体析出-
 ポリイミド前駆体等の製造に際し、固体を析出する工程を含んでいてもよい。具体的には、反応液中のポリイミド前駆体等を、水中に沈殿させ、テトラヒドロフラン等のポリイミド前駆体等が可溶な溶剤に溶解させることによって、固体析出することができる。
 その後、ポリイミド前駆体等を乾燥して、粉末状のポリイミド前駆体等を得ることができる。
-Solid precipitation-
A step of precipitating a solid may be included in the production of a polyimide precursor or the like. Specifically, the polyimide precursor or the like in the reaction solution can be precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
Then, the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.
〔含有量〕
 本発明の組成物における特定樹脂の含有量は、組成物の全固形分に対し20質量%以上であることが好ましく、30質量%以上であることがより好ましく、40質量%以上であることが更に好ましく、50質量%以上であることが一層好ましい。また、本発明の組成物における樹脂の含有量は、組成物の全固形分に対し、99.5質量%以下であることが好ましく、99質量%以下であることがより好ましく、98質量%以下であることが更に好ましく、97質量%以下であることが一層好ましく、95質量%以下であることがより一層好ましい。
 本発明の組成物は、特定樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
〔Content〕
The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the composition. It is more preferably 50% by mass or more, and even more preferably 50% by mass or more. The resin content in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less, based on the total solid content of the composition. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
The composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
 また、本発明の硬化性樹脂組成物は、少なくとも2種の樹脂を含むことが好ましい。
 具体的には、本発明の硬化性樹脂組成物は、特定樹脂と、後述する他の樹脂とを合計で2種以上含んでもよいし、特定樹脂を2種以上含んでいてもよいが、特定樹脂を2種以上含むことが好ましい。
 本発明の硬化性樹脂組成物が特定樹脂を2種以上含む場合、例えば、ポリイミド前駆体であって、二無水物由来の構造(上述の式(2)でいうR115)が異なる2種以上のポリイミド前駆体を含むことが好ましい。
Further, the curable resin composition of the present invention preferably contains at least two kinds of resins.
Specifically, the curable resin composition of the present invention may contain two or more kinds of a specific resin and another resin described later in total, or may contain two or more kinds of a specific resin, but is specific. It is preferable to contain two or more kinds of resins.
When the curable resin composition of the present invention contains two or more kinds of specific resins, for example, two or more kinds of polyimide precursors having different structures derived from dianhydride (R 115 in the above formula (2)). It is preferable to contain the polyimide precursor of.
<他の樹脂>
 本発明の組成物は、上述した特定樹脂と、特定樹脂とは異なる、他の樹脂(以下、単に「他の樹脂」ともいう。)とを含んでもよい。
 他の樹脂としては、ポリアミドイミド、ポリアミドイミド前駆体、フェノール樹脂、ポリアミド、エポキシ樹脂、ポリシロキサン、シロキサン構造を含む樹脂、アクリル樹脂等が挙げられる。
 例えば、アクリル樹脂を更に加えることにより、塗布性に優れた組成物が得られ、また、耐溶剤性に優れた有機膜が得られる。
 例えば、後述する重合性化合物に代えて、又は、後述する重合性化合物に加えて、重量平均分子量が20,000以下の重合性基価の高いアクリル系樹脂を組成物に添加することにより、組成物の塗布性、有機膜の耐溶剤性等を向上させることができる。
<Other resins>
The composition of the present invention may contain the above-mentioned specific resin and another resin (hereinafter, also simply referred to as “other resin”) different from the specific resin.
Examples of other resins include polyamide-imide, polyamide-imide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, acrylic resin and the like.
For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained.
For example, the composition may be obtained 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 solvent resistance of an organic film, and the like.
 本発明の組成物が他の樹脂を含む場合、他の樹脂の含有量は、組成物の全固形分に対し、0.01質量%以上であることが好ましく、0.05質量%以上であることがより好ましく、1質量%以上であることが更に好ましく、2質量%以上であることが一層好ましく、5質量%以上であることがより一層好ましく、10質量%以上であることが更に一層好ましい。
 また、本発明の組成物における、他の樹脂の含有量は、組成物の全固形分に対し、80質量%以下であることが好ましく、75質量%以下であることがより好ましく、70質量%以下であることが更に好ましく、60質量%以下であることが一層好ましく、50質量%以下であることがより一層好ましい。
 また、本発明の組成物の好ましい一態様として、他の樹脂の含有量が低含有量である態様とすることもできる。上記態様において、他の樹脂の含有量は、組成物の全固形分に対し、20質量%以下であることが好ましく、15質量%以下であることがより好ましく、10質量%以下であることが更に好ましく、5質量%以下であることが一層好ましく、1質量%以下であることがより一層好ましい。上記含有量の下限は特に限定されず、0質量%以上であればよい。
 本発明の組成物は、他の樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。
When the composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the composition. It is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, still more preferably 10% by mass or more. ..
The content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass, based on the total solid content of the composition. It is more preferably less than or equal to, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferred embodiment of the composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and more preferably 10% by mass or less, based on the total solid content of the composition. Further, it is more preferably 5% by mass or less, further 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 composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount is within the above range.
<オキサゾリン基を有する化合物>
 本発明の硬化性樹脂組成物は、オキサゾリン基を有する化合物を含む。
 本発明において、オキサゾリン基における水素原子は、公知の置換基により置換されていてもよい。また、オキサゾリン基を有する化合物が、オキサゾリン基として無置換のオキサゾリン基を有する態様も、本発明の好ましい態様の1つである。
 本発明において、オキサゾリン基は、下記式(1-1)で表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000031

 式(1-1)中、R~Rはそれぞれ独立に、水素原子又は置換基を表し、*は他の構造との結合部位を表す。
 式(1-1)中、R~Rは、いずれも水素原子又はアルキル基であることが好ましい。
 上記アルキル基としては、炭素数1~10のアルキル基等が挙げられる。
<Compound with oxazoline group>
The curable resin composition of the present invention contains a compound having an oxazoline group.
In the present invention, the hydrogen atom in the oxazoline group may be substituted with a known substituent. Further, an embodiment in which the compound having an oxazoline group has an unsubstituted oxazoline group as the oxazoline group is also one of the preferred embodiments of the present invention.
In the present invention, the oxazoline group is preferably a group represented by the following formula (1-1).
Figure JPOXMLDOC01-appb-C000031

In the formula (1-1), R 1 to R 4 independently represent a hydrogen atom or a substituent, and * represents a binding site with another structure.
In the formula (1-1), it is preferable that R 1 to R 4 are all hydrogen atoms or alkyl groups.
Examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms.
 オキサゾリン基を有する化合物は、構造中にオキサゾリン基を1個のみ含む化合物であってもよいが、硬化膜の金属との密着性の観点からは、構造中にオキサゾリン基を2個以上含む化合物であることが好ましい。 The compound having an oxazoline group may be a compound containing only one oxazoline group in the structure, but from the viewpoint of adhesion of the cured film to the metal, the compound containing two or more oxazoline groups in the structure is used. It is preferable to have.
 オキサゾリン基を有する化合物は、重合性基を含むことが好ましい。
 上記重合性基としては、ラジカル重合性基、アルコキシシリル基、エポキシ基、オキセタニル基、メチロール基、アルコキシメチル基、(ブロック)イソシアネート基等の公知の重合性基が挙げられる。
 これらの中でも、硬化膜の金属との密着性の観点から、オキサゾリン基を有する化合物は重合性基として、ラジカル重合性基、及び、アルコキシシリル基よりなる群から選ばれた少なくとも1種の基を含むことが好ましい。
The compound having an oxazoline group preferably contains a polymerizable group.
Examples of the polymerizable group include known polymerizable groups such as a radically polymerizable group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group and a (blocking) isocyanate group.
Among these, from the viewpoint of adhesion of the cured film to the metal, the compound having an oxazoline group has at least one group selected from the group consisting of a radically polymerizable group and an alkoxysilyl group as the polymerizable group. It is preferable to include it.
 上記アルコキシシリル基は、モノアルコキシシリル基、ジアルコキシシリル基、トリアルコキシシリル基のいずれであってもよいが、硬化膜の金属との密着性の観点からは、トリアルコキシシリル基が好ましい。
 上記アルコキシシリル基におけるアルコキシ基としては、炭素数1~4のアルコキシ基が好ましく、メトキシ基又はエトキシ基がより好ましく、エトキシ基が更に好ましい。
The alkoxysilyl group may be any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group, but a trialkoxysilyl group is preferable from the viewpoint of adhesion of the cured film to the metal.
As the alkoxy group in the alkoxysilyl group, an alkoxy group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and an ethoxy group is further preferable.
 上記ラジカル重合性基としては、エチレン性不飽和結合を有する基が好ましい。
 エチレン性不飽和結合を有する基としては、ビニル基、アリル基、ビニルフェニル基等の芳香環に直接結合した、置換されていてもよいビニル基を有する基、(メタ)アクリルアミド基、(メタ)アクリロイルオキシ基が好ましく挙げられる。
As the radically polymerizable group, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group. Acryloyloxy groups are preferred.
 オキサゾリン基を有する化合物は、アゾール基を含むことが好ましい。
 上記態様によれば、アゾール基が銅等の金属と配位することにより、金属との密着性がさらに向上すると考えられる。
 オキサゾリン基を有する化合物におけるアゾール基としては、環員として窒素原子を1つ以上含む複素5員環化合物であって、置換基又は縮合環構造を有していてもよい複素5員環化合物から水素原子を1つ以上除いた構造を有する基であればよいが、環員として1以上の窒素原子及び1又は複数の炭素原子のみを含む複素5員環化合物であって、置換基を有していてもよい複素5員環化合物から水素原子を1つ以上除いた構造を有する基であることが好ましい。
 硬化膜の金属との密着性の観点から、アゾール基としては、ピロール環、ピラゾール環、インダゾール環、イミダゾール環、ベンゾイミダゾール環、1,2,3-トリアゾール環、1,2,4-トリアゾール環、ベンゾトリアゾール環、又は、テトラゾール環から水素原子を1つ以上除いた構造を有する基であることが好ましく、イミダゾール環、ベンゾイミダゾール環、1,2,4-トリアゾール環、又は、ベンゾトリアゾール環から水素原子を1つ以上除いた構造を有する基であることがより好ましい。
The compound having an oxazoline group preferably contains an azole group.
According to the above aspect, it is considered that the adhesion with the metal is further improved by coordinating the azole group with a metal such as copper.
The azole group in the compound having an oxazoline group is a complex 5-membered ring compound containing one or more nitrogen atoms as a ring member, and hydrogen from a complex 5-membered ring compound which may have a substituent or a fused ring structure. It may be a group having a structure excluding one or more atoms, but it is a complex 5-membered ring compound containing only one or more nitrogen atoms and one or a plurality of carbon atoms as ring members, and has a substituent. It is preferable that the group has a structure in which one or more hydrogen atoms are removed from the complex 5-membered ring compound which may be used.
From the viewpoint of adhesion of the cured film to the metal, the azole groups include a pyrrole ring, a pyrazole ring, an indazole ring, an imidazole ring, a benzimidazole ring, a 1,2,3-triazole ring, and a 1,2,4-triazole ring. , A benzotriazole ring, or a group having a structure in which one or more hydrogen atoms are removed from the tetrazole ring, preferably from an imidazole ring, a benzimidazole ring, 1,2,4-triazole ring, or a benzotriazole ring. It is more preferable that the group has a structure excluding one or more hydrogen atoms.
 また、オキサゾリン基を有する化合物におけるアゾール基は、下記式(B-1)又は下記式(B-2)で表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000032

 式(B-1)中、RB1は他の構造との結合部位、水素原子又は1価の有機基を表し、ZB1~ZB4はそれぞれ独立に、=CRB7-又は窒素原子を表し、RB7は他の構造との結合部位、水素原子又は1価の有機基を表し、式(B-1)に含まれるRB1及びRB7のうち、少なくとも1つは他の構造との結合部位を表す;
 式(B-2)中、RB2~RB6はそれぞれ独立に、他の構造との結合部位、水素原子又は1価の有機基を表し、ZB5及びZB6はそれぞれ独立に、=CRB8-または窒素原子を表し、RB8は他の構造との結合部位、水素原子又は1価の有機基を表し、式(B-2)に含まれるRB2~RB6及びRB8のうち、少なくとも1つは他の構造との結合部位を表す。
Further, the azole group in the compound having an oxazoline group is preferably a group represented by the following formula (B-1) or the following formula (B-2).
Figure JPOXMLDOC01-appb-C000032

In formula (B-1), RB1 represents a binding site with another structure, a hydrogen atom or a monovalent organic group, and Z B1 to Z B4 independently represent = CR B7 -or a nitrogen atom. R B7 represents a binding site, a hydrogen atom or a monovalent organic group with other structures, of R B1 and R B7 contained in the formula (B1), the binding site of the at least one other structure Represents;
In formula (B-2), RB2 to RB6 independently represent a bond site with another structure, a hydrogen atom or a monovalent organic group, and Z B5 and Z B6 independently represent = CR B8. - or a nitrogen atom, the binding site of the R B8 other structures, represent a hydrogen atom or a monovalent organic group, of R B2 ~ R B6 and R B8 included in the formula (B2), at least One represents a binding site with another structure.
 式(B-1)中、RB1は他の構造との結合部位、水素原子又は1価の有機基を表し、他の構造との結合部位であることがより好ましい。
 上記RB1における1価の有機基としては、特に限定されず、本発明の効果が得られる限りにおいて公知の有機基を使用することが可能であるが、炭化水素基又はカルボキシ基であることが好ましく、アルキル基又はカルボキシ基であることがより好ましい。上記炭化水素基又はアルキル基の炭素数は特に限定されないが、1~10であることが好ましく、1~4であることがより好ましい。
In the formula (B-1), RB1 represents a binding site with another structure, a hydrogen atom or a monovalent organic group, and is more preferably a binding site with another structure.
The monovalent organic group represented by R B1, not particularly limited, but as long as the effect of the present invention are obtained can be used known organic group, a hydrocarbon group or a carboxy group It is preferably an alkyl group or a carboxy group, more preferably. The number of carbon atoms of the hydrocarbon group or the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 4.
 式(B-1)中、ZB1~ZB4はそれぞれ独立に、=CRB7-又は窒素原子を表す。
 中でも、ZB1~ZB4のうち2つが窒素原子であり、2つが=CRB7-である態様、ZB1~ZB4のうち1つが窒素原子であり、3つが=CRB7-である態様、又は、ZB1~ZB4のうち3つが窒素原子であり、1つが=CRB7-である態様が好ましい。
 また、これらの中でも、ZB1及びZB3が窒素原子であり、ZB2及びZB4が=CRB7-である態様、ZB1及びZB2が窒素原子であり、ZB3及びZB4が=CRB7-である態様、ZB2が窒素原子であり、ZB1、ZB3及びZB4が=CRB7-である態様、又は、ZB1、ZB2及びZB3が窒素原子であり、ZB4が=CRB7-である態様が好ましく、ZB1及びZB3が窒素原子であり、ZB2及びZB4が=CRB7-である態様がより好ましい。
 上記RB7は水素原子又は1価の有機基であることが好ましい。
 また、ZB1、ZB2及びZB3が窒素原子であり、ZB4が=CRB7-である場合、RB7は他の構造との結合部位であることが好ましい。
 RB7における1価の有機基の好ましい態様は、上述のRB1における1価の有機基の好ましい態様と同様である。
In formula (B-1), Z B1 to Z B4 independently represent = CR B7 − or a nitrogen atom.
Among them, two of Z B1 to Z B4 are nitrogen atoms and two are = CR B7- , and one of Z B1 to Z B4 is a nitrogen atom and three are = CR B7- . Alternatively, it is preferable that three of Z B1 to Z B4 are nitrogen atoms and one is = CR B7 −.
Among these, Z B1 and Z B3 are nitrogen atoms, Z B2 and Z B4 are = CR B7 −, Z B1 and Z B2 are nitrogen atoms, and Z B3 and Z B4 are = CR. B7 -in which Z B2 is a nitrogen atom and Z B1 , Z B3 and Z B4 are = CR B7 -or in which Z B1 , Z B2 and Z B3 are nitrogen atoms and Z B4 is. The embodiment in which = CR B7 − is preferable, and the embodiment in which Z B1 and Z B3 are nitrogen atoms and Z B2 and Z B4 are = CR B7 − is more preferable.
The RB7 is preferably a hydrogen atom or a monovalent organic group.
Further, when Z B1 , Z B2 and Z B3 are nitrogen atoms and Z B4 is = CR B7 −, RB7 is preferably a binding site with another structure.
A preferred embodiment of the monovalent organic group in R B7 is similar to the preferred embodiment of the monovalent organic group in the above R B1.
 式(B-1)に含まれるRB1及びRB7のうち、少なくとも1つは他の構造との結合部位を表し、少なくともRB1が他の構造との結合部位を表すことが好ましい。また、式(B-1)において、RB1のみが他の構造との結合部位を表し、RB7はそれぞれ独立に水素原子又は1価の有機基を表す態様も、本発明の好ましい態様の1つである。 Of R B1 and R B7 contained in the formula (B1), at least one represents a bonding site with the other structures, it is preferable that at least R B1 represents a binding site with another structure. Further, in the equation (B1), only the R B1 represents a binding site with another structure, embodiments each represent R B7 independently a hydrogen atom or a monovalent organic group, preferred embodiments of the present invention 1 It is one.
 式(B-2)中、ZB5及びZB6はそれぞれ独立に、=CRB8-又は窒素原子を表す。
 中でも、ZB5及びZB6がいずれも窒素原子を表す態様、又は、ZB5が窒素原子を、ZB6が=CRB8-をそれぞれ表す態様が好ましい。
 式(B-2)において、ZB5及びZB6がいずれも窒素原子を表す場合、RB6が他の構造との結合部位を表すことが好ましい。また、式(B-2)において、ZB5及びZB6がいずれも窒素原子を表し、かつ、RB6のみが他の構造との結合部位を表す態様も、本発明の好ましい態様の1つである。
 式(B-2)において、ZB5が窒素原子を、ZB6が=CRB8-をそれぞれ表す場合、RB8が他の構造との結合部位を表すことが好ましい。また、式(B-2)において、ZB5が窒素原子を、ZB6が=CRB8-をそれぞれ表し、かつ、RB8のみが他の構造との結合部位を表す態様も、本発明の好ましい態様の1つである。
In formula (B-2), Z B5 and Z B6 each independently represent = CR B8 -or a nitrogen atom.
Above all, aspects represents the Z B5 and Z B6 are both nitrogen atom, or, the Z B5 nitrogen atom, Z B6 is = CR B8 - aspects that represent each desirable.
In formula (B-2), when Z B5 and Z B6 is representative of the either nitrogen atom, it is preferred that R B6 represents a binding site with another structure. Further, in the formula (B-2), a mode in which both Z B5 and Z B6 represent a nitrogen atom and only RB6 represents a binding site with another structure is also one of the preferred embodiments of the present invention. be.
In formula (B-2), the Z B5 nitrogen atom, Z B6 is = CR B8 - If the representative respectively, it is preferred that R B8 represents a binding site with another structure. Further, in the formula (B-2), it is also preferable that Z B5 represents a nitrogen atom, Z B6 represents = CR B8 −, and only RB8 represents a binding site with another structure. It is one of the embodiments.
 式(B-2)中、RB2~RB5はそれぞれ独立に、水素原子又は1価の有機基を表すことが好ましい。RB2~RB5における1価の有機基の好ましい態様は、上述のRB1における1価の有機基の好ましい態様と同様である。
 式(B-2)中、ZB5が窒素原子を、ZB6が=CRB8-をそれぞれ表す場合、RB6は水素原子又は1価の有機基を表すことが好ましい。RB6における1価の有機基の好ましい態様は、上述のRB1における1価の有機基の好ましい態様と同様である。
 他の場合には、RB6は他の構造との結合部位を表すことが好ましい。特に、ZB5が窒素原子を、ZB6が=CRB8-をそれぞれ表す場合、RB8が他の構造との結合部位を表すことが好ましい。
 式(B-2)中、RB8は他の構造との結合部位を表すことが好ましい。
B5及びZB6がいずれも=CRB8-を表す場合、一方のRB8が他の構造との結合部位を表し、他方が水素原子又は1価の有機基を表すことが好ましい。RB8における1価の有機基の好ましい態様は、上述のRB1における1価の有機基の好ましい態様と同様である。
In the formula (B-2), it is preferable that RB2 to RB5 each independently represent a hydrogen atom or a monovalent organic group. A preferred embodiment of the monovalent organic group in R B2 ~ R B5 is the same as the preferred embodiment of the monovalent organic group in the above R B1.
In formula (B-2), the Z B5 nitrogen atom, Z B6 is = CR B8 - If the representative respectively, R B6 preferably represents a hydrogen atom or a monovalent organic group. A preferred embodiment of the monovalent organic group in R B6 are the same as the preferred embodiment of the monovalent organic group in the above R B1.
In other cases, RB6 preferably represents a binding site with another structure. In particular, the Z B5 nitrogen atom, Z B6 is = CR B8 - If the representative respectively, it is preferred that R B8 represents a binding site with another structure.
In formula (B-2), RB8 preferably represents a binding site with another structure.
Z B5 and Z B6 are both = CR B8 - When referring to, one of R B8 represents a binding site with another structure, it is preferable that the other represents a hydrogen atom or a monovalent organic group. A preferred embodiment of the monovalent organic group in R B8 are the same as the preferred embodiment of the monovalent organic group in the above R B1.
 式(B-2)に含まれるRB2~RB6及びRB8のうち、少なくとも1つは他の構造との結合部位を表し、少なくともRB6又はRB8が他の構造との結合部位を表すことが好ましい。また、式(B-2)において、RB6及びRB8のうち一方のみが他の構造との結合部位を表し、RB6及びRB8のうち他方及びRB2~RB5はそれぞれ独立に水素原子又は1価の有機基を表す態様も、本発明の好ましい態様の1つである。 Of R B2 ~ R B6 and R B8 included in the formula (B2), at least one represents a binding site with another structure, at least R B6 or R B8 represents a binding site with another structure Is preferable. Further, in the formula (B-2), only one of RB6 and RB8 represents a binding site with another structure, and the other of RB6 and RB8 and RB2 to RB5 are independently hydrogen atoms. Alternatively, an embodiment representing a monovalent organic group is also one of the preferred embodiments of the present invention.
 これらの中でも、アゾール基は、下記式(B-3)~式(B-6)のいずれかで表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000033
Among these, the azole group is preferably a group represented by any of the following formulas (B-3) to (B-6).
Figure JPOXMLDOC01-appb-C000033
 式(B-3)~式(B-6)中、RB9~RB20はそれぞれ独立に、水素原子又は1価の有機基を表し、*は他の構造との結合部位を表す。
 式(B-3)~式(B-6)中、RB9~RB20における1価の有機基の好ましい態様は、上述のRB1における1価の有機基の好ましい態様と同様である。
In formulas (B-3) to (B-6), RB9 to RB20 each independently represent a hydrogen atom or a monovalent organic group, and * represents a binding site with another structure.
Wherein (B-3) ~ formula (B-6), preferred embodiments of the monovalent organic group in R B9 ~ R B20 are the same as the preferred embodiment of the monovalent organic group in the above R B1.
 オキサゾリン基を有する化合物は、分子量2,000未満の化合物(以下、「オキサゾリン基含有低分子化合物」ともいう。)であってもよいし、樹脂(以下、「オキサゾリン基含有樹脂」ともいう。)であってもよい。
 また、硬化膜の金属との密着性の観点からは、硬化性樹脂組成物は、オキサゾリン基含有低分子化合物と、オキサゾリン基含有樹脂との両方を含むことも好ましい。
 密着性の観点からは、オキサゾリン基を有する化合物は樹脂であることが好ましい。
The compound having an oxazoline group may be a compound having a molecular weight of less than 2,000 (hereinafter, also referred to as “oxazoline group-containing low molecular weight compound”) or a resin (hereinafter, also referred to as “oxazoline group-containing resin”). May be.
Further, from the viewpoint of adhesion of the cured film to the metal, it is also preferable that the curable resin composition contains both an oxazoline group-containing low molecular weight compound and an oxazoline group-containing resin.
From the viewpoint of adhesion, the compound having an oxazoline group is preferably a resin.
〔オキサゾリン基含有低分子化合物〕
 オキサゾリン基含有低分子化合物の分子量は、2,000未満であり、1,500以下であることが好ましく、1,000以下であることがより好ましい。
[Oxazoline group-containing low molecular weight compound]
The molecular weight of the oxazoline group-containing low molecular weight compound is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.
 オキサゾリン基含有低分子化合物におけるオキサゾリン基の数は、1~10であることが好ましく、1~4であることがより好ましく、1又は2であることが更に好ましい。
 また、密着性の観点からは、オキサゾリン基含有低分子化合物におけるオキサゾリン基の数は、2~10であることが好ましく、2~4であることがより好ましく、2であることが更に好ましい。
The number of oxazoline groups in the oxazoline group-containing low molecular weight compound is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
From the viewpoint of adhesion, the number of oxazoline groups in the oxazoline group-containing low molecular weight compound is preferably 2 to 10, more preferably 2 to 4, and even more preferably 2.
 オキサゾリン基含有低分子化合物としては、下記式(BL-1)又は式(BL-2)で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000034

 式(BL-1)中、R~Rはそれぞれ独立に、水素原子又は置換基を表し、Rは置換基を表す。
 式(BL-2)中、R~Rはそれぞれ独立に、水素原子又は置換基を表し、Lは単結合又はn+1価の連結基を表し、nは2以上の整数を表す。
 式(BL-1)中、R~Rはそれぞれ独立に、式(1―1)中のR~Rと同義であり、好ましい態様も同様である。
 式(BL-1)中、Rは置換基を表し、上述のアゾール基、又は、上述の重合性基を含む基であることが好ましく、上述の重合性基を含む基であることがより好ましい。また、Rがビニル基である態様が、本発明の好ましい態様の1つである。
 式(BL-2)中、R~Rはそれぞれ独立に、式(1―1)中のR~Rと同義であり、好ましい態様も同様である。
 式(BL-2)中、Lは単結合又はn+1価の連結基を表し、単結合又は炭化水素基が好ましい。上記炭化水素基としては、芳香族炭化水素基であってもよいし、脂肪族炭化水素基であってもよいが、芳香族炭化水素基又は飽和脂肪族炭化水素基が好ましく、芳香族炭化水素基がより好ましく、ベンゼン環からn+1個の水素原子を除いた基が更に好ましい。
 式(BL-2)中、nは2以上の整数を表し、2~10の整数であることが好ましく、2~4の整数であることがより好ましく、2であること更に好ましい。
As the oxazoline group-containing low molecular weight compound, a compound represented by the following formula (BL-1) or formula (BL-2) is preferable.
Figure JPOXMLDOC01-appb-C000034

In the formula (BL-1), R 1 to R 4 independently represent a hydrogen atom or a substituent, and R 5 represents a substituent.
In the formula (BL-2), R 1 to R 4 independently represent a hydrogen atom or a substituent, L 1 represents a single bond or an n + 1 valent linking group, and n represents an integer of 2 or more.
In the formula (BL-1), R 1 to R 4 are independently synonymous with R 1 to R 4 in the formula (1-1), and the preferred embodiments are also the same.
Wherein (BL-1), R 5 represents a substituent, an azole group described above or, preferably a group containing a polymerizable group include more be a group containing a polymerizable group described above preferable. Further, embodiments R 5 is a vinyl group is one of the preferred embodiments of the present invention.
In the formula (BL-2), R 1 to R 4 are independently synonymous with R 1 to R 4 in the formula (1-1), and the preferred embodiments are also the same.
In the formula (BL-2), L 1 represents a single bond or an n + 1 valent linking group, and a single bond or a hydrocarbon group is preferable. The hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but an aromatic hydrocarbon group or a saturated aliphatic hydrocarbon group is preferable, and an aromatic hydrocarbon group is preferable. A group is more preferable, and a group obtained by removing n + 1 hydrogen atoms from the benzene ring is further preferable.
In the formula (BL-2), n represents an integer of 2 or more, preferably an integer of 2 to 10, more preferably an integer of 2 to 4, and even more preferably 2.
〔オキサゾリン基含有樹脂〕
 オキサゾリン基含有樹脂の重量平均分子量は、3,000~150,000であることが好ましく、3,000~80,000であることがより好ましく、6,000~50,000であることが更に好ましい。
[Oxazoline group-containing resin]
The weight average molecular weight of the oxazoline group-containing resin is preferably 3,000 to 150,000, more preferably 3,000 to 80,000, and even more preferably 6,000 to 50,000. ..
 1gのオキサゾリン基含有樹脂におけるオキサゾリン基のモル量は、0.001~10mmol/gであることが好ましく、0.1~10mmol/gであることがより好ましく、0.5~9mmol/gであることが更に好ましい。 The molar amount of the oxazoline group in 1 g of the oxazoline group-containing resin is preferably 0.001 to 10 mmol / g, more preferably 0.1 to 10 mmol / g, and 0.5 to 9 mmol / g. Is even more preferable.
 オキサゾリン基含有樹脂は、オキサゾリン基を含む繰り返し単位を有する樹脂であることが好ましい。
 オキサゾリン基を含む繰り返し単位としては、下記式(BO-1)で表される繰り返し単位が好ましい。
Figure JPOXMLDOC01-appb-C000035
 式(BO-1)中、Lは単結合又は2価の連結基を表し、Xはオキサゾリン基を表し、Rは水素原子又はメチル基を表す。
式(BO-1)中、Lは単結合が好ましい。Lが2価の連結基である場合、炭化水素基、又は、炭化水素基と、-O-、-S-、-C(=O)-、-S(=O)-及び-NR-よりなる群から選ばれた少なくとも1つの基との結合により表される基が好ましい。
 上記Rは水素原子又は炭化水素基を表し、水素原子、アルキル基又はアリール基がより好ましく、水素原子又はアルキル基が更に好ましく、水素原子が特に好ましい。
式(BO-1)中、Xであるオキサゾリン基の詳細は上述の通りであり、式(1-1)で表される基が好ましい。
式(BO-1)中、Rはメチル基が好ましい。
The oxazoline group-containing resin is preferably a resin having a repeating unit containing an oxazoline group.
As the repeating unit containing an oxazoline group, a repeating unit represented by the following formula (BO-1) is preferable.
Figure JPOXMLDOC01-appb-C000035
Wherein (BO-1), L B represents a single bond or a divalent linking group, X B represents an oxazoline group, R B represents a hydrogen atom or a methyl group.
Wherein (BO-1), L B represents a single bond. If L B is a divalent linking group, a hydrocarbon group, or a hydrocarbon group, -O -, - S -, - C (= O) -, - S (= O) 2 - and -NR Groups represented by binding to at least one group selected from the group consisting of N-are preferred.
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.
Wherein (BO-1), the details of the oxazoline group is X B is as described above, a group represented by the formula (1-1) is preferred.
Wherein (BO-1), R B is preferably a methyl group.
 オキサゾリン基含有樹脂は、オキサゾリン基を含む繰り返し単位とは異なる、他の繰り返し単位を更に含むことが好ましい。
 他の繰り返し単位としては、アゾール基を含む繰り返し単位、重合性基を含む繰り返し単位等が挙げられる。
The oxazoline group-containing resin preferably further contains other repeating units that are different from the repeating units containing the oxazoline group.
Examples of the other repeating unit include a repeating unit containing an azole group, a repeating unit containing a polymerizable group, and the like.
-アゾール基を含む繰り返し単位-
 オキサゾリン基含有樹脂は、アゾール基を含む繰り返し単位として下記式(BA-1)で表される繰り返し単位を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000036

 式(BA-1)中、Lは単結合又は2価の連結基を表し、Xはアゾール基を表し、Rは水素原子又はメチル基を表す。
 式(BA-1)中、Lは単結合又は2価の連結基を表す。
 上記2価の連結基としては、炭化水素基、又は、炭化水素基と、-O-、-S-、-C(=O)-、-S(=O)-及び-NR-よりなる群から選ばれた少なくとも1つの基との結合により表される基が好ましく、炭化水素基がより好ましい。
 上記Rは上述のとおりである。
 上記炭化水素基としては、飽和脂肪族炭化水素基が好ましく、アルキレン基がより好ましい。
 上記炭化水素基又はアルキレン基の炭素数は、2~20が好ましく、2~10がより好ましい。
 これらの中でも、Lは単結合、下記式(BA-1-1)で表される基又は下記式(BA-1-2)で表される基が好ましい。
Figure JPOXMLDOC01-appb-C000037

 式(BA-1-1)又は式(BA-1-2)中、Lは2価の連結基を表し、Lは単結合又は2価の連結基を表し、Lは2価の連結基を表し、Lは単結合又は2価の連結基を表し、*は式(BA-1)中のカルボニル基との結合部位を表し、A及びAは-O-又はーNR-を表し、#は(BA-1)中のXとの結合部位を表す。
-Repeating unit containing azole group-
The oxazoline group-containing resin preferably contains a repeating unit represented by the following formula (BA-1) as a repeating unit containing an azole group.
Figure JPOXMLDOC01-appb-C000036

In formula (BA-1), L 3 represents a single bond or a divalent linking group, X 3 represents an azole group, and R represents a hydrogen atom or a methyl group.
In formula (BA-1), L 3 represents a single bond or a divalent linking group.
The above-mentioned divalent linking group includes a hydrocarbon group or a hydrocarbon group, and -O-, -S-, -C (= O)-, -S (= O) 2- and -NR N-. A group represented by a bond with at least one group selected from the group is preferable, and a hydrocarbon group is more preferable.
The above RN is as described above.
As the hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
The hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
Among these, L 3 is a single bond, preferably a group represented by the following formula (BA-1-1) a group or the following formula represented (BA-1-2).
Figure JPOXMLDOC01-appb-C000037

In formula (BA-1-1) or formula (BA-1-2), L 4 represents a divalent linking group, L 5 represents a single-bonded or divalent linking group, and L 6 represents a divalent linking group. Representing a linking group, L 7 represents a single bond or a divalent linking group, * represents a bonding site with a carbonyl group in the formula (BA-1), and A 1 and A 2 represent -O- or -NR. It represents N −, and # represents the binding site with X 3 in (BA-1).
 式(BA-1-1)中、Lは炭化水素基、又は、炭化水素基と、-O-、-S-、-C(=O)-、-S(=O)-及び-NR-よりなる群から選ばれた少なくとも1つの基との結合により表される基が好ましく、炭化水素基がより好ましい。
 上記Rは上述のとおりである。
 上記炭化水素基としては、飽和脂肪族炭化水素基が好ましく、アルキレン基がより好ましい。
 上記炭化水素基又はアルキレン基の炭素数は、2~20が好ましく、2~10がより好ましい。
In the formula (BA-1-1), L 4 is a hydrocarbon group or a hydrocarbon group, and -O-, -S-, -C (= O)-, -S (= O) 2-and-. A group represented by a bond with at least one group selected from the group consisting of NR N − is preferable, and a hydrocarbon group is more preferable.
The above RN is as described above.
As the hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
The hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
 式(BA-1-1)中、Lは単結合であることが好ましい。Lが2価の連結基である場合、Lは炭化水素基、又は、炭化水素基と、-O-、-S-、-C(=O)-、-S(=O)-及び-NR-よりなる群から選ばれた少なくとも1つの基との結合により表される基が好ましく、炭化水素基がより好ましい。 Wherein (BA-1-1), it is preferred that L 5 represents a single bond. When L 5 is a divalent linking group, L 5 is a hydrocarbon group or a hydrocarbon group and -O-, -S-, -C (= O)-, -S (= O) 2- A group represented by a bond with at least one group selected from the group consisting of and -NR N- is preferable, and a hydrocarbon group is more preferable.
 式(BA-1-2)中、Lは式(BA-1-1)中のLと同義であり、好ましい態様も同様である。 In the formula (BA-1-2), L 6 is synonymous with L 4 in the formula (BA-1-1), and the preferred embodiment is also the same.
 式(BA-1-2)中、Lは2価の連結基であることが好ましい。Lが2価の連結基である場合、Lの好ましい態様は上述の式(BA-1-1)におけるLが2価の連結基である場合の好ましい態様と同様である。 In formula (BA-1-2), L 7 is preferably a divalent linking group. When L 7 is a divalent linking group, the preferred embodiment of L 7 is the same as the preferred embodiment when L 5 is a divalent linking group in the above formula (BA-1-1).
 式(BA-1-1)又は式(BA-1-2)中、A及びAは-O-又はーNR-を表し、-O-が好ましい。Rは上述のとおりである。 In the formula (BA-1-1) or the formula (BA-1-2), A 1 and A 2 represent -O- or -NR N- , and -O- is preferable. RN is as described above.
 式(BA-1)中、Xにおけるアゾール基の好ましい態様は上述のとおりである。上述のアゾール基における他の構造との結合部位が、式(BA-1)中のLとの結合部位に該当する。 Wherein (BA-1), preferred embodiments of the azole group in X 3 are as described above. Binding sites with other structures in the azole group described above, corresponds to the binding site of the L 3 in the formula (BA-1).
 オキサゾリン基含有樹脂は、式(BA-1)で表される繰り返し単位を1種のみ含んでもよいし、2種以上含んでもよい。
 オキサゾリン基含有樹脂がアゾール基を含む繰り返し単位を含む場合、1gのオキサゾリン基含有樹脂におけるアゾール基の含有モル量は、0.001~10mmol/gであることが好ましく、0.1~8mmol/gであることがより好ましい。
The oxazoline group-containing resin may contain only one type of repeating unit represented by the formula (BA-1), or may contain two or more types.
When the oxazoline group-containing resin contains a repeating unit containing an azole group, the molar amount of the azole group contained in 1 g of the oxazoline group-containing resin is preferably 0.001 to 10 mmol / g, preferably 0.1 to 8 mmol / g. Is more preferable.
-重合性基を含む繰り返し単位-
 オキサゾリン基含有樹脂は、重合性基を含む繰り返し単位として下記式(BA-2)で表される繰り返し単位を含むことが好ましい。
Figure JPOXMLDOC01-appb-C000038

 式(BA-2)中、Aは-O-又は-NR-を表し、LP1は2価の連結基を表し、XP1は重合性基を表し、Rは水素原子又はメチル基を表す。
-Repeating unit containing polymerizable group-
The oxazoline group-containing resin preferably contains a repeating unit represented by the following formula (BA-2) as a repeating unit containing a polymerizable group.
Figure JPOXMLDOC01-appb-C000038

Wherein (BA-2), A 3 is -O- or -NR N - represents, L P1 represents a divalent linking group, X P1 represents a polymerizable group, R represents a hydrogen atom or a methyl group show.
 式(BA-2)中、Aは-O-又は-NR-を表し、-O-が好ましい。Rは上述のとおりである。 Wherein (BA-2), A 3 is -O- or -NR N - represents, -O- it is preferable. RN is as described above.
 式(BA-2)中、LP1は2価の連結基を表し、炭化水素基、又は、炭化水素基と、-O-、-S-、-C(=O)-、-S(=O)-及び-NR-よりなる群から選ばれた少なくとも1つの基との結合により表される基が好ましく、炭化水素基がより好ましい。
 上記Rは上述のとおりである。
 上記炭化水素基としては、飽和脂肪族炭化水素基が好ましく、アルキレン基がより好ましい。
 上記炭化水素基又はアルキレン基の炭素数は、2~20が好ましく、2~10がより好ましい。
In the formula (BA-2), LP1 represents a divalent linking group, which is a hydrocarbon group or a hydrocarbon group, and —O—, —S—, —C (= O) −, —S (=). O) A group represented by a bond with at least one group selected from the group consisting of 2- and -NR N- is preferable, and a hydrocarbon group is more preferable.
The above RN is as described above.
As the hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
The hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
 XP1は重合性基を表し、アルコキシシリル基、エポキシ基、オキセタニル基又はラジカル重合性基が好ましく、アルコキシシリル基がより好ましい。アルコキシシリル基及びラジカル重合性基の好ましい態様は上述のとおりである。 X P1 represents a polymerizable group, alkoxysilyl group, an epoxy group, oxetanyl group or preferably a radical polymerizable group, alkoxysilyl group is more preferable. Preferred embodiments of the alkoxysilyl group and the radically polymerizable group are as described above.
 オキサゾリン基含有樹脂は、式(BA-2)で表される繰り返し単位を1種のみ含んでもよいし、2種以上含んでもよい。
 特に、オキサゾリン基含有樹脂が、重合性基が異なる複数種の式(BA-2)で表される繰り返し単位を含むことも本発明の好ましい態様の一つである。上記態様において、オキサゾリン基含有樹脂は、重合性基としてアルコキシシリル基を含む式(BA-2)で表される繰り返し単位と、重合性基としてアルコキシシリル基とは異なる基を含む式(BA-2)で表される繰り返し単位とを含むことが好ましい。
 オキサゾリン基含有樹脂が重合性基を含む繰り返し単位を含む場合、1gのオキサゾリン基含有樹脂における重合性基の含有モル量は、0.001~10mmol/gであることが好ましく、0.01~5mmol/gであることがより好ましい。
The oxazoline group-containing resin may contain only one type of repeating unit represented by the formula (BA-2), or may contain two or more types.
In particular, it is one of the preferred embodiments of the present invention that the oxazoline group-containing resin contains a repeating unit represented by a plurality of kinds of formulas (BA-2) having different polymerizable groups. In the above embodiment, the oxazoline group-containing resin contains a repeating unit represented by the formula (BA-2) containing an alkoxysilyl group as a polymerizable group and a group different from the alkoxysilyl group as a polymerizable group (BA-). It is preferable to include the repeating unit represented by 2).
When the oxazoline group-containing resin contains a repeating unit containing a polymerizable group, the molar amount of the polymerizable group in 1 g of the oxazoline group-containing resin is preferably 0.001 to 10 mmol / g, preferably 0.01 to 5 mmol. It is more preferably / g.
-他の繰り返し単位-
 また、オキサゾリン基含有樹脂は、上述の式(BA-1)又は式(BA-2)で表される繰り返し単位とは異なる、他の繰り返し単位を更に有してもよい。
 他の繰り返し単位としては、例えば、スチレン又は置換スチレンに由来の繰り返し単位が挙げられる。
-Other repeating units-
Further, the oxazoline group-containing resin may further have another repeating unit different from the repeating unit represented by the above formula (BA-1) or the formula (BA-2).
Other repeating units include, for example, repeating units derived from styrene or substituted styrene.
〔具体例〕
 オキサゾリン基を有する化合物の具体例としては、実施例で使用された化合物が挙げられるが、これに限定されるものではない。
〔Concrete example〕
Specific examples of the compound having an oxazoline group include, but are not limited to, the compound used in the examples.
〔含有量〕
 オキサゾリン基を有する化合物の含有量は、本発明の硬化性樹脂組成物の全固形分に対して0.05~10質量%であることが好ましく、0.10~5質量%であることがより好ましく、0.15~2質量%であることが更に好ましい。
 本発明の硬化性樹脂組成物は、オキサゾリン基を有する化合物を1種のみ含有していてもよいし、2種以上含有していてもよい。オキサゾリン基を有する化合物を2種以上含有する場合は、合計量が上記範囲であることが好ましい。
〔Content〕
The content of the compound having an oxazoline group is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, based on the total solid content of the curable resin composition of the present invention. It is preferably 0.15 to 2% by mass, more preferably 0.15 to 2% by mass.
The curable resin composition of the present invention may contain only one compound having an oxazoline group, or may contain two or more compounds. When two or more compounds having an oxazoline group are contained, the total amount is preferably in the above range.
<酸基及びアルコキシシリル基を含む化合物>
 本発明の硬化性樹脂組成物は、酸基及びアルコキシシリル基を含む化合物を含む。
 酸基及びアルコキシシリル基を含む化合物における酸基としては、カルボキシ基、フェノール性ヒドロキシ基、芳香族チオール基が好ましく、カルボキシ基がより好ましい。
 酸基及びアルコキシシリル基を含む化合物におけるアルコキシシリル基の好ましい態様は、上述のオキサゾリン基を有する化合物におけるアルコキシシリル基の好ましい態様と同様である。
<Compound containing acid group and alkoxysilyl group>
The curable resin composition of the present invention contains a compound containing an acid group and an alkoxysilyl group.
As the acid group in the compound containing the acid group and the alkoxysilyl group, a carboxy group, a phenolic hydroxy group and an aromatic thiol group are preferable, and a carboxy group is more preferable.
The preferred embodiment of the alkoxysilyl group in the compound containing an acid group and the alkoxysilyl group is the same as the preferred embodiment of the alkoxysilyl group in the above-mentioned compound having an oxazoline group.
 酸基及びアルコキシシリル基を含む化合物は、アルコキシシリル基とは異なる重合性基を含むことも好ましい。
 アルコキシシリル基とは異なる重合性基としては、ラジカル重合性基、エポキシ基、オキセタニル基、メチロール基、アルコキシメチル基、(ブロック)イソシアネート基等の公知の重合性基が挙げられ、ラジカル重合性基又はエポキシ基が好ましく、ラジカル重合性基がより好ましい。
 酸基及びアルコキシシリル基を含む化合物は、アゾール基を含むことも好ましい。
 上記アゾール基としては、上述のオキサゾリン基を有する化合物において記載したアゾール基が挙げられ、好ましい態様も同様である。
 これらの中でも、硬化膜の金属との密着性の観点からは、酸基及びアルコキシシリル基を含む化合物が、ラジカル重合性基及びアゾール基よりなる群から選ばれた少なくとも1種の基を含むことが好ましい。
It is also preferable that the compound containing an acid group and an alkoxysilyl group contains a polymerizable group different from the alkoxysilyl group.
Examples of the polymerizable group different from the alkoxysilyl group include known polymerizable groups such as a radically polymerizable group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group and a (blocking) isocyanate group, and a radically polymerizable group. Alternatively, an epoxy group is preferable, and a radically polymerizable group is more preferable.
The compound containing an acid group and an alkoxysilyl group preferably contains an azole group.
Examples of the azole group include the azole groups described in the above-mentioned compounds having an oxazoline group, and the same applies to preferred embodiments.
Among these, from the viewpoint of adhesion of the cured film to the metal, the compound containing an acid group and an alkoxysilyl group contains at least one group selected from the group consisting of a radically polymerizable group and an azole group. Is preferable.
 酸基及びアルコキシシリル基を含む化合物は、分子量2,000未満の化合物(以下、「低分子化合物C」ともいう。)であってもよいし、樹脂(以下、「樹脂C」ともいう。)であってもよい。
 また、硬化膜の金属との密着性の観点からは、硬化性樹脂組成物は、低分子化合物Cと、樹脂Cとの両方を含むことも好ましい。
 密着性の観点からは、酸基及びアルコキシシリル基を含む化合物は、樹脂であることが好ましい。
The compound containing an acid group and an alkoxysilyl group may be a compound having a molecular weight of less than 2,000 (hereinafter, also referred to as “low molecular weight compound C”) or a resin (hereinafter, also referred to as “resin C”). May be.
Further, from the viewpoint of the adhesion of the cured film to the metal, it is also preferable that the curable resin composition contains both the low molecular weight compound C and the resin C.
From the viewpoint of adhesion, the compound containing an acid group and an alkoxysilyl group is preferably a resin.
〔低分子化合物C〕
 低分子化合物Cの分子量は、2,000未満であり、1,500以下であることが好ましく、1,000以下であることがより好ましい。
[Low molecular weight compound C]
The molecular weight of the low molecular weight compound C is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.
 低分子化合物Cにおける酸基の数は、1~10であることが好ましく、1~4であることがより好ましく、1又は2であることが更に好ましく、1であることが特に好ましい。
 低分子化合物Cにおけるアルコキシシリル基の数は、1~10であることが好ましく、1~4であることがより好ましく、1又は2であることが更に好ましく、1であることが特に好ましい。
The number of acid groups in the low molecular weight compound C is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.
The number of alkoxysilyl groups in the low molecular weight compound C is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.
〔樹脂C〕
 樹脂Cの重量平均分子量は、3,000~100,000であることが好ましく、5,000~80,000であることがより好ましく、5,000~50,000であることが更に好ましい。
[Resin C]
The weight average molecular weight of the resin C is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, and even more preferably 5,000 to 50,000.
 1gの樹脂Cにおける酸基のモル量は、0.01mmol/g~15mmol/gである事が好ましく、0.05mmol/g~10mmol/gである事がより好ましく、0.1~3mmol/gである事が更に好ましい。
 1gの樹脂Cにおけるアルコキシシリル基のモル量は、0.001~10mmol/gであることが好ましく、0.01~10mmol/gであることがより好ましく、0.1~5mmol/gであることが更に好ましい。
The molar amount of the acid group in 1 g of the resin C is preferably 0.01 mmol / g to 15 mmol / g, more preferably 0.05 mmol / g to 10 mmol / g, and 0.1 to 3 mmol / g. Is more preferable.
The molar amount of the alkoxysilyl group in 1 g of the resin C is preferably 0.001 to 10 mmol / g, more preferably 0.01 to 10 mmol / g, and 0.1 to 5 mmol / g. Is more preferable.
 樹脂Cは、酸基を含む繰り返し単位と、アルコキシシリル基を含む繰り返し単位とを有する樹脂であるか、又は、酸基及びアルコキシシリル基を含む繰り返し単位を有する樹脂であることが好ましく、酸基を含む繰り返し単位と、アルコキシシリル基を含む繰り返し単位とを有する樹脂であることがより好ましい。 The resin C is preferably a resin having a repeating unit containing an acid group and a repeating unit containing an alkoxysilyl group, or a resin having a repeating unit containing an acid group and an alkoxysilyl group, preferably an acid group. It is more preferable that the resin has a repeating unit containing the above and a repeating unit containing an alkoxysilyl group.
-酸基を含む繰り返し単位-
 酸基を含む繰り返し単位としては、下記式(CA-1)又は式(CA-2)で表される繰り返し単位が好ましい。
Figure JPOXMLDOC01-appb-C000039

 式(CA-1)又は式(CA-2)中、Aは-O-又は-NR-を表し、Lは2価の連結基を表し、Xは酸基を表し、Rは水素原子又はメチル基を表す。
 式(CA-2)中、Aは-O-であることが好ましい。
 式(CA-2)中、Lは炭化水素基、又は、炭化水素基と、-O-、-S-、-C(=O)-、-S(=O)-及び-NR-よりなる群から選ばれた少なくとも1つの基との結合により表される基が好ましい。
 上記Rは上述のとおりである。
 上記炭化水素基としては、飽和脂肪族炭化水素基が好ましく、アルキレン基がより好ましい。
 上記炭化水素基又はアルキレン基の炭素数は、2~20が好ましく、2~10がより好ましい。
 式(CA-2)中、Xはカルボキシ基、フェノール性ヒドロキシ基又は芳香族チオール基が好ましく、カルボキシ基がより好ましい。
-Repeating unit containing acid group-
As the repeating unit containing an acid group, a repeating unit represented by the following formula (CA-1) or formula (CA-2) is preferable.
Figure JPOXMLDOC01-appb-C000039

Wherein (CA-1) or Formula (CA-2), A C is -O- or -NR N - represents, L C represents a divalent linking group, X C denotes a group, R represents Represents a hydrogen atom or a methyl group.
Wherein (CA-2), it is preferred that A C is -O-.
Wherein (CA-2), L C is a hydrocarbon group or a hydrocarbon group, -O -, - S -, - C (= O) -, - S (= O) 2 - and -NR N -Preferably, a group represented by a bond with at least one group selected from the group consisting of.
The above RN is as described above.
As the hydrocarbon group, a saturated aliphatic hydrocarbon group is preferable, and an alkylene group is more preferable.
The hydrocarbon group or the alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
Wherein (CA-2), X C is a carboxy group, a phenolic hydroxy group or an aromatic thiol group is preferred, a carboxyl group is more preferable.
-アルコキシシリル基を含む繰り返し単位-
 樹脂Cにおける、アルコキシシリル基を含む繰り返し単位としては、上述の式(BA-2)で表される繰り返し単位であって、XP1がアルコキシシリル基である繰り返し単位が好ましく挙げられる。
-Repeating unit containing alkoxysilyl group-
As the repeating unit containing an alkoxysilyl group in the resin C, a repeating unit represented by the above formula (BA-2), wherein XP1 is an alkoxysilyl group is preferably mentioned.
-アゾール基を含む繰り返し単位-
 樹脂Cはアゾール基を含む繰り返し単位を有してもよい。
 樹脂Cにおける、アゾール基を含む繰り返し単位としては、上述の式(BA-1)で表される繰り返し単位が好ましく挙げられる。
 樹脂Cがアゾール基を含む繰り返し単位を有する場合、1gの樹脂Cにおけるアゾール基の含有モル量は、0.001~10mmol/gである事が好ましく、0.1~5mmol/gである事がより好ましい。
-Repeating unit containing azole group-
The resin C may have a repeating unit containing an azole group.
As the repeating unit containing an azole group in the resin C, the repeating unit represented by the above formula (BA-1) is preferably mentioned.
When the resin C has a repeating unit containing an azole group, the molar content of the azole group in 1 g of the resin C is preferably 0.001 to 10 mmol / g, and preferably 0.1 to 5 mmol / g. More preferred.
-他の繰り返し単位-
 樹脂Cは他の繰り返し単位を更に有していてもよい。
 他の繰り返し単位としては、上述の式(BA-2)で表される繰り返し単位であって、XP1がアルコキシシリル基とは異なる重合性基である繰り返し単位等が挙げられる。
-Other repeating units-
The resin C may further have other repeating units.
As other repeating units, a repeating unit represented by the above formula (BA-2), X P1 can be mentioned a repeating unit such as a different polymerizable group and alkoxysilyl group.
〔具体例〕
 酸基及びアルコキシシリル基を含む化合物の具体例としては、実施例に使用された化合物が挙げられるが、これに限定されるものではない。
〔Concrete example〕
Specific examples of the compound containing an acid group and an alkoxysilyl group include, but are not limited to, the compounds used in the examples.
〔含有量〕
 酸基及びアルコキシシリル基を含む化合物の含有量は、本発明の硬化性樹脂組成物の全固形分に対して0.05~10質量%であることが好ましく、0.10~5質量%であることがより好ましく、0.15~2質量%であることが更に好ましい。
 硬化性樹脂組成物は酸基及びアルコキシシリル基を含む化合物を1種のみ含有していてもよいし、2種以上含有していてもよい。酸基及びアルコキシシリル基を含む化合物を2種以上含有する場合は、合計量が上記範囲であることが好ましい。
〔Content〕
The content of the compound containing an acid group and an alkoxysilyl group is preferably 0.05 to 10% by mass, preferably 0.10 to 5% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.15 to 2% by mass, and even more preferably 0.15 to 2% by mass.
The curable resin composition may contain only one kind of compound containing an acid group and an alkoxysilyl group, or may contain two or more kinds. When two or more compounds containing an acid group and an alkoxysilyl group are contained, the total amount is preferably in the above range.
<アゾール基を有する他の化合物>
 硬化性樹脂組成物は、アゾール基を有する化合物であって、上述のオキサゾリン基を有する化合物、並びに、酸基及びアルコキシシリル基を含む化合物のいずれにも該当しない化合物(「アゾール基を有する他の化合物」ともいう。)を更に含んでもよい。
 アゾール基を有する他の化合物におけるアゾール基の好ましい態様は、上述のオキサゾリン基を有する化合物におけるアゾール基の好ましい態様と同様である。
 また、アゾール基を有する他の化合物は重合性基を有しない化合物であることが好ましい。重合性基の詳細は、上述のオキサゾリン基を有する化合物における重合性基と同義である。
<Other compounds having an azole group>
The curable resin composition is a compound having an azole group and does not fall under any of the above-mentioned compounds having an oxazoline group and compounds containing an acid group and an alkoxysilyl group (“other compounds having an azole group”). Also referred to as "compound").
The preferred embodiment of the azole group in the other compound having an azole group is the same as the preferred embodiment of the azole group in the above-mentioned compound having an oxazoline group.
Further, the other compound having an azole group is preferably a compound having no polymerizable group. The details of the polymerizable group are synonymous with the polymerizable group in the above-mentioned compound having an oxazoline group.
 アゾール基を有する他の化合物は、下記式(AZ-1)又は下記式(AZ-2)で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000040

 式(AZ-1)中、Z~Zはそれぞれ独立に、=CR-または窒素原子を表し、Rは水素原子又は1価の有機基を表し、Rは水素原子又は1価の有機基を表し、式(AZ-1)で表される構造中に重合性基は含まない;
式(AZ-2)中、Z~Zはそれぞれ独立に、=CR-または窒素原子を表し、R~Rはそれぞれ独立に、水素原子又は1価の有機基を表し、Rは水素原子又は1価の有機基を表し、式(AZ-2)で表される構造中に重合性基は含まない。
The other compound having an azole group is preferably a compound represented by the following formula (AZ-1) or the following formula (AZ-2).
Figure JPOXMLDOC01-appb-C000040

Wherein (AZ-1), respectively Z 1 ~ Z 4 are independently, = CR 7 - or a nitrogen atom, R 1 represents a hydrogen atom or a monovalent organic group, R 7 is a hydrogen atom or a monovalent Represents an organic group of, and does not contain a polymerizable group in the structure represented by the formula (AZ-1);
Wherein (AZ-2), the Z 5 ~ Z 6 are each independently, = CR 8 - or a nitrogen atom, are each R 2 ~ R 6 independently represent a hydrogen atom or a monovalent organic radical, R Reference numeral 8 represents a hydrogen atom or a monovalent organic group, and the structure represented by the formula (AZ-2) does not contain a polymerizable group.
 式(AZ-1)中、Z~Zはそれぞれ独立に、=CR-または窒素原子を表す。
 中でも、Z~Zのうち1つが窒素原子であり、3つが=CR-である態様、Z~Zのうち2つが窒素原子であり、2つが=CR-である態様、又は、Z~Zのうち3つが窒素原子であり、1つが=CR-である態様が好ましい。
 また、これらの中でも、Z及びZが窒素原子であり、Z及びZが=CR-である態様、Z及びZが窒素原子であり、Z及びZが=CR-である態様、又は、Z、Z及びZが窒素原子であり、Zが=CR-である態様が好ましく、Z及びZが窒素原子であり、Z及びZが=CRB7-である態様、又は、Z、Z及びZが窒素原子であり、Zが=CR-である態様がより好ましい。
In formula (AZ-1), Z 1 to Z 4 independently represent = CR 7 − or a nitrogen atom.
Among them, one is a nitrogen atom of Z 1 ~ Z 4, 3 one is = CR 7 - aspects is, two of Z 1 ~ Z 4 is a nitrogen atom, two are = CR 7 - in which embodiment, Alternatively, it is preferable that three of Z 1 to Z 4 are nitrogen atoms and one is = CR 7 −.
Further, among these, are Z 1 and Z 3 is a nitrogen atom, Z 2 and Z 4 is = CR 7 - embodiment is a Z 1 and Z 2 is a nitrogen atom, Z 3 and Z 4 is = CR 7- or a mode in which Z 1 , Z 2 and Z 3 are nitrogen atoms and Z 4 is = CR 7 -is preferable, Z 1 and Z 3 are nitrogen atoms, and Z 2 and Z are It is more preferable that 4 is = CR B7 −, or Z 1 , Z 2 and Z 3 are nitrogen atoms and Z 4 is = CR 7 −.
 式(AZ-1)中、Rは水素原子又は炭化水素基であることが好ましく、水素原子又はアルキル基であることがより好ましく、水素原子であることが特に好ましい。
 上記炭化水素基又はアルキル基の炭素数は、1~20であることが好ましく、1~10であることがより好ましく、1~4であることが更に好ましい。
In the formula (AZ-1), R 1 is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
The hydrocarbon group or the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms.
 式(AZ-1)中、Rの好ましい態様はRと同様である。 In the formula (AZ-1), the preferred embodiment of R 7 is the same as that of R 1.
 式(AZ-2)中、Z及びZはそれぞれ独立に、=CR-又は窒素原子を表す。
 中でも、Z及びZがいずれも窒素原子を表す態様、又は、Zが窒素原子を、Zが=CR-をそれぞれ表す態様が好ましい。
Wherein (AZ-2), the Z 5 and Z 6 are each independently, = CR 8 - represents a group or a nitrogen atom.
Above all, aspects Z 5 and Z 6 represent both nitrogen atoms, or a Z 5 is a nitrogen atom, Z 6 is = CR 8 - aspects that represent each desirable.
 式(AZ-2)中、R~R、Rはそれぞれ独立に、水素原子又は炭化水素基であることが好ましく、水素原子又はアルキル基であることがより好ましく、水素原子であることが特に好ましい。 In the formula (AZ-2), R 2 to R 6 and R 8 are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and a hydrogen atom. Is particularly preferable.
〔分子量〕
 アゾール基を有する他の化合物の分子量は、67~500であることが好ましく、68~300であることがより好ましい。
[Molecular weight]
The molecular weight of the other compound having an azole group is preferably 67 to 500, more preferably 68 to 300.
〔具体例〕
 アゾール基を有する他の化合物の具体例としては、実施例で使用された化合物が挙げられるが、これに限定されるものではない。
〔Concrete example〕
Specific examples of other compounds having an azole group include, but are not limited to, the compounds used in the examples.
〔含有量〕
 アゾール基を有する他の化合物の含有量は、本発明の硬化性樹脂組成物の全固形分に対して0.05~10質量%であることが好ましく、0.10~5質量%であることがより好ましく、0.15~2質量%であることが更に好ましい。
 硬化性樹脂組成物はアゾール基を有する他の化合物を1種のみ含有していてもよいし、2種以上含有していてもよい。アゾール基を有する他の化合物を2種以上含有する場合は、合計量が上記範囲であることが好ましい。
〔Content〕
The content of the other compound having an azole group is preferably 0.05 to 10% by mass, preferably 0.10 to 5% by mass, based on the total solid content of the curable resin composition of the present invention. Is more preferable, and 0.15 to 2% by mass is further preferable.
The curable resin composition may contain only one kind of other compounds having an azole group, or may contain two or more kinds. When two or more other compounds having an azole group are contained, the total amount is preferably in the above range.
<他のシランカップリング剤>
 本発明の硬化性樹脂組成物は、上述のオキサゾリン基を有する化合物、並びに、酸基及びアルコキシシリル基を含む化合物のいずれとも異なるシランカップリング剤(「他のシランカップリング剤」)を含んでもよい。
 他のシランカップリング剤としては、アルコキシシリル基を有し、かつ、酸基及びオキサゾリン基を有しない化合物が好ましい。
 また、他のシランカップリング剤として、アルコキシシリル基を含む繰り返し単位を含む樹脂を用いてもよい。
 上記樹脂は、アルコキシシリルとは異なる重合性基を含む繰り返し単位を更に含んでもよい。
 上記アルコキシシリル基を含む繰り返し単位、及び、アルコキシシリルとは異なる重合性基を含む繰り返し単位としては、上述の式(BA-2)で表される繰り返し単位が挙げられる。
<Other silane coupling agents>
The curable resin composition of the present invention may contain the above-mentioned compound having an oxazoline group and a silane coupling agent (“other silane coupling agent”) different from any of the compounds containing an acid group and an alkoxysilyl group. good.
As the other silane coupling agent, a compound having an alkoxysilyl group and no acid group and an oxazoline group is preferable.
Further, as another silane coupling agent, a resin containing a repeating unit containing an alkoxysilyl group may be used.
The resin may further contain repeating units containing a polymerizable group different from alkoxysilyl.
Examples of the repeating unit containing the alkoxysilyl group and the repeating unit containing a polymerizable group different from the alkoxysilyl include the repeating unit represented by the above formula (BA-2).
 他のシランカップリング剤の例としては、国際公開第2015/199219号の段落0167に記載の化合物、特開2014-191002号公報の段落0062~0073に記載の化合物、国際公開第2011/080992号の段落0063~0071に記載の化合物、特開2014-191252号公報の段落0060~0061に記載の化合物、特開2014-041264号公報の段落0045~0052に記載の化合物、国際公開第2014/097594号の段落0055に記載の化合物のうち、上述のオキサゾリン基を有する化合物、並びに、酸基及びアルコキシシリル基を含む化合物のいずれにも該当しない化合物が挙げられる。また、特開2011-128358号公報の段落0050~0058に記載のように異なる2種以上のシランカップリング剤を用いることも好ましい。
 また、他のシランカップリング剤としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、p-スチリルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン、又は、下記化合物を用いることも好ましい。以下の式中、Etはエチル基を表す。
Examples of other silane coupling agents 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, and International Publication No. 2011/080992. The compounds described in paragraphs 0063 to 0071, the compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, the compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/07594. Among the compounds described in paragraph 0055 of the item, the above-mentioned compounds having an oxazoline group and compounds not falling under any of the compounds containing an acid group and an alkoxysilyl group can be mentioned. Further, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358.
Examples of other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid. Xipropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxy It is also preferable to use silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, or the following compounds. In the following formula, Et represents an ethyl group.
Figure JPOXMLDOC01-appb-C000041
 
Figure JPOXMLDOC01-appb-C000041
 
〔含有量〕
 他のシランカップリング剤の含有量は、本発明の硬化性樹脂組成物の全固形分に対して0.05~10質量%であることが好ましく、0.10~5質量%であることがより好ましく、0.15~2質量%であることが更に好ましい。
 硬化性樹脂組成物は他のシランカップリング剤を1種のみ含有していてもよいし、2種以上含有していてもよい。他のシランカップリング剤を2種以上含有する場合は、合計量が上記範囲であることが好ましい。
〔Content〕
The content of the other silane coupling agent is preferably 0.05 to 10% by mass, preferably 0.10 to 5% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.15 to 2% by mass, and even more preferably 0.15 to 2% by mass.
The curable resin composition may contain only one type of other silane coupling agent, or may contain two or more types. When two or more other silane coupling agents are contained, the total amount is preferably in the above range.
<溶剤>
 本発明の硬化性樹脂組成物は、溶剤を含有することが好ましい。溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、環式炭化水素類、スルホキシド類、アミド類、ウレア類、アルコール類などの化合物が挙げられる。
<Solvent>
The curable resin composition of the present invention preferably contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.
 エステル類として、例えば、酢酸エチル、酢酸-n-ブチル、酢酸イソブチル、酢酸へキシル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ-ブチロラクトン、ε-カプロラクトン、δ-バレロラクトン、アルキルオキシ酢酸アルキル(例えば、アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル(例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等))、3-アルキルオキシプロピオン酸アルキルエステル類(例えば、3-アルキルオキシプロピオン酸メチル、3-アルキルオキシプロピオン酸エチル等(例えば、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル等))、2-アルキルオキシプロピオン酸アルキルエステル類(例えば、2-アルキルオキシプロピオン酸メチル、2-アルキルオキシプロピオン酸エチル、2-アルキルオキシプロピオン酸プロピル等(例えば、2-メトキシプロピオン酸メチル、2-メトキシプロピオン酸エチル、2-メトキシプロピオン酸プロピル、2-エトキシプロピオン酸メチル、2-エトキシプロピオン酸エチル))、2-アルキルオキシ-2-メチルプロピオン酸メチル及び2-アルキルオキシ-2-メチルプロピオン酸エチル(例えば、2-メトキシ-2-メチルプロピオン酸メチル、2-エトキシ-2-メチルプロピオン酸エチル等)、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、2-オキソブタン酸メチル、2-オキソブタン酸エチル、ヘキサン酸エチル、ヘプタン酸エチル、マロン酸ジメチル、マロン酸ジエチル等が好適なものとして挙げられる。 Examples of 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 γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkyl oxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.) 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, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Suitable examples thereof include ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutate, ethyl hexanoate, ethyl heptate, dimethyl malonate, diethyl malonate and the like. ..
 エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、エチレングリコールモノブチルエーテル、エチレングリコールモノブチルエーテルアセテート、ジエチレングリコールエチルメチルエーテル、プロピレングリコールモノプロピルエーテルアセテート等が好適なものとして挙げられる。 Examples of 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.
 ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、2-ヘプタノン、3-ヘプタノン、3-メチルシクロヘキサノン、レボグルコセノン、ジヒドロレボグルコセノン等が好適なものとして挙げられる。 As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.
 環状炭化水素類として、例えば、トルエン、キシレン、アニソール等の芳香族炭化水素類、リモネン等の環式テルペン類が好適なものとして挙げられる。 As the cyclic hydrocarbons, for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.
 スルホキシド類として、例えば、ジメチルスルホキシドが好適なものとして挙げられる。 As the sulfoxides, for example, dimethyl sulfoxide is preferable.
 アミド類として、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、N,N-ジメチルイソブチルアミド、3-メトキシ-N,N-ジメチルプロピオンアミド、3-ブトキシ-N,N-ジメチルプロピオンアミド、N-ホルミルモルホリン、N-アセチルモルホリン等が好適なものとして挙げられる。 As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylisobutyramide, 3-methoxy-N, N- Suitable examples include dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.
 ウレア類として、N,N,N’,N’-テトラメチルウレア、1,3-ジメチル-2-イミダゾリジノン等が好適なものとして挙げられる。 As ureas, N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.
 アルコール類として、メタノール、エタノール、1-プロパノール、2-プロパノール、1-ブタノール、1-ペンタノール、1-ヘキサノール、ベンジルアルコール、エチレングリコールモノメチルエーテル、1-メトキシ-2-プロパノール、2-エトキシエタノール、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノヘキシルエーテル、トリエチレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、ポリエチレングリコールモノメチルエーテル、ポリプロピレングリコール、テトラエチレングリコール、エチレングリコールモノブチルエーテル、エチレングリコールモノベンジルエーテル、エチレングリコールモノフェニルエーテル、メチルフェニルカルビノール、n-アミルアルコール、メチルアミルアルコール、および、ダイアセトンアルコール等が挙げられる。 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.
 溶剤は、塗布面性状の改良などの観点から、2種以上を混合する形態も好ましい。 The solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
 本発明では、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、シクロヘキサノン、シクロペンタノン、γ-ブチロラクトン、ジメチルスルホキシド、エチルカルビトールアセテート、ブチルカルビトールアセテート、N-メチル-2-ピロリドン、プロピレングリコールメチルエーテル、及びプロピレングリコールメチルエーテルアセテートから選択される1種の溶剤、又は、2種以上で構成される混合溶剤が好ましい。ジメチルスルホキシドとγ-ブチロラクトンとの併用が特に好ましい。また、N-メチル-2-ピロリドンと乳酸エチル、N-メチル-2-ピロリドンと乳酸エチル、ジアセトンアルコールと乳酸エチル、シクロペンタノンとγ-ブチロラクトン、の組み合わせも好ましい。 In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- Consists of one solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be mixed is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. Further, a combination of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and γ-butyrolactone is also preferable.
 本発明の硬化性樹脂組成物は、これらの中でも、エステル類を含むことが好ましく、ラクトン系溶剤を含むことがより好ましい。
 ラクトン系溶剤とは、ラクトン構造を含む溶剤をいい、γ-ブチロラクトン、ε-カプロラクトン、δ-バレロラクトン等が挙げられる。
 溶剤の全質量に対するラクトン系溶剤の含有量は、特に限定されないが、30~100質量%であることが好ましく、40~95質量%であることがより好ましく、50~90質量%であることが更に好ましい。
Among these, the curable resin composition of the present invention preferably contains esters, and more preferably contains a lactone-based solvent.
The lactone-based solvent refers to a solvent containing a lactone structure, and examples thereof include γ-butyrolactone, ε-caprolactone, and δ-valerolactone.
The content of the lactone-based solvent with respect to the total mass of the solvent is not particularly limited, but is preferably 30 to 100% by mass, more preferably 40 to 95% by mass, and more preferably 50 to 90% by mass. More preferred.
 溶剤の含有量は、塗布性の観点から、本発明の硬化性樹脂組成物の全固形分濃度が5~80質量%になる量とすることが好ましく、5~75質量%となる量にすることがより好ましく、10~70質量%となる量にすることが更に好ましく、40~70質量%となるようにすることが一層好ましい。溶剤含有量は、塗膜の所望の厚さと塗布方法に応じて調節すればよい。 From the viewpoint of coatability, 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 preferably 10 to 70% by mass, and even 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.
 溶剤は1種のみ含有していてもよいし、2種以上含有していてもよい。溶剤を2種以上含有する場合は、その合計が上記範囲であることが好ましい。 The solvent may be contained in only one kind, or may be contained in two or more kinds. When two or more kinds of solvents are contained, the total is preferably in the above range.
<感光剤>
 本発明の組成物は、感光剤を含むことが好ましい。
 感光剤としては、光重合開始剤が好ましい。
<Photosensitizer>
The composition of the present invention preferably contains a photosensitive agent.
As the photosensitive agent, a photopolymerization initiator is preferable.
〔光重合開始剤〕
 本発明の組成物は、感光剤として、光重合開始剤を含むことが好ましい。
 光重合開始剤は、光ラジカル重合開始剤であることが好ましい。光ラジカル重合開始剤としては、特に制限はなく、公知の光ラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する光ラジカル重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。
 また、上記光ラジカル重合開始剤としては、後述のオキシム化合物が好ましい。
[Photopolymerization initiator]
The composition of the present invention preferably contains a photopolymerization initiator as the photosensitive agent.
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. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an active agent that causes some action with a photoexcited sensitizer and generates an active radical.
Further, as the photoradical polymerization initiator, the oxime compound described later is preferable.
 光ラジカル重合開始剤は、約300~800nm(好ましくは330~500nm)の範囲内で少なくとも約50L・mol-1・cm-1のモル吸光係数を有する化合物を、少なくとも1種含有していることが好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、紫外可視分光光度計(Varian社製Cary-5 spectrophotometer)にて、酢酸エチル溶剤を用い、0.01g/Lの濃度で測定することが好ましい。 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).
 光ラジカル重合開始剤としては、公知の化合物を任意に使用できる。例えば、ハロゲン化炭化水素誘導体(例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物、トリハロメチル基を有する化合物など)、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル、アミノアセトフェノン化合物、ヒドロキシアセトフェノン、アゾ系化合物、アジド化合物、メタロセン化合物、有機ホウ素化合物、鉄アレーン錯体などが挙げられる。これらの詳細については、特開2016-027357号公報の段落0165~0182、国際公開第2015/199219号の段落0138~0151の記載を参酌でき、この内容は本明細書に組み込まれる。 A known compound can be arbitrarily used as the photoradical polymerization initiator. For example, 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, hexaarylbiimidazoles, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azido compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description in paragraphs 0165 to 0182 of JP-A-2016-027357 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.
 ケトン化合物としては、例えば、特開2015-087611号公報の段落0087に記載の化合物が例示され、この内容は本明細書に組み込まれる。市販品では、カヤキュアーDETX(日本化薬(株)製)も好適に用いられる。 As the ketone compound, for example, the compound described in paragraph 0087 of JP-A-2015-087611 is exemplified, and the content thereof is incorporated in the present specification. As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.
 本発明の一実施態様において、光ラジカル重合開始剤としては、ヒドロキシアセトフェノン化合物、アミノアセトフェノン化合物、及び、アシルホスフィン化合物を好適に用いることができる。より具体的には、例えば、特開平10-291969号公報に記載のアミノアセトフェノン系開始剤、特許第4225898号に記載のアシルホスフィンオキシド系開始剤を用いることができる。 In one embodiment of the present invention, 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 No. 10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.
 ヒドロキシアセトフェノン系開始剤としては、IRGACURE 184(IRGACUREは登録商標)、DAROCUR 1173、IRGACURE 500、IRGACURE-2959、IRGACURE 127(商品名:いずれもBASF社製)を用いることができる。 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
 アミノアセトフェノン系開始剤としては、市販品であるIRGACURE 907、IRGACURE 369、及び、IRGACURE 379(商品名:いずれもBASF社製)を用いることができる。 As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
 アミノアセトフェノン系開始剤として、365nm又は405nm等の波長光源に吸収極大波長がマッチングされた特開2009-191179号公報に記載の化合物も用いることができる。 As the aminoacetophenone-based initiator, 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.
 アシルホスフィン系開始剤としては、2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイドなどが挙げられる。また、市販品であるIRGACURE-819やIRGACURE-TPO(商品名:いずれもBASF社製)を用いることができる。 Examples of the acylphosphine-based initiator 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.
 メタロセン化合物としては、IRGACURE-784、IRGACURE-784EG(いずれもBASF社製)などが例示される。 Examples of the metallocene compound include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF).
 光ラジカル重合開始剤として、より好ましくはオキシム化合物が挙げられる。オキシム化合物を用いることにより、露光ラチチュードをより効果的に向上させることが可能になる。オキシム化合物は、露光ラチチュード(露光マージン)が広く、かつ、光硬化促進剤としても働くため、特に好ましい。 The photoradical polymerization initiator is more preferably an oxime compound. By using the oxime compound, it becomes possible to improve the exposure latitude more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
 オキシム化合物の具体例としては、特開2001-233842号公報に記載の化合物、特開2000-080068号公報に記載の化合物、特開2006-342166号公報に記載の化合物を用いることができる。 As specific examples of the oxime compound, 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.
 好ましいオキシム化合物としては、例えば、下記の構造の化合物や、3-ベンゾイルオキシイミノブタン-2-オン、3-アセトキシイミノブタン-2-オン、3-プロピオニルオキシイミノブタン-2-オン、2-アセトキシイミノペンタン-3-オン、2-アセトキシイミノ-1-フェニルプロパン-1-オン、2-ベンゾイルオキシイミノ-1-フェニルプロパン-1-オン、3-(4-トルエンスルホニルオキシ)イミノブタン-2-オン、及び2-エトキシカルボニルオキシイミノ-1-フェニルプロパン-1-オンなどが挙げられる。本発明の組成物においては、特に光ラジカル重合開始剤としてオキシム化合物(オキシム系の光重合開始剤)を用いることが好ましい。オキシム系の光重合開始剤は、分子内に >C=N-O-C(=O)- の連結基を有する。 Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of> C = N—O—C (= O)-in the molecule.
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
 市販品ではIRGACURE OXE 01、IRGACURE OXE 02、IRGACURE OXE 03、IRGACURE OXE 04(以上、BASF社製)、アデカオプトマーN-1919((株)ADEKA製、特開2012-014052号公報に記載の光ラジカル重合開始剤2)も好適に用いられる。また、TR-PBG-304(常州強力電子新材料有限公司製)、アデカアークルズNCI-831及びアデカアークルズNCI-930((株)ADEKA製)も用いることができる。また、DFI-091(ダイトーケミックス(株)製)を用いることができる。また、下記の構造のオキシム化合物を用いることもできる。
Figure JPOXMLDOC01-appb-C000043
Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PTOMER N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014052). A radical polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), ADEKA Arklus NCI-831 and ADEKA Arklus NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used. Further, an oxime compound having the following structure can also be used.
Figure JPOXMLDOC01-appb-C000043
 光重合開始剤としては、フルオレン環を有するオキシム化合物を用いることもできる。フルオレン環を有するオキシム化合物の具体例としては、特開2014-137466号公報に記載の化合物、特許06636081号に記載の化合物が挙げられる。 As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081.
 光重合開始剤としては、カルバゾール環の少なくとも1つのベンゼン環がナフタレン環となった骨格を有するオキシム化合物を用いることもできる。そのようなオキシム化合物の具体例としては、国際公開第2013/083505号に記載の化合物が挙げられる。 As the photopolymerization initiator, 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.
 また、フッ素原子を有するオキシム化合物を用いることも可能である。そのようなオキシム化合物の具体例としては、特開2010-262028号公報に記載されている化合物、特表2014-500852号公報の段落0345に記載されている化合物24、36~40、特開2013-164471号公報の段落0101に記載されている化合物(C-3)などが挙げられる。 It is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include the compounds described in JP-A-2010-262028, the 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 Japanese Patent Publication No. 164471.
 最も好ましいオキシム化合物としては、特開2007-269779号公報に示される特定置換基を有するオキシム化合物や、特開2009-191061号公報に示されるチオアリール基を有するオキシム化合物などが挙げられる。 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.
 光ラジカル重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α-ヒドロキシケトン化合物、α-アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム塩化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物及びその誘導体、シクロペンタジエン-ベンゼン-鉄錯体及びその塩、ハロメチルオキサジアゾール化合物、3-アリール置換クマリン化合物よりなる群から選択される化合物が好ましい。 From the viewpoint of exposure sensitivity, the photoradical polymerization initiator includes a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxadiazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.
 更に好ましい光ラジカル重合開始剤は、トリハロメチルトリアジン化合物、α-アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム塩化合物、ベンゾフェノン化合物、アセトフェノン化合物であり、トリハロメチルトリアジン化合物、α-アミノケトン化合物、オキシム化合物、トリアリールイミダゾールダイマー、ベンゾフェノン化合物よりなる群から選ばれる少なくとも1種の化合物が一層好ましく、メタロセン化合物又はオキシム化合物を用いるのがより一層好ましく、オキシム化合物が更に一層好ましい。 Further preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-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 a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, a metallocene compound or an oxime compound is further preferable, and an oxime compound is further preferable. Is even more preferable.
 また、光ラジカル重合開始剤は、ベンゾフェノン、N,N’-テトラメチル-4,4’-ジアミノベンゾフェノン(ミヒラーケトン)等のN,N’-テトラアルキル-4,4’-ジアミノベンゾフェノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタノン-1,2-メチル-1-[4-(メチルチオ)フェニル]-2-モルホリノ-プロパノン-1等の芳香族ケトン、アルキルアントラキノン等の芳香環と縮環したキノン類、ベンゾインアルキルエーテル等のベンゾインエーテル化合物、ベンゾイン、アルキルベンゾイン等のベンゾイン化合物、ベンジルジメチルケタール等のベンジル誘導体などを用いることもできる。また、下記式(I)で表される化合物を用いることもできる。 The photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). -Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanol-1, alkylanthraquinone, etc. It is also possible to use quinones fused to the aromatic ring of the above, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
 式(I)中、RI00は、炭素数1~20のアルキル基、1個以上の酸素原子によって中断された炭素数2~20のアルキル基、炭素数1~12のアルコキシ基、フェニル基、炭素数1~20のアルキル基、炭素数1~12のアルコキシ基、ハロゲン原子、シクロペンチル基、シクロヘキシル基、炭素数2~12のアルケニル基、1個以上の酸素原子によって中断された炭素数2~18のアルキル基及び炭素数1~4のアルキル基の少なくとも1つで置換されたフェニル基、又はビフェニルであり、RI01は、式(II)で表される基であるか、RI00と同じ基であり、RI02~RI04は各々独立に炭素数1~12のアルキル、炭素数1~12のアルコキシ基又はハロゲンである。 In formula (I), R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like. An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms. 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms, or biphenyl, R I01 is a group represented by formula (II), the same as R I00 The groups, R I02 to R I 04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
 式中、RI05~RI07は、上記式(I)のRI02~RI04と同じである。 In the formula, R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
 また、光ラジカル重合開始剤は、国際公開第2015/125469号の段落0048~0055に記載の化合物を用いることもできる。 Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used.
 光重合開始剤を含む場合、その含有量は、本発明の組成物の全固形分に対し0.1~30質量%であることが好ましく、より好ましくは0.1~20質量%であり、更に好ましくは0.5~15質量%であり、一層好ましくは1.0~10質量%である。光重合開始剤は1種のみ含有していてもよいし、2種以上含有していてもよい。光重合開始剤を2種以上含有する場合は、合計量が上記範囲であることが好ましい。 When the photopolymerization 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 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.
〔光酸発生剤〕
 また、本発明の組成物は、感光剤として、光酸発生剤を含むことも好ましい。
 光酸発生剤を含有することで、例えば、組成物層の露光部に酸が発生して、上記露光部の現像液(例えば、アルカリ水溶液)に対する溶解性が増大し、露光部が現像液により除去されるポジ型のパターンを得ることができる。
 また、組成物が、光酸発生剤と、後述するラジカル重合性化合物以外の重合性化合物とを含有することにより、例えば、露光部に発生した酸により上記重合性化合物の架橋反応が促進され、露光部が非露光部よりも現像液により除去されにくくなる態様とすることもできる。このような態様によれば、ネガ型のパターンを得ることができる。
[Photoacid generator]
Further, it is also preferable that the composition of the present invention contains a photoacid generator as a photosensitive agent.
By containing the photoacid generator, for example, acid is generated in the exposed portion of the composition layer, the solubility of the exposed portion in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed portion is formed by the developing solution. A positive pattern to be removed can be obtained.
Further, when the composition contains a photoacid generator and a polymerizable compound other than the radically polymerizable compound described later, for example, the acid generated in the exposed portion promotes the crosslinking reaction of the polymerizable compound. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion. According to such an embodiment, a negative pattern can be obtained.
 光酸発生剤としては、露光により酸を発生するものであれば特に限定されるものではないが、キノンジアジド化合物、ジアゾニウム塩、ホスホニウム塩、スルホニウム塩、ヨードニウム塩などのオニウム塩化合物、イミドスルホネート、オキシムスルホネート、ジアゾジスルホン、ジスルホン、o-ニトロベンジルスルホネート等のスルホネート化合物などを挙げることができる。 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. Examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzylsulfonate.
 キノンジアジド化合物としては、ポリヒドロキシ化合物にキノンジアジドのスルホン酸がエステルで結合したもの、ポリアミノ化合物にキノンジアジドのスルホン酸がスルホンアミド結合したもの、ポリヒドロキシポリアミノ化合物にキノンジアジドのスルホン酸がエステル結合及びスルホンアミド結合の少なくとも一方により結合したものなどが挙げられる。本発明においては、例えば、これらポリヒドロキシ化合物やポリアミノ化合物の官能基全体の50モル%以上がキノンジアジドで置換されていることが好ましい。 The quinone-diazide compound includes 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 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.
 本発明において、キノンジアジドは5-ナフトキノンジアジドスルホニル基、4-ナフトキノンジアジドスルホニル基のいずれも好ましく用いられる。4-ナフトキノンジアジドスルホニルエステル化合物は水銀灯のi線領域に吸収を持っており、i線露光に適している。5-ナフトキノンジアジドスルホニルエステル化合物は水銀灯のg線領域まで吸収が伸びており、g線露光に適している。本発明においては、露光する波長によって4-ナフトキノンジアジドスルホニルエステル化合物、5-ナフトキノンジアジドスルホニルエステル化合物を選択することが好ましい。また、同一分子中に4-ナフトキノンジアジドスルホニル基、5-ナフトキノンジアジドスルホニル基を有するナフトキノンジアジドスルホニルエステル化合物を含有してもよいし、4-ナフトキノンジアジドスルホニルエステル化合物と5-ナフトキノンジアジドスルホニルエステル化合物を含有してもよい。 In the present invention, as 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. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazido sulfonyl ester compound depending on the wavelength to be exposed. Further, 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.
 上記ナフトキノンジアジド化合物は、フェノール性ヒドロキシ基を有する化合物と、キノンジアジドスルホン酸化合物とのエステル化反応によって合成可能であり、公知の方法により合成することができる。これらのナフトキノンジアジド化合物を使用することで解像度、感度、残膜率がより向上する。
 上記ナフトキノンジアジド化合物としては、例えば、1,2-ナフトキノン-2-ジアジド-5-スルホン酸又は1,2-ナフトキノン-2-ジアジド-4-スルホン酸、これらの化合物の塩又はエステル化合物等が挙げられる。
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.
 オニウム塩化合物、又は、スルホネート化合物としては、特開2008-013646号公報の段落0064~0122に記載の化合物等が挙げられる。 Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
 光酸発生剤は、オキシムスルホネート基を含む化合物(以下、単に「オキシムスルホネート化合物」ともいう)であることも好ましい。
 オキシムスルホネート化合物は、オキシムスルホネート基を有していれば特に制限はないが、下記式(OS-1)、後述する式(OS-103)、式(OS-104)、又は、式(OS-105)で表されるオキシムスルホネート化合物であることが好ましい。
The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-). It is preferably the oxime sulfonate compound represented by 105).
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
 式(OS-1)中、Xは、アルキル基、アルコキシル基、又は、ハロゲン原子を表す。Xが複数存在する場合は、それぞれ同一であってもよいし、異なっていてもよい。上記Xにおけるアルキル基及びアルコキシル基は、置換基を有していてもよい。上記Xにおけるアルキル基としては、炭素数1~4の、直鎖状又は分岐状アルキル基が好ましい。上記Xにおけるアルコキシル基としては、炭素数1~4の直鎖状又は分岐状アルコキシル基が好ましい。上記Xにおけるハロゲン原子としては、塩素原子又はフッ素原子が好ましい。
 式(OS-1)中、m3は、0~3の整数を表し、0又は1が好ましい。m3が2又は3であるとき、複数のXは同一でも異なっていてもよい。
 式(OS-1)中、R34は、アルキル基又はアリール基を表し、炭素数1~10のアルキル基、炭素数1~10のアルコキシル基、炭素数1~5のハロゲン化アルキル基、炭素数1~5のハロゲン化アルコキシル基、Wで置換されていてもよいフェニル基、Wで置換されていてもよいナフチル基又はWで置換されていてもよいアントラニル基であることが好ましい。Wは、ハロゲン原子、シアノ基、ニトロ基、炭素数1~10のアルキル基、炭素数1~10のアルコキシル基、炭素数1~5のハロゲン化アルキル基又は炭素数1~5のハロゲン化アルコキシル基、炭素数6~20のアリール基、炭素数6~20のハロゲン化アリール基を表す。
Wherein (OS-1), X 3 is an alkyl group, an alkoxyl group, or a halogen atom. If X 3 there are a plurality, each be the same or may be different. Alkyl group and an alkoxyl group represented by X 3 may have a substituent. The alkyl group in the above X 3, 1 to 4 carbon atoms, straight-chain or branched alkyl group is preferable. The alkoxyl group represented by X 3, preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in the X 3, a chlorine atom or a fluorine atom is preferable.
In the formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X 3 may be the same or different.
In the formula (OS-1), R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl group of numbers 1 to 5, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms. Represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
 式(OS-1)中、m3が3であり、Xがメチル基であり、Xの置換位置がオルト位であり、R34が炭素数1~10の直鎖状アルキル基、7,7-ジメチル-2-オキソノルボルニルメチル基、又は、p-トリル基である化合物が特に好ましい。 Wherein (OS-1), m3 is 3, X 3 is a methyl group, the substitution position of X 3 is ortho, R 34 is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound having a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group is particularly preferable.
 式(OS-1)で表されるオキシムスルホネート化合物の具体例としては、特開2011-209692号公報の段落番号0064~0068、特開2015-194674号公報の段落番号0158~0167に記載された以下の化合物が例示され、これらの内容は本明細書に組み込まれる。 Specific examples of the oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-200969A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
 式(OS-103)~式(OS-105)中、Rs1はアルキル基、アリール基又はヘテロアリール基を表し、複数存在する場合のあるRs2はそれぞれ独立に、水素原子、アルキル基、アリール基又はハロゲン原子を表し、複数存在する場合のあるRs6はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基又はアルコキシスルホニル基を表し、XsはO又はSを表し、nsは1又は2を表し、msは0~6の整数を表す。
 式(OS-103)~式(OS-105)中、Rs1で表されるアルキル基(炭素数1~30が好ましい)、アリール基(炭素数6~30が好ましい)又はヘテロアリール基(炭素数4~30が好ましい)は、置換基Tを有していてもよい。
In formulas (OS-103) to (OS-105), R s1 represents an alkyl group, an aryl group or a heteroaryl group, and R s2, which may be present in a plurality of R s2, independently represents a hydrogen atom, an alkyl group and an aryl group. R s6 , which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and Xs represents O or S. Represented, ns represents 1 or 2, ms represents an integer from 0 to 6.
In formulas (OS-103) to (OS-105), an alkyl group represented by R s1 (preferably 1 to 30 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms) or a heteroaryl group (carbon). (Preferably numbers 4 to 30) may have a substituent T.
 式(OS-103)~式(OS-105)中、Rs2は、水素原子、アルキル基(炭素数1~12が好ましい)又はアリール基(炭素数6~30が好ましい)であることが好ましく、水素原子又はアルキル基であることがより好ましい。化合物中に2以上存在する場合のあるRs2のうち、1つ又は2つがアルキル基、アリール基又はハロゲン原子であることが好ましく、1つがアルキル基、アリール基又はハロゲン原子であることがより好ましく、1つがアルキル基であり、かつ残りが水素原子であることが特に好ましい。Rs2で表されるアルキル基又はアリール基は、置換基Tを有していてもよい。
 式(OS-103)、式(OS-104)、又は、式(OS-105)中、XsはO又はSを表し、Oであることが好ましい。上記式(OS-103)~(OS-105)において、Xsを環員として含む環は、5員環又は6員環である。
In the formulas (OS-103) to (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms) or an aryl group (preferably 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable. Of the Rs2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom. The alkyl group or aryl group represented by R s2 may have a substituent T.
In the formula (OS-103), the formula (OS-104), or the formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
 式(OS-103)~式(OS-105)中、nsは1又は2を表し、XsがOである場合、nsは1であることが好ましく、また、XsがSである場合、nsは2であることが好ましい。
 式(OS-103)~式(OS-105)中、Rs6で表されるアルキル基(炭素数1~30が好ましい)及びアルキルオキシ基(炭素数1~30が好ましい)は、置換基を有していてもよい。
 式(OS-103)~式(OS-105)中、msは0~6の整数を表し、0~2の整数であることが好ましく、0又は1であることがより好ましく、0であることが特に好ましい。
In the formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
In the formulas (OS-103) to (OS-105), the alkyl group represented by R s6 (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) are substituted groups. You may have.
In the formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
 また、上記式(OS-103)で表される化合物は、下記式(OS-106)、式(OS-110)又は式(OS-111)で表される化合物であることが特に好ましく、上記式(OS-104)で表される化合物は、下記式(OS-107)で表される化合物であることが特に好ましく、上記式(OS-105)で表される化合物は、下記式(OS-108)又は式(OS-109)で表される化合物であることが特に好ましい。
Figure JPOXMLDOC01-appb-C000048
Further, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111). The compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.
Figure JPOXMLDOC01-appb-C000048
 式(OS-106)~式(OS-111)中、Rt1はアルキル基、アリール基又はヘテロアリール基を表し、Rt7は、水素原子又は臭素原子を表し、Rt8は水素原子、炭素数1~8のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、Rt9は水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、Rt2は水素原子又はメチル基を表す。
 式(OS-106)~式(OS-111)中、Rt7は、水素原子又は臭素原子を表し、水素原子であることが好ましい。
In formulas (OS-106) to (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, and R t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups, R t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups, and R t2 represents a hydrogen atom or a methyl group.
In the formulas (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
 式(OS-106)~式(OS-111)中、Rt8は、水素原子、炭素数1~8のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基又はクロロフェニル基を表し、炭素数1~8のアルキル基、ハロゲン原子又はフェニル基であることが好ましく、炭素数1~8のアルキル基であることがより好ましく、炭素数1~6のアルキル基であることが更に好ましく、メチル基であることが特に好ましい。 In formulas (OS-106) to (OS-111), R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, and a phenyl group. Alternatively, it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.
 式(OS-106)~式(OS-111)中、Rt9は、水素原子、ハロゲン原子、メチル基又はメトキシ基を表し、水素原子であることが好ましい。
 Rt2は、水素原子又はメチル基を表し、水素原子であることが好ましい。
 また、上記オキシムスルホネート化合物において、オキシムの立体構造(E,Z)については、いずれか一方であっても、混合物であってもよい。
 上記式(OS-103)~式(OS-105)で表されるオキシムスルホネート化合物の具体例としては、特開2011-209692号公報の段落番号0088~0095、特開2015-194674号公報の段落番号0168~0194に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。
In the formulas (OS-106) to (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
Specific examples of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692 and paragraphs of JP-A-2015-194674. The compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
 オキシムスルホネート基を少なくとも1つを含むオキシムスルホネート化合物の好適な他の態様としては、下記式(OS-101)、式(OS-102)で表される化合物が挙げられる。 Other suitable embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
 式(OS-101)又は式(OS-102)中、Ru9は、水素原子、アルキル基、アルケニル基、アルコキシル基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基又はヘテロアリール基を表す。Ru9がシアノ基又はアリール基である態様がより好ましく、Ru9がシアノ基、フェニル基又はナフチル基である態様が更に好ましい。
 式(OS-101)又は式(OS-102)中、Ru2aは、アルキル基又はアリール基を表す。
 式(OS-101)又は式(OS-102)中、Xuは、-O-、-S-、-NH-、-NRu5-、-CH-、-CRu6H-又はCRu6u7-を表し、Ru5~Ru7はそれぞれ独立に、アルキル基又はアリール基を表す。
In the formula (OS-101) or the formula (OS-102), Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, and the like. Represents an aryl group or a heteroaryl group. The embodiment in which R u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
In formula (OS-101) or formula (OS-102), Ru2a represents an alkyl group or an aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH- , -NR u5-, -CH 2- , -CR u6 H- or CR u6 R u7. -, R u5 to R u7 independently represent an alkyl group or an aryl group, respectively.
 式(OS-101)又は式(OS-102)中、Ru1~Ru4はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシル基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基又はアリール基を表す。Ru1~Ru4のうちの2つがそれぞれ互いに結合して環を形成してもよい。このとき、環が縮環してベンゼン環ともに縮合環を形成していてもよい。Ru1~Ru4としては、水素原子、ハロゲン原子又はアルキル基が好ましく、また、Ru1~Ru4のうちの少なくとも2つが互いに結合してアリール基を形成する態様も好ましい。中でも、Ru1~Ru4がいずれも水素原子である態様が好ましい。上記した置換基は、いずれも、更に置換基を有していてもよい。 In the formula (OS-101) or the formula (OS-102), Ru1 to Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. 2 in turn, each may be bonded to each other to form a ring of the R u1 ~ R u4. At this time, the ring may be condensed to form a fused ring together with the benzene ring. The R u1 ~ R u4, a hydrogen atom, preferably a halogen atom or an alkyl group, also aspects to form the at least two aryl groups bonded to each other of R u1 ~ R u4 preferred. Above all, it is preferable that all of Ru1 to Ru4 are hydrogen atoms. Any of the above-mentioned substituents may further have a substituent.
 上記式(OS-101)で表される化合物は、式(OS-102)で表される化合物であることがより好ましい。
 また、上記オキシムスルホネート化合物において、オキシムやベンゾチアゾール環の立体構造(E,Z等)についてはそれぞれ、いずれか一方であっても、混合物であってもよい。
 式(OS-101)で表される化合物の具体例としては、特開2011-209692号公報の段落番号0102~0106、特開2015-194674号公報の段落番号0195~0207に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。
 上記化合物の中でも、b-9、b-16、b-31、b-33が好ましい。
The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP-A-2011-20969 and paragraph numbers 0195 to 0207 of JP-A-2015-194674. And these contents are incorporated herein.
Among the above compounds, b-9, b-16, b-31, and b-33 are preferable.
 その他、光酸発生剤としては市販品を使用してもよい。市販品としては、WPAG-145、WPAG-149、WPAG-170、WPAG-199、WPAG-336、WPAG-367、WPAG-370、WPAG-443、WPAG-469、WPAG-638、WPAG-699(いずれも富士フイルム和光純薬(株)製)、Omnicat 250、Omnicat 270(いずれもIGM Resins B.V.社製)、Irgacure 250、Irgacure 270、Irgacure 290(いずれもBASF社製)、MBZ-101(みどり化学(株)製)等が挙げられる。 In addition, 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-443, WPAG-469, WPAG-638, and WPAG-690 (any of which). Also Fujifilm Wako Pure Chemical Industries, Ltd., Omnicat 250, Omnicat 270 (all manufactured by IGM Resins BV), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF), MBZ-101 (all manufactured by BASF). (Made by Midori Chemical Industries, Ltd.) and the like.
 また、下記構造式で表される化合物も好ましい例として挙げられる。
Figure JPOXMLDOC01-appb-C000050
Further, a compound represented by the following structural formula is also mentioned as a preferable example.
Figure JPOXMLDOC01-appb-C000050
 光酸発生剤としては、有機ハロゲン化化合物も適用できる。有機ハロゲン化化合物としては、具体的には、若林等「Bull Chem.Soc Japan」42、2924(1969)、米国特許第3,905,815号明細書、特公昭46-4605号、特開昭48-36281号、特開昭55-32070号、特開昭60-239736号、特開昭61-169835号、特開昭61-169837号、特開昭62-58241号、特開昭62-212401号、特開昭63-70243号、特開昭63-298339号、M.P.Hutt“Jurnal of Heterocyclic Chemistry”1(No3),(1970)などに記載の化合物が挙げられ、特に、トリハロメチル基が置換したオキサゾール化合物:S-トリアジン化合物が挙げられる。
 より好適には、すくなくとも一つのモノ、ジ、又はトリハロゲン置換メチル基がs-トリアジン環に結合したs-トリアジン誘導体、具体的には、例えば、2,4,6-トリス(モノクロロメチル)-s-トリアジン、2,4,6-トリス(ジクロロメチル)-s-トリアジン、2,4,6-トリス(トリクロロメチル)-s-トリアジン、2-メチル-4,6-ビス(トリクロロメチル)-s-トリアジン、2―n-プロピル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(α,α,β-トリクロロエチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(3,4-エポキシフェニル)-4、6-ビス(トリクロロメチル)-s-トリアジン、2-(p-クロロフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-〔1-(p-メトキシフェニル)-2,4-ブタジエニル〕-4,6-ビス(トリクロロメチル)-s-トリアジン、2-スチリル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-i-プロピルオキシスチリル)-4、6-ビス(トリクロロメチル)-s-トリアジン、2-(p-トリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-ナトキシナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニルチオ-4,6-ビス(トリクロロメチル)-s-トリアジン、2-ベンジルチオ-4,6-ビス(トリクロロメチル)-s-トリアジン、2,4,6-トリス(ジブロモメチル)-s-トリアジン、2,4,6-トリス(トリブロモメチル)-s-トリアジン、2-メチル-4,6-ビス(トリブロモメチル)-s-トリアジン、2-メトキシ-4,6-ビス(トリブロモメチル)-s-トリアジン等が挙げられる。
As the photoacid generator, an organic halogenated compound can also be applied. Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP-A. 48-36281, JP-A-55-3207, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62- 212401, JP-A-63-70243, JP-A-63-298339, M.D. P. The compounds described in Hutt “Jurnal of Heterocyclic Chemistry” 1 (No3), (1970) and the like can be mentioned, and in particular, oxazole compounds substituted with a trihalomethyl group: S-triazine compounds can be mentioned.
More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example 2,4,6-tris (monochromomethyl)-. s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine , 2-Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-Butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine , 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s- Examples thereof include triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like.
 光酸発生剤としては、有機ホウ酸塩化合物も適用できる。有機ホウ酸塩化合物としては、例えば、特開昭62-143044号、特開昭62-150242号、特開平9-188685号、特開平9-188686号、特開平9-188710号、特開2000-131837、特開2002-107916、特許第2764769号、特願2000-310808号、等の各公報、及び、Kunz,Martin“Rad Tech'98.Proceeding April 19-22,1998,Chicago”等に記載される有機ホウ酸塩、特開平6-157623号公報、特開平6-175564号公報、特開平6-175561号公報に記載の有機ホウ素スルホニウム錯体或いは有機ホウ素オキソスルホニウム錯体、特開平6-175554号公報、特開平6-175553号公報に記載の有機ホウ素ヨードニウム錯体、特開平9-188710号公報に記載の有機ホウ素ホスホニウム錯体、特開平6-348011号公報、特開平7-128785号公報、特開平7-140589号公報、特開平7-306527号公報、特開平7-292014号公報等の有機ホウ素遷移金属配位錯体等が具体例として挙げられる。 As a photoacid generator, an organic borate compound can also be applied. Examples of the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, and JP-A-2000. -131837, JP-A-2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin "Rad Tech'98. Proceeding Compound 19-22, 1998, Chicago", etc. Organic borate, organic boron sulfonium complex or organic boron oxosulfonium complex described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554. Japanese Patent Laid-Open No. 6-175553, Organic Boron Iodonium Complex, Japanese Patent Application Laid-Open No. 9-188710, Organic Boron Phosphorium Complex, Japanese Patent Application Laid-Open No. 6-348011, JP-A-7-128785, JP-A. Specific examples thereof include organic boron transition metal coordination complexes of JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014.
 光酸発生剤としては、ジスルホン化合物も適用できる。ジスルホン化合物としては、特開昭61-166544号、特願2001-132318公報等に記載されている化合物およびジアゾジスルホン化合物が挙げられる。 A disulfone compound can also be applied as a photoacid generator. Examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.
 上記オニウム塩化合物としては、例えば、S.I.Schlesinger,Photogr.Sci.Eng.,18,387(1974)、T.S.Bal et al,Polymer,21,423(1980)に記載のジアゾニウム塩、米国特許第4,069,055号明細書、特開平4-365049号等に記載のアンモニウム塩、米国特許第4,069,055号、同4,069,056号の各明細書に記載のホスホニウム塩、欧州特許第104、143号、米国特許第339,049号、同第410,201号の各明細書、特開平2-150848号、特開平2-296514号に記載のヨードニウム塩、欧州特許第370,693号、同390,214号、同233,567号、同297,443号、同297,442号、米国特許第4,933,377号、同161,811号、同410,201号、同339,049号、同4,760,013号、同4,734,444号、同2,833,827号、独国特許第2,904,626号、同3,604,580号、同3,604,581号の各明細書に記載のスルホニウム塩、J.V.Crivello et al,Macromolecules,10(6),1307(1977)、J.V.Crivello et al,J.Polymer Sci.,Polymer Chem.Ed.,17,1047(1979)に記載のセレノニウム塩、C.S.Wen et al,Teh,Proc.Conf.Rad.Curing ASIA,p478 Tokyo,Oct(1988)に記載のアルソニウム塩、ピリジニウム塩等のオニウム塩等が挙げられる。 Examples of the onium salt compound include S. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.I. S. The diazonium salt described in Bal et al, Polymer, 21, 423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365049, etc., US Pat. No. 4,069, Phosphonium salts described in 055 and 4,069,056, European Patents 104 and 143, US Patents 339,049 and 410,201, JP-A-2. -150848, Iodonium salt described in JP-A-2-296514, European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, US Patent. No. 4,933,377, No. 161,811, No. 410,201, No. 339,049, No. 4,760,013, No. 4,734,444, No. 2,833,827, The sulfonium salt according to each specification of German Patent No. 2,904,626, 3,604,580, and 3,604,581. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. Mol. V. Crivello et al, J. et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), selenonium salt, C.I. S. Wen et al, Theh, Proc. Conf. Rad. Examples thereof include onium salts such as the arsonium salt and the pyridinium salt described in Curing ASIA, p478 Tokyo, Oct (1988).
 オニウム塩としては、下記一般式(RI-I)~(RI-III)で表されるオニウム塩が挙げられる。
Figure JPOXMLDOC01-appb-C000051

 式(RI-I)中、Ar11は置換基を1~6有していても良い炭素数20以下のアリール基を表し、好ましい置換基としては炭素数1~12のアルキル基、炭素数1~12のアルケニル基、炭素数1~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数1~12のジアルキルアミノ基、炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシル基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z11は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオンが好ましい。式(RI-II)中、Ar21、Ar22は各々独立に置換基を1~6有していても良い炭素数20以下のアリール基を表し、好ましい置換基としては炭素数1~12のアルキル基、炭素数1~12のアルケニル基、炭素数1~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数1~12のジアルキルアミノ基、炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシル基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z21は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。式(RI-III)中、R31、R32、R33は各々独立に置換基を1~6有していても良い炭素数20以下のアリール基又はアルキル基、アルケニル基、アルキニル基を表し、好ましくは反応性、安定性の面から、アリール基であることが望ましい。好ましい置換基としては炭素数1~12のアルキル基、炭素数1~12のアルケニル基、炭素数1~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数1~12のジアルキルアミノ基、炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシル基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z31は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。
Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).
Figure JPOXMLDOC01-appb-C000051

In the formula (RI-I), Ar11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 1 to 12 carbon atoms. 12 alkenyl groups, alkynyl groups with 1 to 12 carbon atoms, aryl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, allyloxy groups with 1 to 12 carbon atoms, halogen atoms, 1 to 12 carbon atoms Alkylamino group, dialkylamino group with 1 to 12 carbon atoms, alkylamide or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group with 1 to 12 carbon atoms, carbon Examples thereof include thioaryl groups having the number 1 to 12. Z11 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, surface stability Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion are preferable. In the formula (RI-II), Ar21 and Ar22 each represent an aryl group having 20 or less carbon atoms which may independently have 1 to 6 substituents, and a preferable substituent is an alkyl group having 1 to 12 carbon atoms. , An alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, and carbon. Alkylamino group with 1 to 12 carbon atoms, dialkylamino group with 1 to 12 carbon atoms, alkylamide group or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, 1 to 12 carbon atoms Examples thereof include a thioalkyl group of 1 to 12 and a thioaryl group having 1 to 12 carbon atoms. Z21 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable. In the formula (RI-III), R31, R32, and R33 each represent an aryl group or an alkyl group having 20 or less carbon atoms, an alkenyl group, and an alkynyl group, which may independently have 1 to 6 substituents, and are preferable. From the viewpoint of reactivity and stability, an aryl group is desirable. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. Allyloxy group with 1 to 12 carbon atoms, halogen atom, alkylamino group with 1 to 12 carbon atoms, dialkylamino group with 1 to 12 carbon atoms, alkylamide group or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl Examples thereof include a group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z31 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of sex, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
 具体例としては、以下のものが挙げられる。
Figure JPOXMLDOC01-appb-C000052
 
Figure JPOXMLDOC01-appb-C000053
 
Figure JPOXMLDOC01-appb-C000054

Figure JPOXMLDOC01-appb-C000055
Specific examples include the following.
Figure JPOXMLDOC01-appb-C000052

Figure JPOXMLDOC01-appb-C000053

Figure JPOXMLDOC01-appb-C000054

Figure JPOXMLDOC01-appb-C000055
 光酸発生剤を含む場合、その含有量は、本発明の組成物の全固形分に対し0.1~30質量%であることが好ましく、0.1~20質量%であることがより好ましく、2~15質量%であることが更に好ましい。光酸発生剤は1種のみ含有していてもよいし、2種以上含有していてもよい。光酸発生剤を2種以上含有する場合は、その合計が上記範囲であることが好ましい。 When the photoacid generator 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 composition of the present invention. It is more preferably 2 to 15% by mass. 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.
〔光塩基発生剤〕
 本発明の硬化性樹脂組成物は、感光剤として、光塩基発生剤を含んでもよい。
 硬化性樹脂組成物が、光塩基発生剤と、後述する架橋剤とを含有することにより、例えば、露光部に発生した塩基により特定樹脂の環化が促進される、架橋剤の架橋反応が促進される等の作用により、露光部が非露光部よりも現像液により除去されにくくなる態様とすることもできる。このような態様によれば、ネガ型のレリーフパターンを得ることができる。
[Photobase generator]
The curable resin composition of the present invention may contain a photobase generator as a photosensitive agent.
When the curable resin composition contains a photobase generator and a cross-linking agent described later, for example, the cross-linking reaction of the cross-linking agent is promoted by promoting the cyclization of the specific resin by the base generated in the exposed portion. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion due to such an action. According to such an aspect, a negative type relief pattern can be obtained.
 光塩基発生剤としては、露光により塩基を発生するものであれば特に限定されず、公知のものを用いることが出来る。
 例えば、M.Shirai,and M.Tsunooka, Prog.Polym.Sci.,21,1(1996);角岡正弘,高分子加工,46,2(1997);C.Kutal,Coord.Chem.Rev.,211,353(2001);Y.Kaneko,A.Sarker,  and  D.Neckers,Chem.Mater.,11,170(1999);H.Tachi,M.Shirai,  and  M.Tsunooka,J.Photopolym.Sci.Technol.,13,153(2000);M.Winkle,  and  K.Graziano,J.Photopolym.Sci.Technol.,3,419(1990);M.Tsunooka,H.Tachi,  and  S.Yoshitaka,J.Photopolym.Sci.Technol.,9,13(1996);K.Suyama,H.Araki,M.Shirai,J.Photopolym.Sci.Technol.,19,81(2006)に記載されているように、遷移金属化合物錯体や、アンモニウム塩などの構造を有するものや、アミジン部分がカルボン酸と塩形成することで潜在化されたもののように、塩基成分が塩を形成することにより中和されたイオン性の化合物や、カルバメート誘導体、オキシムエステル誘導体、アシル化合物などのウレタン結合やオキシム結合などにより塩基成分が潜在化された非イオン性の化合物を挙げることができる。
 本発明では、光塩基発生剤として、カルバメート誘導体、アミド誘導体、イミド誘導体、αコバルト錯体類、イミダゾール誘導体、桂皮酸アミド誘導体、オキシム誘導体等がより好ましい例として挙げられる。
The photobase generator is not particularly limited as long as it generates a base by exposure, and known ones can be used.
For example, M. Shirai, and M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C.I. Kutal, Code. Chem. Rev. , 211,353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mother. , 11, 170 (1999); H. Tachi, M. et al. Shirai, and M. Tsunooka, J.M. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K. Graziano, J.M. Photopolym. Sci. Technol. , 3,419 (1990); Tsunooka, H. et al. Tachi, and S. Yoshitaka, J.M. Photopolym. Sci. Technol. , 9, 13 (1996); K.K. Suyama, H. et al. Araki, M. et al. Shirai, J.M. Photopolym. Sci. Technol. , 19, 81 (2006), such as those having a structure such as a transition metal compound complex or an ammonium salt, or those latent by salt formation of an amidin moiety with a carboxylic acid. Ionic compounds whose base components are neutralized by forming salts, and nonionic compounds whose base components are latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds. Can be mentioned.
In the present invention, carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamic acid amide derivatives, oxime derivatives and the like are more preferable examples of the photobase generator.
 光塩基発生剤から発生する塩基性物質としては、特に限定されないが、アミノ基を有する化合物、特にモノアミンや、ジアミンなどのポリアミン、また、アミジンなどが挙げられる。
 イミド化率の観点からは、上記塩基性物質は、共役酸のDMSO(ジメチルスルホキシド)中のpKaが大きいものであることが好ましい。上記pKaは、1以上であることが好ましく、3以上であることがより好ましい。上記pKaの上限は特に限定されないが、20以下であることが好ましい。
 ここで、上記pKaとは、酸の第一解離定数の逆数の対数を表し、Determination of Organic Structures by Physical Methods(著者:Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; 編纂:Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955)や、Data for Biochemical Research(著者:Dawson, R.M.C.et al; Oxford, Clarendon Press, 1959)に記載の値を参照することができる。これらの文献に記載の無い化合物については、ACD/pKa(ACD/Labs製)のソフトを用いて構造式より算出した値をpKaとして用いることとする。
The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
From the viewpoint of the imidization rate, it is preferable that the basic substance has a large pKa in DMSO (dimethyl sulfoxide) of the conjugate acid. The pKa is preferably 1 or more, and more preferably 3 or more. The upper limit of the above pKa is not particularly limited, but is preferably 20 or less.
Here, pKa represents the logarithm of the reciprocal of the first dissociation constant of acid, and the Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; You can refer to the values described in Braude, EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMCet al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) shall be used as pKa.
 硬化性樹脂組成物の保存安定性の観点からは、光塩基発生剤としては、構造中に塩を含まない光塩基発生剤であることが好ましく、光塩基発生剤において発生する塩基部分の窒素原子上に電荷がないことが好ましい。光塩基発生剤としては、発生する塩基が共有結合を用いて潜在化されていることが好ましく、塩基の発生機構が、発生する塩基部分の窒素原子と隣接する原子との間の共有結合が切断されて塩基が発生するものであることが好ましい。構造中に塩を含まない光塩基発生剤であると、光塩基発生剤を中性にすることができるため、溶剤溶解性がより良好であり、ポットライフが向上する。このような理由から、本発明で用いられる光塩基発生剤から発生するアミンは、1級アミン又は2級アミンが好ましい。
 また、パターンの耐薬品性の観点からは、光塩基発生剤としては、構造中に塩を含む光塩基発生剤であることが好ましい。
From the viewpoint of storage stability of the curable resin composition, the photobase generator is preferably a photobase generator that does not contain a salt in the structure, and the nitrogen atom of the base portion generated in the photobase generator is preferable. It is preferable that there is no charge on the top. As the photobase generator, it is preferable that the generated base is latent using a covalent bond, and the mechanism of base generation is such that the covalent bond between the nitrogen atom of the generated base portion and the adjacent atom is cleaved. It is preferable that the base is generated. When the photobase generator does not contain a salt in the structure, the photobase generator can be neutralized, so that the solvent solubility is better and the pot life is improved. For this reason, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
Further, from the viewpoint of chemical resistance of the pattern, the photobase generator is preferably a photobase generator containing a salt in the structure.
 また、上記のような理由から光塩基発生剤としては、上述のように発生する塩基が共有結合を用いて潜在化されていることが好ましく、発生する塩基がアミド結合、カルバメート結合、オキシム結合を用いて潜在化されていることが好ましい。
 本発明に係る光塩基発生剤としては、例えば、特開2009-080452号公報及び国際公開第2009/123122号で開示されたような桂皮酸アミド構造を有する光塩基発生剤、特開2006-189591号公報及び特開2008-247747号公報で開示されたようなカルバメート構造を有する光塩基発生剤、特開2007-249013号公報及び特開2008-003581号公報で開示されたようなオキシム構造、カルバモイルオキシム構造を有する光塩基発生剤等が挙げられるが、これらに限定されず、その他にも公知の光塩基発生剤の構造を用いることができる。
Further, for the above reasons, as the photobase generator, it is preferable that the base generated as described above is latent using a covalent bond, and the generated base has an amide bond, a carbamate bond, and an oxime bond. It is preferably latent using.
Examples of the photobase generator according to the present invention include a photobase generator having a cinnamon acid amide structure as disclosed in JP-A-2009-080452 and International Publication No. 2009/123122, JP-A-2006-189591. A photobase generator having a carbamate structure as disclosed in JP-A and JP-A-2008-247747, an oxime structure as disclosed in JP-A-2007-249013 and JP-A-2008-003581, Carbamoyl. Examples thereof include a photobase generator having an oxime structure, but the present invention is not limited to these, and other known photobase generator structures can be used.
 その他、光塩基発生剤としては、特開2012-093746号公報の段落番号0185~0188、0199~0200及び0202に記載の化合物、特開2013-194205号公報の段落番号0022~0069に記載の化合物、特開2013-204019号公報の段落番号0026~0074に記載の化合物、及び、国際公開第2010/064631号の段落番号0052に記載の化合物が例として挙げられる。 In addition, as the photobase generator, the compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746, and the compounds described in paragraphs 0022 to 0069 of JP2013-194205. Examples thereof include the compounds described in paragraphs 0026 to 0074 of JP2013-204319A, and the compounds described in paragraph number 0052 of International Publication No. 2010/064631.
 その他、光塩基発生剤としては市販品を使用してもよい。市販品としては、WPBG-266、WPBG-300、WPGB-345、WPGB-140、WPBG-165、WPBG-027、WPBG-018、WPGB-015、WPBG-041、WPGB-172、WPGB-174、WPBG-166、WPGB-158、WPGB-025、WPGB-168、WPGB-167、WPBG-082(いずれも富士フイルム和光純薬(株)製)、A2502、B5085、N0528、N1052、O0396、O0447、O0448(東京化成工業(株)製)等が挙げられる。 In addition, a commercially available product may be used as the photobase generator. Commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-207, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG. -166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), A2502, B5085, N0528, N1052, O0396, O0447, O0448 ( (Made by Tokyo Chemical Industry Co., Ltd.) and the like.
 光塩基発生剤を含む場合、その含有量は、本発明の硬化性樹脂組成物の全固形分に対し0.1~30質量%であることが好ましく、0.1~20質量%であることがより好ましく、2~15質量%であることが更に好ましい。光塩基発生剤は1種のみ含有していてもよいし、2種以上含有していてもよい。光塩基発生剤を2種以上含有する場合は、その合計が上記範囲であることが好ましい。 When the photobase generator is contained, 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 photobase generator may be contained, or two or more types may be contained. When two or more photobase generators are contained, the total is preferably in the above range.
<熱重合開始剤>
 本発明の組成物は、熱重合開始剤を含んでもよく、特に熱ラジカル重合開始剤を含んでもよい。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始又は促進させる化合物である。熱ラジカル重合開始剤を添加することによって、後述する加熱工程において、樹脂及び重合性化合物の重合反応を進行させることもできるので、より耐溶剤性を向上できる。
<Thermal polymerization initiator>
The composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. The 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 resin and the polymerizable compound can be promoted in the heating step described later, so that the solvent resistance can be further improved.
 熱ラジカル重合開始剤として、具体的には、特開2008-063554号公報の段落0074~0118に記載されている化合物が挙げられる。 Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
 熱重合開始剤を含む場合、その含有量は、本発明の組成物の全固形分に対し0.1~30質量%であることが好ましく、より好ましくは0.1~20質量%であり、更に好ましくは5~15質量%である。熱重合開始剤は1種のみ含有していてもよいし、2種以上含有していてもよい。熱重合開始剤を2種以上含有する場合は、合計量が上記範囲であることが好ましい。 When the thermal polymerization 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 composition of the present invention. More preferably, it is 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.
<熱酸発生剤>
 本発明の組成物は、熱酸発生剤を含んでもよい。
 熱酸発生剤は、加熱により酸を発生し、ヒドロキシメチル基、アルコキシメチル基又はアシルオキシメチル基を有する化合物、エポキシ化合物、オキセタン化合物及びベンゾオキサジン化合物から選ばれる少なくとも1種の化合物の架橋反応を促進させる効果がある。
<Thermal acid generator>
The composition of the present invention may contain a thermoacid generator.
The thermoacid generator generates an acid by heating and promotes a cross-linking reaction of 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. It has the effect of making it.
 熱酸発生剤の熱分解開始温度は、50℃~270℃が好ましく、50℃~250℃がより好ましい。また、組成物を基板に塗布した後の乾燥(プリベーク:約70~140℃)時には酸を発生せず、その後の露光、現像でパターニングした後の最終加熱(キュア:約100~400℃)時に酸を発生するものを熱酸発生剤として選択すると、現像時の感度低下を抑制できるため好ましい。
 熱分解開始温度は、熱酸発生剤を耐圧カプセル中5℃/分で500℃まで加熱した場合に、最も温度が低い発熱ピークのピーク温度として求められる。
 熱分解開始温度を測定する際に用いられる機器としては、Q2000(TAインスツルメント社製)等が挙げられる。
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 the composition is applied to the substrate, and at the time of final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
The thermal decomposition start temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the thermal acid 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).
 熱酸発生剤から発生する酸は強酸が好ましく、例えば、p-トルエンスルホン酸、ベンゼンスルホン酸などのアリールスルホン酸、メタンスルホン酸、エタンスルホン酸、ブタンスルホン酸などのアルキルスルホン酸、あるいはトリフルオロメタンスルホン酸などのハロアルキルスルホン酸などが好ましい。このような熱酸発生剤の例としては、特開2013-072935号公報の段落0055に記載のものが挙げられる。 The acid generated from the thermal acid 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. Haloalkyl sulfonic acid such as sulfonic acid is preferable. Examples of such a thermoacid generator include those described in paragraph 0055 of JP2013-072935.
 中でも、有機膜中の残留が少なく有機膜物性を低下させにくいという観点から、炭素数1~4のアルキルスルホン酸や炭素数1~4のハロアルキルスルホン酸を発生するものがより好ましく、メタンスルホン酸(4-ヒドロキシフェニル)ジメチルスルホニウム、メタンスルホン酸(4-((メトキシカルボニル)オキシ)フェニル)ジメチルスルホニウム、メタンスルホン酸ベンジル(4-ヒドロキシフェニル)メチルスルホニウム、メタンスルホン酸ベンジル(4-((メトキシカルボニル)オキシ)フェニル)メチルスルホニウム、メタンスルホン酸(4-ヒドロキシフェニル)メチル((2-メチルフェニル)メチル)スルホニウム、トリフルオロメタンスルホン酸(4-ヒドロキシフェニル)ジメチルスルホニウム、トリフルオロメタンスルホン酸(4-((メトキシカルボニル)オキシ)フェニル)ジメチルスルホニウム、トリフルオロメタンスルホン酸ベンジル(4-ヒドロキシフェニル)メチルスルホニウム、トリフルオロメタンスルホン酸ベンジル(4-((メトキシカルボニル)オキシ)フェニル)メチルスルホニウム、トリフルオロメタンスルホン酸(4-ヒドロキシフェニル)メチル((2-メチルフェニル)メチル)スルホニウム、3-(5-(((プロピルスルホニル)オキシ)イミノ)チオフェン-2(5H)-イリデン)-2-(o-トリル)プロパンニトリル、2,2-ビス(3-(メタンスルホニルアミノ)-4-ヒドロキシフェニル)ヘキサフルオロプロパンが、熱酸発生剤として好ましい。 Among them, those that generate an alkyl sulfonic acid having 1 to 4 carbon atoms or a haloalkyl sulfonic acid having 1 to 4 carbon atoms are more preferable from the viewpoint that there is little residue in the organic film and it is difficult to deteriorate the physical properties of the organic film. (4-Hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonic acid (4-hydroxyphenyl) methylsulfonium, benzyl methanesulfonic acid (4-((methoxycarbonyl)) Carbonyl) oxy) phenyl) methyl sulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, trifluoromethanesulfonic acid (4-) ((Methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl trifluoromethanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, trifluoromethanesulfonic acid (4-Hydroxyphenyl) Methyl ((2-Methylphenyl) Methyl) Sulfonium, 3-(5-(((propylsulfonyl) Oxy) Imino) Thiophen-2 (5H) -Ilidene) -2- (o-Trill) Propanenitrile and 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane are preferred as the thermal acid generator.
 また、特開2013-167742号公報の段落0059に記載の化合物も熱酸発生剤として好ましい。 Further, the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.
 熱酸発生剤の含有量は、特定樹脂100質量部に対して0.01質量部以上が好ましく、0.1質量部以上がより好ましい。0.01質量部以上含有することで、架橋反応が促進されるため、有機膜の機械特性及び耐溶剤性をより向上させることができる。また、有機膜の電気絶縁性の観点から、20質量部以下が好ましく、15質量部以下がより好ましく、10質量部以下が更に好ましい。 The content of the thermoacid generator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin. By containing 0.01 part by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved. Further, from the viewpoint of electrical insulation of the organic film, 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.
<オニウム塩>
 本発明の硬化性樹脂組成物は、オニウム塩を更に含んでもよい。
 特に、本発明の硬化性樹脂組成物が特定樹脂としてポリイミド前駆体又はポリベンゾオキサゾール前駆体を含む場合、オニウム塩を含むことが好ましい。
 オニウム塩の種類等は特に定めるものではないが、アンモニウム塩、イミニウム塩、スルホニウム塩、ヨードニウム塩又はホスホニウム塩が好ましく挙げられる。
 これらの中でも、熱安定性が高い観点からはアンモニウム塩又はイミニウム塩が好ましく、ポリマーとの相溶性の観点からはスルホニウム塩、ヨードニウム塩又はホスホニウム塩が好ましい。
<Onium salt>
The curable resin composition of the present invention may further contain an onium salt.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain an onium salt.
The type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt or phosphonium salt are preferably mentioned.
Among these, an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.
 また、オニウム塩はオニウム構造を有するカチオンとアニオンとの塩であり、上記カチオンとアニオンとは、共有結合を介して結合していてもよいし、共有結合を介して結合していなくてもよい。
 すなわち、オニウム塩は、同一の分子構造内に、カチオン部と、アニオン部と、を有する分子内塩であってもよいし、それぞれ別分子であるカチオン分子と、アニオン分子と、がイオン結合した分子間塩であってもよいが、分子間塩であることが好ましい。また、本発明の硬化性樹脂組成物において、上記カチオン部又はカチオン分子と、上記アニオン部又はアニオン分子と、はイオン結合により結合されていてもよいし、解離していてもよい。
 オニウム塩におけるカチオンとしては、アンモニウムカチオン、ピリジニウムカチオン、スルホニウムカチオン、ヨードニウムカチオン又はホスホニウムカチオンが好ましく、テトラアルキルアンモニウムカチオン、スルホニウムカチオン及びヨードニウムカチオンよりなる群から選択される少なくとも1種のカチオンがより好ましい。
Further, the onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may or may not be bonded via a covalent bond. ..
That is, the onium salt may be an intramolecular salt having a cation part and an anion part 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.
As the cation in the onium salt, 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.
 本発明において用いられるオニウム塩は、後述する熱塩基発生剤であってもよい。
 熱塩基発生剤とは、加熱により塩基を発生する化合物をいい、例えば、40℃以上に加熱すると塩基を発生する化合物等が挙げられる。
 オニウム塩としては、例えば、国際公開第2018/043262号の段落0122~0138に記載のオニウム塩等が挙げられる。また、その他、ポリイミド前駆体の分野で使用されるオニウム塩を、特に制限なく使用することが可能である。
The onium salt used in the present invention may be a thermal base generator described later.
The thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.
Examples of the onium salt include the onium salt described in paragraphs 0122 to 0138 of International Publication No. 2018/043262. In addition, onium salts used in the field of polyimide precursors can be used without particular limitation.
 本発明の硬化性樹脂組成物がオニウム塩を含む場合、オニウム塩の含有量は、本発明の硬化性樹脂組成物の全固形分に対し、0.1~50質量%が好ましい。下限は、0.5質量%以上がより好ましく、0.85質量%以上が更に好ましく、1質量%以上が一層好ましい。上限は、30質量%以下がより好ましく、20質量%以下が更に好ましく、10質量%以下が一層好ましく、5質量%以下であってもよく、4質量%以下であってもよい。
 オニウム塩は、1種又は2種以上を用いることができる。2種以上を用いる場合は、合計量が上記範囲であることが好ましい。
When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% 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.
As the onium salt, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
<熱塩基発生剤>
 本発明の硬化性樹脂組成物は、熱塩基発生剤を更に含んでもよい。
 特に、本発明の硬化性樹脂組成物が特定樹脂としてポリイミド前駆体又はポリベンゾオキサゾール前駆体を含む場合、熱塩基発生剤を含むことが好ましい。
 他の熱塩基発生剤は、上述のオニウム塩に該当する化合物であってもよいし、上述のオニウム塩以外の熱塩基発生剤であってもよい。
 上述のオニウム塩以外の熱塩基発生剤としては、ノニオン系熱塩基発生剤が挙げられる。
 ノニオン系熱塩基発生剤としては、式(B1)又は式(B2)で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000056
<Thermal base generator>
The curable resin composition of the present invention may further contain a thermosetting agent.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain a thermobase generator.
The other 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 the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators.
Examples of the nonionic thermal base generator include compounds represented by the formula (B1) or the formula (B2).
Figure JPOXMLDOC01-appb-C000056
 式(B1)及び式(B2)中、Rb、Rb及びRbはそれぞれ独立に、第3級アミン構造を有しない有機基、ハロゲン原子又は水素原子である。ただし、Rb及びRbが同時に水素原子となることはない。また、Rb、Rb及びRbはいずれもカルボキシ基を有することはない。なお、本明細書で第三級アミン構造とは、3価の窒素原子の3つの結合手がいずれも炭化水素系の炭素原子と共有結合している構造を指す。したがって、結合した炭素原子がカルボニル基をなす炭素原子の場合、つまり窒素原子とともにアミド基を形成する場合はこの限りではない。 In the formula (B1) and 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. In the present specification, 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.
 式(B1)、(B2)中、Rb、Rb及びRbは、これらのうち少なくとも1つが環状構造を含むことが好ましく、少なくとも2つが環状構造を含むことがより好ましい。環状構造としては、単環及び縮合環のいずれであってもよく、単環又は単環が2つ縮合した縮合環が好ましい。単環は、5員環又は6員環が好ましく、6員環が好ましい。単環は、シクロヘキサン環及びベンゼン環が好ましく、シクロヘキサン環がより好ましい。 In the formulas (B1) and (B2), it is preferable that at least one of 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 monocyclic ring or a condensed ring in which 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. As the single ring, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
 より具体的にRb及びRbは、水素原子、アルキル基(炭素数1~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アルケニル基(炭素数2~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~10が更に好ましい)、又はアリールアルキル基(炭素数7~25が好ましく、7~19がより好ましく、7~12が更に好ましい)であることが好ましい。これらの基は、本発明の効果を奏する範囲で置換基を有していてもよい。RbとRbとは互いに結合して環を形成していてもよい。形成される環としては、4~7員の含窒素複素環が好ましい。Rb及びRbは特に、置換基を有してもよい直鎖、分岐、又は環状のアルキル基(炭素数1~24が好ましく、2~18がより好ましく、3~12が更に好ましい)であることが好ましく、置換基を有してもよいシクロアルキル基(炭素数3~24が好ましく、3~18がより好ましく、3~12が更に好ましい)であることがより好ましく、置換基を有してもよいシクロヘキシル基が更に好ましい。 More specifically, Rb 1 and Rb 2 are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and an alkenyl group (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 a substituent as long as the effect of the present invention is exhibited. Rb 1 and Rb 2 may be coupled to each other to form a ring. As the ring to be formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb 1 and Rb 2 are particularly linear, branched, or cyclic alkyl groups which 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. Maybe cyclohexyl groups are more preferred.
 Rbとしては、アルキル基(炭素数1~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~10が更に好ましい)、アルケニル基(炭素数2~24が好ましく、2~12がより好ましく、2~6が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)、アリールアルケニル基(炭素数8~24が好ましく、8~20がより好ましく、8~16が更に好ましい)、アルコキシル基(炭素数1~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アリールオキシ基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、又はアリールアルキルオキシ基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)が挙げられる。中でも、シクロアルキル基(炭素数3~24が好ましく、3~18がより好ましく、3~12が更に好ましい)、アリールアルケニル基、アリールアルキルオキシ基が好ましい。Rbには更に本発明の効果を奏する範囲で置換基を有していてもよい。 Examples of Rb 3 include an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 18 carbon atoms). ~ 10 is more preferable), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms are more preferable). Preferably, 7 to 12 are more preferable), an arylalkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxyl group (preferably 1 to 24 carbon atoms, 2 to 2 to 24). 18 is more preferred, 3 to 12 are more preferred), aryloxy groups (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 12 are even more preferred), or arylalkyloxy groups (7 to 12 carbon atoms are preferred). 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). Among them, a cycloalkyl group (preferably 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.
 式(B1)で表される化合物は、下記式(B1-1)又は下記式(B1-2)で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000057
The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
Figure JPOXMLDOC01-appb-C000057
 式中、Rb11及びRb12、並びに、Rb31及びRb32は、それぞれ、式(B1)におけるRb及びRbと同じである。
 Rb13はアルキル基(炭素数1~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アルケニル基(炭素数2~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、本発明の効果を奏する範囲で置換基を有していてもよい。中でも、Rb13はアリールアルキル基が好ましい。
In the formula, 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 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), 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 effect of the present invention is exhibited. Among them, Rb 13 is preferably an arylalkyl group.
 Rb33及びRb34は、それぞれ独立に、水素原子、アルキル基(炭素数1~12が好ましく、1~8がより好ましく、1~3が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~8がより好ましく、2~3が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~10が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~11が更に好ましい)であり、水素原子が好ましい。 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), and arylalkyl groups (7 to 7 to carbon atoms 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.
 Rb35は、アルキル基(炭素数1~24が好ましく、1~12がより好ましく、3~8が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~10がより好ましく、3~8が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、アリール基が好ましい。 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 preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). , 7-12 is more preferable), and an aryl group is preferable.
 式(B1-1)で表される化合物は、式(B1-1a)で表される化合物もまた好ましい。
Figure JPOXMLDOC01-appb-C000058
As the compound represented by the formula (B1-1), the compound represented by the formula (B1-1a) is also preferable.
Figure JPOXMLDOC01-appb-C000058
 Rb11及びRb12は式(B1-1)におけるRb11及びRb12と同義である。
 Rb15及びRb16は水素原子、アルキル基(炭素数1~12が好ましく、1~6がより好ましく、1~3が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~6がより好ましく、2~3が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~10が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~11が更に好ましい)であり、水素原子又はメチル基が好ましい。
 Rb17はアルキル基(炭素数1~24が好ましく、1~12がより好ましく、3~8が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~10がより好ましく、3~8が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、中でもアリール基が好ましい。
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, still more 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, still more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 are more preferable), and a hydrogen atom or a methyl group is preferable.
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), and 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.
 ノニオン系熱塩基発生剤の分子量は、800以下であることが好ましく、600以下であることがより好ましく、500以下であることが更に好ましい。下限としては、100以上であることが好ましく、200以上であることがより好ましく、300以上であることが更に好ましい。 The molecular weight of the nonionic thermal base 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.
 上述のオニウム塩のうち、熱塩基発生剤である化合物の具体例、又は、上述のオニウム塩以外の熱塩基発生剤の具体例としては、以下の化合物を挙げることができる。 Among the above-mentioned onium salts, specific examples of compounds that are thermal base generators or specific examples of thermal base generators other than the above-mentioned onium salts include the following compounds.
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
 他の熱塩基発生剤の含有量は、本発明の硬化性樹脂組成物の全固形分に対し、0.1~50質量%が好ましい。下限は、0.5質量%以上がより好ましく、1質量%以上が更に好ましい。上限は、30質量%以下がより好ましく、20質量%以下が更に好ましい。熱塩基発生剤は、1種又は2種以上を用いることができる。2種以上を用いる場合は、合計量が上記範囲であることが好ましい。 The content of the other 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, 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. As the thermal base generator, one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
<架橋剤>
 本発明の硬化性樹脂組成物は、架橋剤を含むことが好ましい。
 架橋剤としては、ラジカル架橋剤、又は、他の架橋剤が挙げられる。
<Crosslinking agent>
The curable resin composition of the present invention preferably contains a cross-linking agent.
Examples of the cross-linking agent include radical cross-linking agents and other cross-linking agents.
<ラジカル架橋剤>
 本発明の硬化性樹脂組成物は、ラジカル架橋剤を更に含むことが好ましい。
 ラジカル架橋剤は、ラジカル重合性基を有する化合物である。ラジカル重合性基としては、エチレン性不飽和結合を含む基が好ましい。上記エチレン性不飽和結合を含む基としては、ビニル基、アリル基、ビニルフェニル基、(メタ)アクリロイル基などのエチレン性不飽和結合を有する基が挙げられる。
 これらの中でも、上記エチレン性不飽和結合を含む基としては、(メタ)アクリロイル基が好ましく、反応性の観点からは、(メタ)アクリロキシ基がより好ましい。
<Radical cross-linking agent>
The curable resin composition of the present invention preferably further contains a radical cross-linking agent.
The radical cross-linking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group and a (meth) acryloyl group.
Among these, the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.
 ラジカル架橋剤は、エチレン性不飽和結合を1個以上有する化合物であればよいが、2以上有する化合物であることがより好ましい。
 エチレン性不飽和結合を2個有する化合物は、上記エチレン性不飽和結合を含む基を2個有する化合物であることが好ましい。
 また、得られるパターン(硬化膜)の膜強度の観点からは、本発明の硬化性樹脂組成物は、ラジカル架橋剤として、エチレン性不飽和結合を3個以上有する化合物を含むことが好ましい。上記エチレン性不飽和結合を3個以上有する化合物としては、エチレン性不飽和結合を3~15個有する化合物が好ましく、エチレン性不飽和結合を3~10個有する化合物がより好ましく、3~6個有する化合物が更に好ましい。
 また、上記エチレン性不飽和結合を3個以上有する化合物は、上記エチレン性不飽和結合を含む基を3個以上有する化合物であることが好ましく、3~15個有する化合物であることがより好ましく、3~10個有する化合物であることが更に好ましく、3~6個有する化合物であることが特に好ましい。
 また、得られるパターン(硬化膜)の膜強度の観点からは、本発明の硬化性樹脂組成物は、エチレン性不飽和結合を2個有する化合物と、上記エチレン性不飽和結合を3個以上有する化合物とを含むことも好ましい。
The radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more ethylenically unsaturated bonds.
The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the ethylenically unsaturated bond.
Further, from the viewpoint of the film strength of the obtained pattern (cured film), the curable resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent. As the compound having 3 or more ethylenically unsaturated bonds, a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable. The compound having is more preferable.
Further, the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds. A compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
Further, from the viewpoint of the film strength of the obtained pattern (cured film), the curable resin composition of the present invention has a compound having two ethylenically unsaturated bonds and three or more ethylenically unsaturated bonds. It is also preferable to contain a compound.
 ラジカル架橋剤の分子量は、2,000以下が好ましく、1,500以下がより好ましく、900以下が更に好ましい。ラジカル架橋剤の分子量の下限は、100以上が好ましい。 The molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
 ラジカル架橋剤の具体例としては、不飽和カルボン酸(例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など)やそのエステル類、アミド類が挙げられ、好ましくは、不飽和カルボン酸と多価アルコール化合物とのエステル、及び不飽和カルボン酸と多価アミン化合物とのアミド類である。また、ヒドロキシ基やアミノ基、スルファニル基等の求核性置換基を有する不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能イソシアネート類又はエポキシ類との付加反応物や、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基やエポキシ基等の親電子性置換基を有する不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物、更に、ハロゲノ基やトシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン等のビニルベンゼン誘導体、ビニルエーテル、アリルエーテル等に置き換えた化合物群を使用することも可能である。具体例としては、特開2016-027357号公報の段落0113~0122の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Specific examples of the radical cross-linking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and are preferable. Esters of saturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyhydric amine compound. Further, 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 group or an epoxy group, or a monofunctional or polyfunctional group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a polyelectron substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a halogeno group. Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the above-mentioned unsaturated carboxylic acid is replaced with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether, allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.
 また、ラジカル架橋剤は、常圧下で100℃以上の沸点を持つ化合物も好ましい。その例としては、ポリエチレングリコールジ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ヘキサンジオール(メタ)アクリレート、トリメチロールプロパントリ(アクリロイルオキシプロピル)エーテル、トリ(アクリロイルオキシエチル)イソシアヌレート、グリセリンやトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後、(メタ)アクリレート化した化合物、特公昭48-041708号公報、特公昭50-006034号公報、特開昭51-037193号各公報に記載されているようなウレタン(メタ)アクリレート類、特開昭48-064183号、特公昭49-043191号、特公昭52-030490号各公報に記載されているポリエステルアクリレート類、エポキシ樹脂と(メタ)アクリル酸との反応生成物であるエポキシアクリレート類等の多官能のアクリレートやメタクリレート及びこれらの混合物を挙げることができる。また、特開2008-292970号公報の段落0254~0257に記載の化合物も好適である。また、多官能カルボン酸にグリシジル(メタ)アクリレート等の環状エーテル基とエチレン性不飽和結合を有する化合物を反応させて得られる多官能(メタ)アクリレートなども挙げることができる。 Further, as the radical cross-linking agent, 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. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropanetri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. 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-51-0379193. Urethane (meth) acrylates as described above, polyester acrylates, epoxy resins and (meth) acrylics described in JP-A-48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490. 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. Further, 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.
 また、上述以外の好ましいラジカル架橋剤として、特開2010-160418号公報、特開2010-129825号公報、特許第4364216号公報等に記載される、フルオレン環を有し、エチレン性不飽和結合を有する基を2個以上有する化合物や、カルド樹脂も使用することが可能である。 Further, as a preferable radical cross-linking agent 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. Compounds having two or more groups and cardo resins can also be used.
 更に、その他の例としては、特公昭46-043946号公報、特公平01-040337号公報、特公平01-040336号公報に記載の特定の不飽和化合物や、特開平02-025493号公報に記載のビニルホスホン酸系化合物等もあげることができる。また、特開昭61-022048号公報に記載のペルフルオロアルキル基を含む化合物を用いることもできる。更に日本接着協会誌 vol.20、No.7、300~308ページ(1984年)に光重合性モノマー及びオリゴマーとして紹介されているものも使用することができる。 Further, as other examples, the specific unsaturated compound described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, and Japanese Patent Application Laid-Open No. 02-025493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, the magazine of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.
 上記のほか、特開2015-034964号公報の段落0048~0051に記載の化合物、国際公開第2015/199219号の段落0087~0131に記載の化合物も好ましく用いることができ、これらの内容は本明細書に組み込まれる。 In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents thereof are described in the present specification. Incorporated into the book.
 また、特開平10-062986号公報において式(1)及び式(2)としてその具体例と共に記載の、多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後に(メタ)アクリレート化した化合物も、ラジカル架橋剤として用いることができる。 Further, the compound described in JP-A No. 10-062986 together with specific examples as the formulas (1) and (2), which is obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated, is also available. It can be used as a radical cross-linking agent.
 更に、特開2015-187211号公報の段落0104~0131に記載の化合物もラジカル架橋剤として用いることができ、これらの内容は本明細書に組み込まれる。 Further, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical cross-linking agents, and their contents are incorporated in the present specification.
 ラジカル架橋剤としては、ジペンタエリスリトールトリアクリレート(市販品としては KAYARAD D-330;日本化薬(株)製)、ジペンタエリスリトールテトラアクリレート(市販品としては KAYARAD D-320;日本化薬(株)製、A-TMMT:新中村化学工業(株)製)、ジペンタエリスリトールペンタ(メタ)アクリレート(市販品としては KAYARAD D-310;日本化薬(株)製)、ジペンタエリスリトールヘキサ(メタ)アクリレート(市販品としては KAYARAD DPHA;日本化薬(株)製、A-DPH;新中村化学工業(株)製)、及びこれらの(メタ)アクリロイル基がエチレングリコール残基又はプロピレングリコール残基を介して結合している構造が好ましい。これらのオリゴマータイプも使用できる。 As radical cross-linking agents, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol residues or propylene glycol residues. A structure that is bonded via the above is preferable. These oligomer types can also be used.
 ラジカル架橋剤の市販品としては、例えばサートマー社製のエチレンオキシ鎖を4個有する4官能アクリレートであるSR-494、エチレンオキシ鎖を4個有する2官能メタクリレートであるサートマー社製のSR-209、231、239、日本化薬(株)製のペンチレンオキシ鎖を6個有する6官能アクリレートであるDPCA-60、イソブチレンオキシ鎖を3個有する3官能アクリレートであるTPA-330、ウレタンオリゴマーUAS-10、UAB-140(日本製紙社製)、NKエステルM-40G、NKエステル4G、NKエステルM-9300、NKエステルA-9300、UA-7200(新中村化学工業(株)製)、DPHA-40H(日本化薬(株)製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(共栄社化学社製)、ブレンマーPME400(日油(株)製)などが挙げられる。 Commercially available products of the radical cross-linking agent include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209 manufactured by Sartmer, which is a bifunctional methacrylate having four ethyleneoxy chains. 231 and 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, and 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 (Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.) And so on.
 ラジカル架橋剤としては、特公昭48-041708号公報、特開昭51-037193号公報、特公平02-032293号公報、特公平02-016765号公報に記載されているようなウレタンアクリレート類や、特公昭58-049860号公報、特公昭56-017654号公報、特公昭62-039417号公報、特公昭62-039418号公報に記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。更に、ラジカル架橋剤として、特開昭63-277653号公報、特開昭63-260909号公報、特開平01-105238号公報に記載される、分子内にアミノ構造やスルフィド構造を有する化合物を用いることもできる。 Examples of the radical cross-linking agent include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-0322293, and Japanese Patent 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. Further, as the radical cross-linking agent, compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, are used. You can also do it.
 ラジカル架橋剤は、カルボキシ基、リン酸基等の酸基を有するラジカル架橋剤であってもよい。酸基を有するラジカル架橋剤は、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルが好ましく、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシ基に非芳香族カルボン酸無水物を反応させて酸基を持たせたラジカル架橋剤がより好ましい。特に好ましくは、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシ基に非芳香族カルボン酸無水物を反応させて酸基を持たせたラジカル架橋剤において、脂肪族ポリヒドロキシ化合物がペンタエリスリトール又はジペンタエリスリトールである化合物である。市販品としては、例えば、東亞合成(株)製の多塩基酸変性アクリルオリゴマーとして、M-510、M-520などが挙げられる。 The radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The radical cross-linking agent provided with the above is more preferable. Particularly preferably, in a radical cross-linking agent 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, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
 酸基を有するラジカル架橋剤の好ましい酸価は、0.1~40mgKOH/gであり、特に好ましくは5~30mgKOH/gである。ラジカル架橋剤の酸価が上記範囲であれば、製造上の取扱性に優れ、更には、現像性に優れる。また、重合性が良好である。一方、アルカリ現像する場合の現像速度の観点では、酸基を有するラジカル架橋剤の好ましい酸価は、0.1~300mgKOH/gであり、特に好ましくは1~100mgKOH/gである。上記酸価は、JIS K 0070:1992の記載に準拠して測定される。 The acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturable handling and further excellent in developability. Moreover, the polymerizability is good. On the other hand, from the viewpoint of the development speed in the case of alkaline development, 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.
 本発明の硬化性樹脂組成物は、パターンの解像性と膜の伸縮性の観点から、2官能のメタアクリレート又はアクリレートを用いることが好ましい。具体的な化合物としては、トリエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、テトラエチレングリコールジアクリレート、PEG200ジアクリレート、PEG200ジメタクリレート、PEG600ジアクリレート、PEG600ジメタクリレート、ポリテトラエチレングリコールジアクリレート、ポリテトラエチレングリコールジメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、3-メチル-1,5-ペンタンジオールジアクリレート、1,6-ヘキサンジオールジアクリレート、1,6ヘキサンジオールジメタクリレート、ジメチロール-トリシクロデカンジアクリレート、ジメチロール-トリシクロデカンジメタクリレート、ビスフェノールAのEO付加物ジアクリレート、ビスフェノールAのEO付加物ジメタクリレート、ビスフェノールAのPO付加物ジアクリレート、ビスフェノールAのPO付加物ジメタクリレート、2-ヒドロキシー3-アクリロイロキシプロピルメタクリレート、イソシアヌル酸EO変性ジアクリレート、イソシアヌル酸変性ジメタクリレート、その他ウレタン結合を有する2官能アクリレート、ウレタン結合を有する2官能メタクリレートを使用することができる。これらは必要に応じ、2種以上を混合し使用することができる。
 また、パターン(硬化膜)の弾性率制御に伴う反り抑制の観点から、ラジカル架橋剤として、単官能ラジカル架橋剤を好ましく用いることができる。単官能ラジカル架橋剤としては、n-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、カルビトール(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、グリシジル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等の(メタ)アクリル酸誘導体、N-ビニルピロリドン、N-ビニルカプロラクタム等のN-ビニル化合物類、アリルグリシジルエーテル、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類等が好ましく用いられる。単官能ラジカル架橋剤としては、露光前の揮発を抑制するため、常圧下で100℃以上の沸点を持つ化合物も好ましい。
In the curable resin composition of the present invention, it is preferable to use a bifunctional metal acrylate or acrylate from the viewpoint of pattern resolution and film elasticity. 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. Glycoglycyl diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol Dimethacrylate, dimethyrol-tricyclodecanediacrylate, dimethyrol-tricyclodecanedimethacrylate, EO adduct diacrylate of bisphenol A, EO adux glycol dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO of bisphenol A Additives dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having a urethane bond, and bifunctional methacrylate having a urethane bond can be used. can. If necessary, two or more of these can be mixed and used.
Further, from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern (cured film), a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent. Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) N-vinyl compounds such as acrylic acid derivatives, N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate and triallyl trimellitate are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
 ラジカル架橋剤を含有する場合、その含有量は、本発明の硬化性樹脂組成物の全固形分に対して、0質量%超60質量%以下であることが好ましい。下限は5質量%以上がより好ましい。上限は、50質量%以下であることがより好ましく、30質量%以下であることが更に好ましい。 When a radical cross-linking agent is contained, the content thereof 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.
 ラジカル架橋剤は1種を単独で用いてもよいが、2種以上を混合して用いてもよい。2種以上を併用する場合にはその合計量が上記の範囲となることが好ましい。 The radical cross-linking agent may be used alone or in combination of two or more. When two or more kinds are used in combination, the total amount is preferably in the above range.
<他の架橋剤>
 本発明の硬化性樹脂組成物は、上述したラジカル架橋剤とは異なる、他の架橋剤を含むことも好ましい。
 本発明において、他の架橋剤とは、上述したラジカル架橋剤以外の架橋剤をいい、上述の感光剤の感光により、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が促進される基を分子内に複数個有する化合物であることが好ましく、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が酸又は塩基の作用によって促進される基を分子内に複数個有する化合物が好ましい。
 上記酸又は塩基は、露光工程において、感光剤である光酸発生剤又は光塩基発生剤から発生する酸又は塩基であることが好ましい。
 他の架橋剤としては、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも一種の基を有する化合物が好ましく、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも一種の基が窒素原子に直接結合した構造を有する化合物がより好ましい。
 他の架橋剤としては、例えば、メラミン、グリコールウリル、尿素、アルキレン尿素、ベンゾグアナミンなどのアミノ基含有化合物にホルムアルデヒド又はホルムアルデヒドとアルコールを反応させ、上記アミノ基の水素原子をメチロール基又はアルコキシメチル基で置換した構造を有する化合物が挙げられる。これらの化合物の製造方法は特に限定されず、上記方法により製造された化合物と同様の構造を有する化合物であればよい。また、これらの化合物のメチロール基同士が自己縮合してなるオリゴマーであってもよい。
 上記のアミノ基含有化合物として、メラミンを用いた架橋剤をメラミン系架橋剤、グリコールウリル、尿素又はアルキレン尿素を用いた架橋剤を尿素系架橋剤、アルキレン尿素を用いた架橋剤をアルキレン尿素系架橋剤、ベンゾグアナミンを用いた架橋剤をベンゾグアナミン系架橋剤という。
 これらの中でも、本発明の硬化性樹脂組成物は、尿素系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことが好ましく、後述するグリコールウリル系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことがより好ましい。
<Other cross-linking agents>
It is also preferable that the curable resin composition of the present invention contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and a covalent bond is formed with another compound in the composition or a reaction product thereof by exposure to the above-mentioned photosensitizer. It is preferable that the compound has a plurality of groups in the molecule that promote the formation reaction, and the reaction of forming a covalent bond with another compound in the composition or a reaction product thereof is the action of the acid or the base. A compound having a plurality of groups promoted by the above in the molecule is preferable.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator which is a photosensitizer in the exposure step.
As the other cross-linking agent, a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is a nitrogen atom. A compound having a structure directly bonded to is more preferable.
As another cross-linking agent, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to a methylol group or an alkoxymethyl group. Examples thereof include compounds having a substituted structure. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
As the above amino group-containing compound, the cross-linking agent using melamine is a melamine-based cross-linking agent, the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent, and the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent. A cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and preferably contains a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. It is more preferable to contain at least one compound selected from the group consisting of system cross-linking agents.
 メラミン系架橋剤の具体例としては、ヘキサメトキシメチルメラミン、ヘキサエトキシメチルメラミン、ヘキサプロポキシメチルメラミン、ヘキサブトキシブチルメラミンなどが挙げられる。 Specific examples of the melamine-based cross-linking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.
 尿素系架橋剤の具体例としては、例えばモノヒドロキシメチル化グリコールウリル、ジヒドロキシメチル化グリコールウリル、トリヒドロキシメチル化グリコールウリル、テトラヒドロキシメチル化グリコールウリル、モノメトキシメチル化グリコールウリル,ジメトキシメチル化グリコールウリル、トリメトキシメチル化グリコールウリル、テトラメトキシメチル化グリコールウリル、モノメトキシメチル化グリコールウリル、ジメトキシメチル化グリコールウリル、トリメトキシメチル化グリコールウリル、テトラエトキシメチル化グリコールウリル、モノプロポキシメチル化グリコールウリル、ジプロポキシメチル化グリコールウリル、トリプロポキシメチル化グリコールウリル、テトラプロポキシメチル化グリコールウリル、モノブトキシメチル化グリコールウリル、ジブトキシメチル化グリコールウリル、トリブトキシメチル化グリコールウリル、又は、テトラブトキシメチル化グリコールウリルなどのグリコールウリル系架橋剤;
 ビスメトキシメチル尿素、ビスエトキシメチル尿素、ビスプロポキシメチル尿素、ビスブトキシメチル尿素等の尿素系架橋剤、
 モノヒドロキシメチル化エチレン尿素又はジヒドロキシメチル化エチレン尿素、モノメトキシメチル化エチレン尿素、ジメトキシメチル化エチレン尿素、モノエトキシメチル化エチレン尿素、ジエトキシメチル化エチレン尿素、モノプロポキシメチル化エチレン尿素、ジプロポキシメチル化エチレン尿素、モノブトキシメチル化エチレン尿素、又は、ジブトキシメチル化エチレン尿素などのエチレン尿素系架橋剤、
 モノヒドロキシメチル化プロピレン尿素、ジヒドロキシメチル化プロピレン尿素、モノメトキシメチル化プロピレン尿素、ジメトキシメチル化プロピレン尿素、モノジエトキシメチル化プロピレン尿素、ジエトキシメチル化プロピレン尿素、モノプロポキシメチル化プロピレン尿素、ジプロポキシメチル化プロピレン尿素、モノブトキシメチル化プロピレン尿素、又は、ジブトキシメチル化プロピレン尿素などのプロピレン尿素系架橋剤、
 1,3-ジ(メトキシメチル)4,5-ジヒドロキシ-2-イミダゾリジノン、1,3-ジ(メトキシメチル)-4,5-ジメトキシ-2-イミダゾリジノンなどが挙げられる。
Specific examples of the urea-based cross-linking agent include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl. , Trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monomethoxymethylated glycol uryl, dimethoxymethylated glycol uryl, trimethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl, di Propoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol uryl, etc. Glycol-uryl-based cross-linking agent;
Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea,
Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea,
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxy A propylene urea-based cross-linking agent such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples thereof include 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone and 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.
 ベンゾグアナミン系架橋剤の具体例としては、例えばモノヒドロキシメチル化ベンゾグアナミン、ジヒドロキシメチル化ベンゾグアナミン、トリヒドロキシメチル化ベンゾグアナミン、テトラヒドロキシメチル化ベンゾグアナミン、モノメトキシメチル化ベンゾグアナミン、ジメトキシメチル化ベンゾグアナミン、トリメトキシメチル化ベンゾグアナミン、テトラメトキシメチル化ベンゾグアナミン、モノメトキシメチル化ベンゾグアナミン、ジメトキシメチル化ベンゾグアナミン、トリメトキシメチル化ベンゾグアナミン、テトラエトキシメチル化ベンゾグアナミン、モノプロポキシメチル化ベンゾグアナミン、ジプロポキシメチル化ベンゾグアナミン、トリプロポキシメチル化ベンゾグアナミン、テトラプロポキシメチル化ベンゾグアナミン、モノブトキシメチル化ベンゾグアナミン、ジブトキシメチル化ベンゾグアナミン、トリブトキシメチル化ベンゾグアナミン、テトラブトキシメチル化ベンゾグアナミンなどが挙げられる。 Specific examples of the benzoguanamine-based cross-linking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine. , Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Examples thereof include methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like.
 その他、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも一種の基を有する化合物としては、芳香環(好ましくはベンゼン環)にメチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも一種の基が直接結合した化合物も好適に用いられる。
 このような化合物の具体例としては、ベンゼンジメタノール、ビス(ヒドロキシメチル)クレゾール、ビス(ヒドロキシメチル)ジメトキシベンゼン、ビス(ヒドロキシメチル)ジフェニルエーテル、ビス(ヒドロキシメチル)ベンゾフェノン、ヒドロキシメチル安息香酸ヒドロキシメチルフェニル、ビス(ヒドロキシメチル)ビフェニル、ジメチルビス(ヒドロキシメチル)ビフェニル、ビス(メトキシメチル)ベンゼン、ビス(メトキシメチル)クレゾール、ビス(メトキシメチル)ジメトキシベンゼン、ビス(メトキシメチル)ジフェニルエーテル、ビス(メトキシメチル)ベンゾフェノン、メトキシメチル安息香酸メトキシメチルフェニル、ビス(メトキシメチル)ビフェニル、ジメチルビス(メトキシメチル)ビフェニル、4,4’,4’’-エチリデントリス[2,6-ビス(メトキシメチル)フェノール]、5,5’-[2,2,2‐トリフルオロ‐1‐(トリフルオロメチル)エチリデン]ビス[2‐ヒドロキシ‐1,3‐ベンゼンジメタノール]、3,3’,5,5’-テトラキス(メトキシメチル)-1,1’-ビフェニル-4,4’-ジオール等が挙げられる。
In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). Compounds to which a group is directly bonded are also preferably used.
Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylphenyl hydroxymethylbenzoate. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzenephenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [2,6-bis (methoxymethyl) phenol], 5 , 5'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3', 5,5'-tetrakis ( Examples thereof include methoxymethyl) -1,1'-biphenyl-4,4'-diol and the like.
 他の架橋剤としては市販品を用いてもよく、好適な市販品としては、46DMOC、46DMOEP(以上、旭有機材工業社製)、DML-PC、DML-PEP、DML-OC、DML-OEP、DML-34X、DML-PTBP、DML-PCHP、DML-OCHP、DML-PFP、DML-PSBP、DML-POP、DML-MBOC、DML-MBPC、DML-MTrisPC、DML-BisOC-Z、DML-BisOCHP-Z、DML-BPC、DMLBisOC-P、DMOM-PC、DMOM-PTBP、DMOM-MBPC、TriML-P、TriML-35XL、TML-HQ、TML-BP、TML-pp-BPF、TML-BPE、TML-BPA、TML-BPAF、TML-BPAP、TMOM-BP、TMOM-BPE、TMOM-BPA、TMOM-BPAF、TMOM-BPAP、HML-TPPHBA、HML-TPHAP、HMOM-TPPHBA、HMOM-TPHAP(以上、本州化学工業社製)、ニカラック(登録商標、以下同様)MX-290、ニカラックMX-280、ニカラックMX-270、ニカラックMX-279、ニカラックMW-100LM、ニカラックMX-750LM(以上、三和ケミカル社製)などが挙げられる。 Commercially available products may be used as other cross-linking agents, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP. , DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, Honshu) Nikarak (registered trademark, the same applies hereinafter) MX-290, Nikarak MX-280, Nikarak MX-270, Nikarak MX-279, Nikarak MW-100LM, Nikarak MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.) ) And so on.
 また、本発明の硬化性樹脂組成物は、他の架橋剤として、エポキシ化合物、オキセタン化合物、及び、ベンゾオキサジン化合物よりなる群から選ばれた少なくとも1種の化合物を含むことも好ましい。 Further, it is also preferable that the curable resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.
〔エポキシ化合物(エポキシ基を有する化合物)〕
 エポキシ化合物としては、一分子中にエポキシ基を2以上有する化合物であることが好ましい。エポキシ基は、200℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、硬化性樹脂組成物の低温硬化及び反りの抑制に効果的である。
[Epoxy compound (compound having an epoxy group)]
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.
 エポキシ化合物は、ポリエチレンオキサイド基を含有することが好ましい。これにより、より弾性率が低下し、また反りを抑制することができる。ポリエチレンオキサイド基は、エチレンオキサイドの繰返し単位数が2以上のものを意味し、繰返し単位数が2~15であることが好ましい。 The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and warpage can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
 エポキシ化合物の例としては、ビスフェノールA型エポキシ樹脂;ビスフェノールF型エポキシ樹脂;プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、ブチレングリコールジグリシジルエーテル、ヘキサメチレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル等のアルキレングリコール型エポキシ樹脂又は多価アルコール炭化水素型エポキシ樹脂;ポリプロピレングリコールジグリシジルエーテル等のポリアルキレングリコール型エポキシ樹脂;ポリメチル(グリシジロキシプロピル)シロキサン等のエポキシ基含有シリコーンなどを挙げることができるが、これらに限定されない。具体的には、エピクロン(登録商標)850-S、エピクロン(登録商標)HP-4032、エピクロン(登録商標)HP-7200、エピクロン(登録商標)HP-820、エピクロン(登録商標)HP-4700、エピクロン(登録商標)EXA-4710、エピクロン(登録商標)HP-4770、エピクロン(登録商標)EXA-859CRP、エピクロン(登録商標)EXA-1514、エピクロン(登録商標)EXA-4880、エピクロン(登録商標)EXA-4850-150、エピクロンEXA-4850-1000、エピクロン(登録商標)EXA-4816、エピクロン(登録商標)EXA-4822、エピクロン(登録商標)EXA-830LVP、エピクロン(登録商標)EXA-8183、エピクロン(登録商標)EXA-8169、エピクロン(登録商標)N-660、エピクロン(登録商標)N-665-EXP-S、エピクロン(登録商標)N-740、リカレジン(登録商標)BEO-20E(以上商品名、DIC(株)製)、リカレジン(登録商標)BEO-60E、リカレジン(登録商標)HBE-100、リカレジン(登録商標)DME-100、リカレジン(登録商標)L-200(商品名、新日本理化(株))、EP-4003S、EP-4000S、EP-4088S、EP-3950S(以上商品名、(株)ADEKA製)、セロキサイド2021P、2081、2000、3000、EHPE3150、エポリードGT400、セルビナースB0134、B0177(以上商品名、(株)ダイセル製)、NC-3000、NC-3000-L、NC-3000-H、NC-3000-FH-75M、NC-3100、CER-3000-L、NC-2000-L、XD-1000、NC-7000L、NC-7300L、EPPN-501H、EPPN-501HY、EPPN-502H、EOCN-1020、EOCN-102S、EOCN-103S、EOCN-104S、CER-1020、EPPN-201、BREN-S、BREN-10S(以上商品名、日本化薬(株)製)などが挙げられる。 Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propanetriglycidyl ether or the like alkylene glycol type epoxy resin or polyhydric alcohol hydrocarbon type epoxy resin; polypropylene glycol diglycidyl ether or the like polyalkylene glycol type epoxy resin; polymethyl (glycidyloxypropyl) siloxane or the like epoxy group Examples include, but are not limited to, the contained silicone. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron® EXA-4816, Epicron® EXA-4822, Epicron® EXA-830LVP, Epicron® EXA-8183, Epicron (Registered Trademark) EXA-8169, Epicron (Registered Trademark) N-660, Epicron (Registered Trademark) N-665-EXP-S, Epicron (Registered Trademark) N-740, Rica Resin (Registered Trademark) BEO-20E (the above products) Name, manufactured by DIC Co., Ltd., Rica Resin (registered trademark) BEO-60E, Rica Resin (registered trademark) HBE-100, Rica Resin (registered trademark) DME-100, Rica Resin (registered trademark) L-200 (trade name, New Japan) Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade name, manufactured by ADEKA Co., Ltd.), Serokiside 2021P, 2081, 2000, 3000, EHPE3150, Epolyde GT400, Servinus B0134, B0177 (trade name, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000 -L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201 , BREN-S, BREN-10S (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like.
〔オキセタン化合物(オキセタニル基を有する化合物)〕
 オキセタン化合物としては、一分子中にオキセタン環を2つ以上有する化合物、3-エチル-3-ヒドロキシメチルオキセタン、1,4-ビス{[(3-エチル-3-オキセタニル)メトキシ]メチル}ベンゼン、3-エチル-3-(2-エチルヘキシルメチル)オキセタン、1,4-ベンゼンジカルボン酸-ビス[(3-エチル-3-オキセタニル)メチル]エステル等を挙げることができる。具体的な例としては、東亞合成(株)製のアロンオキセタンシリーズ(例えば、OXT-121、OXT-221、OXT-191、OXT-223)が好適に使用することができ、これらは単独で、又は2種以上混合してもよい。
[Oxetane compound (compound having an oxetanyl group)]
Examples of 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. As a specific example, 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. Alternatively, two or more types may be mixed.
〔ベンゾオキサジン化合物(ベンゾオキサゾリル基を有する化合物)〕
 ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、更に熱収縮を小さくして反りの発生が抑えられることから好ましい。
[Benzoxazine compound (compound having a benzoxazolyl group)]
Since the benzoxazine compound is a cross-linking reaction derived from the cycloaddition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
 ベンゾオキサジン化合物の好ましい例としては、B-a型ベンゾオキサジン、B-m型ベンゾオキサジン、P-d型ベンゾオキサジン、F-a型ベンゾオキサジン(以上、商品名、四国化成工業社製)、ポリヒドロキシスチレン樹脂のベンゾオキサジン付加物、フェノールノボラック型ジヒドロベンゾオキサジン化合物が挙げられる。これらは単独で用いるか、又は2種以上混合してもよい。 Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (above, 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.
 他の架橋剤の含有量は、本発明の硬化性樹脂組成物の全固形分に対し0.1~30質量%であることが好ましく、0.1~20質量%であることがより好ましく、0.5~15質量%であることが更に好ましく、1.0~10質量%であることが特に好ましい。他の架橋剤は1種のみ含有していてもよいし、2種以上含有していてもよい。他の架橋剤を2種以上含有する場合は、その合計が上記範囲であることが好ましい。 The content of the other cross-linking agent 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 particularly preferably 1.0 to 10% by mass. The other cross-linking agent may be contained in only one kind, or may be contained in two or more kinds. When two or more other cross-linking agents are contained, the total is preferably in the above range.
<スルホンアミド構造を有する化合物、チオウレア構造を有する化合物>
 得られるパターン(硬化膜)の基材への密着性を向上する観点からは、本発明の硬化性樹脂組成物は、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物よりなる群から選ばれた少なくとも1種の化合物を更に含むことが好ましい。
<Compounds having a sulfonamide structure, compounds having a thiourea structure>
From the viewpoint of improving the adhesion of the obtained pattern (cured film) to the substrate, the curable 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.
〔スルホンアミド構造を有する化合物〕
 スルホンアミド構造とは、下記式(S-1)で表される構造である。
Figure JPOXMLDOC01-appb-C000062

 式(S-1)中、Rは水素原子又は有機基を表し、Rは他の構造と結合して環構造を形成してもよく、*はそれぞれ独立に、他の構造との結合部位を表す。
 上記Rは、下記式(S-2)におけるRと同様の基であることが好ましい。
 スルホンアミド構造を有する化合物は、スルホンアミド構造を2以上有する化合物であってもよいが、スルホンアミド構造を1つ有する化合物であることが好ましい。
[Compound having a sulfonamide structure]
The sulfonamide structure is a structure represented by the following formula (S-1).
Figure JPOXMLDOC01-appb-C000062

In the formula (S-1), R represents a hydrogen atom or an organic group, R may be bonded to another structure to form a ring structure, and * may independently form a binding site with another structure. show.
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 is preferably a compound having one sulfonamide structure.
 スルホンアミド構造を有する化合物は、下記式(S-2)で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000063

 式(S-2)中、R、R及びRはそれぞれ独立に、水素原子又は1価の有機基を表し、R、R及びRのうち2つ以上が互いに結合して環構造を形成していてもよい。
 R、R及びRはそれぞれ独立に、1価の有機基であることが好ましい。
 R、R及びRの例としては、水素原子、又は、アルキル基、シクロアルキル基、アルコキシ基、アルキルエーテル基、アルキルシリル基、アルコキシシリル基、アリール基、アリールエーテル基、カルボキシ基、カルボニル基、アリル基、ビニル基、複素環基、若しくはこれらを2以上組み合わせた基などが挙げられる。
 上記アルキル基としては、炭素数1~10のアルキル基が好ましく、炭素数1~6のアルキル基がより好ましい。上記アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、2-エチルへキシル基等が挙げられる。
 上記シクロアルキル基としては、炭素数5~10のシクロアルキル基が好ましく、炭素数6~10のシクロアルキル基がより好ましい。上記シクロアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基及びシクロヘキシル基等が挙げられる。
 上記アルコキシ基としては、炭素数1~10のアルコキシ基が好ましく、炭素数1~5のアルコキシ基がより好ましい。上記アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基及びペントキシ基等が挙げられる。
 上記アルコキシシリル基としては、炭素数1~10のアルコキシシリル基が好ましく、炭素数1~4のアルコキシシリル基がより好ましい。上記アルコキシシリル基としては、メトキシシリル基、エトキシシリル基、プロポキシシリル基及びブトキシシリル基等が挙げられる。
 上記アリール基としては、炭素数6~20のアリール基が好ましく、炭素数6~12のアリール基がより好ましい。上記アリール基は、アルキル基等の置換基を有していてもよい。上記アリール基としては、フェニル基、トリル基、キシリル基及びナフチル基等が挙げられる。
 上記複素環基としては、トリアゾール環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、イソオキサゾール環、イソチアゾール環、テトラゾール環、ピリジン環、ピリダジン環、ピリミジジン環、ピラジン環、ピペリジン環、ピペリジン、ピペラジン環、モルホリン環、ジヒドロピラン環、テトラヒドロピラン基、トリアジン環等の複素環構造から水素原子を1つ除いた基などが挙げられる。
The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).
Figure JPOXMLDOC01-appb-C000063

In formula (S-2), R 1 , R 2 and R 3 each independently represent a hydrogen atom or a monovalent organic group, and two or more of R 1 , R 2 and R 3 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.
Examples of R 1 , R 2 and R 3 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 and a carboxy group. 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.
As 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. Examples of the alkyl group 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.
As the cycloalkyl group, 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.
As the alkoxy group, 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.
As the 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, a naphthyl group and the like.
Examples of the heterocyclic group 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 isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a pyrimididin ring. , Pyrazole ring, piperidine ring, piperidine, piperazine ring, morpholine ring, dihydropyran ring, tetrahydropyran group, triazine ring and other heterocyclic structures from which one hydrogen atom has been removed.
 これらの中でも、Rがアリール基であり、かつ、R及びRがそれぞれ独立に、水素原子又はアルキル基である化合物が好ましい。 Among these, compounds in which R 1 is an aryl group and R 2 and R 3 are independently hydrogen atoms or alkyl groups are preferable.
 スルホンアミド構造を有する化合物の例としては、ベンゼンスルホンアミド、ジメチルベンゼンスルホンアミド、N-ブチルベンゼンスルホンアミド、スルファニルアミド、o-トルエンスルホンアミド、p-トルエンスルホンアミド、ヒドロキシナフタレンスルホンアミド、ナフタレン-1-スルホンアミド、ナフタレン-2-スルホンアミド、m-ニトロベンゼンスルホンアミド、p-クロロベンゼンスルホンアミド、メタンスルホンアミド、N,N-ジメチルメタンスルホンアミド、N,N-ジメチルエタンスルホンアミド、N,N-ジエチルメタンスルホンアミド、N-メトキシメタンスルホンアミド、N-ドデシルメタンスルホンアミド、N-シクロヘキシル-1-ブタンスルホンアミド、2-アミノエタンスルホンアミドなどが挙げられる。 Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfanylamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1. -Sulfonamide, Naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N, N-dimethylmethanesulfonamide, N, N-dimethylethanesulfonamide, N, N-diethyl Examples thereof include methanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, 2-aminoethanesulfonamide and the like.
〔チオウレア構造を有する化合物〕
 チオウレア構造とは、下記式(T-1)で表される構造である。
Figure JPOXMLDOC01-appb-C000064

 式(T-1)中、R及びRはそれぞれ独立に、水素原子又は1価の有機基を表し、R及びRは結合して環構造を形成してもよく、Rは*が結合する他の構造と結合して環構造を形成してもよく、Rは*が結合する他の構造と結合して環構造を形成してもよく、*はそれぞれ独立に、他の構造との結合部位を表す。
[Compound with thiourea structure]
The thiourea structure is a structure represented by the following formula (T-1).
Figure JPOXMLDOC01-appb-C000064

In 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 bonded to form a ring structure, where R 4 is. * it is may form a ring structure and other structures that bind, R 5 may form a ring structure and other structures that bind *, * is independently other Represents the site of connection with the structure of.
 R及びRはそれぞれ独立に、水素原子であることが好ましい。
 R及びRの例としては、水素原子、又は、アルキル基、シクロアルキル基、アルコキシ基、アルキルエーテル基、アルキルシリル基、アルコキシシリル基、アリール基、アリールエーテル基、カルボキシ基、カルボニル基、アリル基、ビニル基、複素環基、若しくは、これらを2以上組み合わせた基などが挙げられる。
 上記アルキル基としては、炭素数1~10のアルキル基が好ましく、炭素数1~6のアルキル基がより好ましい。上記アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、イソプロピル基、2-エチルへキシル基等が挙げられる。
 上記シクロアルキル基としては、炭素数5~10のシクロアルキル基が好ましく、炭素数6~10のシクロアルキル基がより好ましい。上記シクロアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基及びシクロヘキシル基等が挙げられる。
 上記アルコキシ基としては、炭素数1~10のアルコキシ基が好ましく、炭素数1~5のアルコキシ基がより好ましい。上記アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基及びペントキシ基等が挙げられる。
 上記アルコキシシリル基としては、炭素数1~10のアルコキシシリル基が好ましく、炭素数1~4のアルコキシシリル基がより好ましい。上記アルコキシシリル基としては、メトキシシリル基、エトキシシリル基、プロポキシシリル基及びブトキシシリル基等が挙げられる。
 上記アリール基としては、炭素数6~20のアリール基が好ましく、炭素数6~12のアリール基がより好ましい。上記アリール基は、アルキル基等の置換基を有していてもよい。上記アリール基としては、フェニル基、トリル基、キシリル基及びナフチル基等が挙げられる。
 上記複素環基としては、トリアゾール環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、イソオキサゾール環、イソチアゾール環、テトラゾール環、ピリジン環、ピリダジン環、ピリミジジン環、ピラジン環、ピペリジン環、ピペリジン、ピペラジン環、モルホリン環、ジヒドロピラン環、テトラヒドロピラン基、トリアジン環等の複素環構造から水素原子を1つ除いた基などが挙げられる。
 チオウレア構造を有する化合物は、チオウレア構造を2以上有する化合物であってもよいが、チオウレア構造を1つ有する化合物であることが好ましい。
It is preferable that R 4 and R 5 are independently hydrogen atoms.
Examples of 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.
As 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. Examples of the alkyl group 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.
As the cycloalkyl group, 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.
As the alkoxy group, 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.
As the 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, a naphthyl group and the like.
Examples of the heterocyclic group 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 isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring and a pyrimididin ring. , Pyrazole ring, piperidine ring, piperidine, piperazine ring, morpholine ring, dihydropyran ring, tetrahydropyran group, triazine ring and other heterocyclic structures from which one hydrogen atom has been removed.
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.
 チオウレア構造を有する化合物は、下記式(T-2)で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000065

 式(T-2)中、R~Rはそれぞれ独立に、水素原子又は1価の有機基を表し、R~Rのうち少なくとも2つは互いに結合して環構造を形成していてもよい。
The compound having a thiourea structure is preferably a compound represented by the following formula (T-2).
Figure JPOXMLDOC01-appb-C000065

In formula (T-2), R 4 to R 7 each independently represent a hydrogen atom or a monovalent organic group, and at least two of R 4 to R 7 are bonded to each other to form a ring structure. You may.
 式(T-2)中、R及びRは式(T-1)中のR及びRと同義であり、好ましい態様も同様である。
 式(T-2)中、R及びRはそれぞれ独立に、1価の有機基であることが好ましい。
 式(T-2)中、R及びRにおける1価の有機基の好ましい態様は、式(T-1)中のR及びRにおける1価の有機基の好ましい態様と同様である。
Wherein (T-2), 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.
In the formula (T-2), it is preferable that R 6 and R 7 are independently monovalent organic groups.
In the formula (T-2), 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). ..
 チオウレア構造を有する化合物の例としては、N-アセチルチオウレア、N-アリルチオウレア、N-アリル-N’-(2-ヒドロキシエチル)チオウレア、1-アダマンチルチオウレア、N-ベンゾイルチオウレア、N,N’-ジフェニルチオウレア、1-ベンジル-フェニルチオウレア、1,3-ジブチルチオウレア、1,3-ジイソプロピルチオウレア、1,3-ジシクロヘキシルチオウレア、1-(3-(トリメトキシシリル)プロピル)-3-メチルチオウレア、トリメチルチオウレア、テトラメチルチオウレア、N,N-ジフェニルチオウレア、エチレンチオウレア(2-イミダゾリンチオン)、カルビマゾール、1,3-ジメチル-2-チオヒダントインなどが挙げられる。 Examples of compounds having a thiourea structure include N-acetylthiourea, N-allyl thiourea, N-allyl-N'-(2-hydroxyethyl) thiourea, 1-adamantyl thiourea, N-benzoylthiourea, 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-thiohydrantin.
〔含有量〕
 本発明の硬化性樹脂組成物の全質量に対する、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物の合計含有量は、0.05~10質量%であることが好ましく、0.1~5質量%であることがより好ましく、0.2~3質量%であることが更に好ましい。
 本発明の硬化性樹脂組成物は、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物よりなる群から選ばれる化合物を、1種のみ含んでもよいし、2種以上を含んでもよい。1種のみ含む場合にはその化合物の含有量が、2種以上を含む場合にはその合計量が、上記の範囲となることが好ましい。
〔Content〕
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 curable resin composition of the present invention. %, More preferably 0.2 to 3% by mass.
The curable 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 of them. When only one kind is contained, the content of the compound is preferably in the above range, and when two or more kinds are contained, the total amount thereof is preferably in the above range.
<重合禁止剤>
 本発明の硬化性樹脂組成物は、重合禁止剤を含むことが好ましい。
<Polymerization inhibitor>
The curable resin composition of the present invention preferably contains a polymerization inhibitor.
 重合禁止剤としては、例えば、ヒドロキノン、o-メトキシフェノール、メトキシヒドロキノン、p-メトキシフェノール、ジ-tert-ブチル-p-クレゾール、ピロガロール、p-tert-ブチルカテコール(t-ブチルカテコール)、1,4-ベンゾキノン、ジフェニル-p-ベンゾキノン、4,4’-チオビス(3-メチル-6-tert-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)、N-ニトロソ-N-フェニルヒドロキシアミンアルミニウム塩、フェノチアジン、N-ニトロソジフェニルアミン、N-フェニルナフチルアミン、エチレンジアミン四酢酸、1,2-シクロヘキサンジアミン四酢酸、グリコールエーテルジアミン四酢酸、2,6-ジ-tert-ブチル-4-メチルフェノール、5-ニトロソ-8-ヒドロキシキノリン、1-ニトロソ-2-ナフトール、2-ニトロソ-1-ナフトール、2-ニトロソ-5-(N-エチル-N-スルホプロピルアミノ)フェノール、N-ニトロソフェニルヒドロキシアミン第一セリウム塩、N-ニトロソ-N-(1-ナフチル)ヒドロキシアミンアンモニウム塩、ビス(4-ヒドロキシ-3,5-tert-ブチル)フェニルメタン、N,N’-ジフェニル-p-フェニレンジアミン、2,4-ジ-tert-ブチルフェノール、ジ-t-ブチルヒドロキシトルエン、1,4-ナフトキノン、1,3,5-トリス(4-t-ブチル-3-ヒドロキシ-2,6-ジメチルベンジル)-1,3,5-トリアジン-2,4,6-(1H,3H,5H)-トリオン、4‐ヒドロキシ-2,2,6,6-テトラメチルピペリジン1-オキシルフリーラジカル、フェノチアジン、1,1-ジフェニル-2-ピクリルヒドラジル、ジブチルジチオカーバネート銅(II)、ニトロベンゼン、N-ニトロソ-N-フェニルヒドロキシルアミンアルミニウム塩、N-ニトロソ-N-フェニルヒドロキシルアミンアンモニウム塩などが好適に用いられる。また、特開2015-127817号公報の段落0060に記載の重合禁止剤、及び、国際公開第2015/125469号の段落0031~0046に記載の化合物を用いることもできる。 Examples of the polymerization inhibitor include hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol (t-butylcatechol), 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso- N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4 -Methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5 (N-ethyl-N-sulfopropylamino) phenol, N- Nitrosophenyl hydroxyamine first cerium salt, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-hydroxy-3,5-tert-butyl) phenylmethane, N, N'-diphenyl-p -Phenylenediamine, 2,4-di-tert-butylphenol, di-t-butylhydroxytoluene, 1,4-naphthoquinone, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6- Dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl-free radical, phenothiazine , 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. It is preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.
 また、下記化合物を用いることができる(Meはメチル基である)。 In addition, the following compounds can be used (Me is a methyl group).
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
 本発明の硬化性樹脂組成物が重合禁止剤を有する場合、重合禁止剤の含有量は、本発明の硬化性樹脂組成物の全固形分に対して、0.01~20.0質量%が挙げられ、0.01~5質量%であることが好ましく、0.02~3質量%であることがより好ましく、0.05~2.5質量%であることが更に好ましい。 When the curable resin composition of the present invention has a polymerization inhibitor, 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 even more preferably 0.05 to 2.5% by mass.
 重合禁止剤は1種のみでもよいし、2種以上であってもよい。重合禁止剤が2種以上の場合は、その合計が上記範囲であることが好ましい。 The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
<金属接着性改良剤>
 本発明の硬化性樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。
金属接着性改良剤としては、アルミニウム系接着助剤、チタン系接着助剤、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物、リン酸誘導体化合物、βケトエステル化合物、アミノ化合物等などが挙げられる。
<Metal adhesion improver>
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.
Examples of the metal adhesiveness improving agent include aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds and the like.
〔アルミニウム系接着助剤〕
 アルミニウム系接着助剤としては、例えば、アルミニウムトリス(エチルアセトアセテート)、アルミニウムトリス(アセチルアセトネート)、エチルアセトアセテートアルミニウムジイソプロピレート等を挙げることができる。
 また、金属接着性改良剤としては、特開2014-186186号公報の段落0046~0049に記載の化合物、特開2013-072935号公報の段落0032~0043に記載のスルフィド系化合物を用いることができる。
[Aluminum-based adhesive aid]
Examples of the aluminum-based adhesive aid include aluminum tris (ethyl acetoacetate), aluminum tris (acetyl acetonate), ethyl acetoacetate aluminum diisopropylate, and the like.
Further, as the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can be used. ..
 金属接着性改良剤の含有量は特定樹脂100質量部に対して、好ましくは0.1~30質量部であり、より好ましくは0.5~15質量部の範囲であり、更に好ましくは0.5~5質量部の範囲である。上記下限値以上とすることでパターンと金属層との接着性が良好となり、上記上限値以下とすることでパターンの耐熱性、機械特性が良好となる。金属接着性改良剤は1種のみでもよいし、2種以上であってもよい。2種以上用いる場合は、その合計が上記範囲であることが好ましい。 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. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the pattern are good. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more kinds are used, it is preferable that the total is in the above range.
<その他の添加剤>
 本発明の硬化性樹脂組成物は、本発明の効果が得られる範囲で、必要に応じて、各種の添加物、例えば、増感剤、連鎖移動剤、界面活性剤、高級脂肪酸誘導体、無機粒子、硬化剤、硬化触媒、充填剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は硬化性樹脂組成物の固形分の3質量%以下とすることが好ましい。
<Other additives>
The curable resin composition of the present invention contains various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, and inorganic particles, if necessary, to the extent that the effects of the present invention can be obtained. , Curing agent, curing catalyst, filler, antioxidant, ultraviolet absorber, antiaggregating agent 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.
〔増感剤〕
 本発明の硬化性樹脂組成物は、増感剤を含んでいてもよい。増感剤は、特定の活性放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、熱硬化促進剤、熱ラジカル重合開始剤、光ラジカル重合開始剤などと接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより、熱硬化促進剤、熱ラジカル重合開始剤、光ラジカル重合開始剤は化学変化を起こして分解し、ラジカル、酸又は塩基を生成する。
 増感剤としては、例えば、ミヒラーズケトン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、2,5-ビス(4’-ジエチルアミノベンザル)シクロペンタン、2,6-ビス(4’-ジエチルアミノベンザル)シクロヘキサノン、2,6-ビス(4’-ジエチルアミノベンザル)-4-メチルシクロヘキサノン、4,4’-ビス(ジメチルアミノ)カルコン、4,4’-ビス(ジエチルアミノ)カルコン、p-ジメチルアミノシンナミリデンインダノン、p-ジメチルアミノベンジリデンインダノン、2-(p-ジメチルアミノフェニルビフェニレン)-ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)イソナフトチアゾール、1,3-ビス(4’-ジメチルアミノベンザル)アセトン、1,3-ビス(4’-ジエチルアミノベンザル)アセトン、3,3’-カルボニル-ビス(7-ジエチルアミノクマリン)、3-アセチル-7-ジメチルアミノクマリン、3-エトキシカルボニル-7-ジメチルアミノクマリン、3-ベンジロキシカルボニル-7-ジメチルアミノクマリン、3-メトキシカルボニル-7-ジエチルアミノクマリン、3-エトキシカルボニル-7-ジエチルアミノクマリン、N-フェニル-N’-エチルエタノールアミン、N-フェニルジエタノールアミン、N-p-トリルジエタノールアミン、N-フェニルエタノールアミン、4-モルホリノベンゾフェノン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、2-メルカプトベンズイミダゾール、1-フェニル-5-メルカプトテトラゾール、2-メルカプトベンゾチアゾール、2-(p-ジメチルアミノスチリル)ベンズオキサゾール、2-(p-ジメチルアミノスチリル)ベンズチアゾール、2-(p-ジメチルアミノスチリル)ナフト(1,2-d)チアゾール、2-(p-ジメチルアミノベンゾイル)スチレン、ジフェニルアセトアミド、ベンズアニリド、N-メチルアセトアニリド、3‘,4’-ジメチルアセトアニリド等が挙げられる。
 増感剤としては、増感色素を用いてもよい。
 増感色素の詳細については、特開2016-027357号公報の段落0161~0163の記載を参酌でき、この内容は本明細書に組み込まれる。
[Sensitizer]
The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with the thermal curing accelerator, the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate a radical, an acid, or a base.
Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinnamyl Denindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylbinylene) benzothiazole, 2- (p-dimethylaminophenylbinylene) iso Naftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3 -Acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino Kumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercapto Benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) ) Naft (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3', 4'-dimethylacetanilide and the like.
As the sensitizer, a sensitizing dye may be used.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-027355 can be referred to, and the content thereof is incorporated in the present specification.
 本発明の硬化性樹脂組成物が増感剤を含む場合、増感剤の含有量は、本発明の硬化性樹脂組成物の全固形分に対し、0.01~20質量%であることが好ましく、0.1~15質量%であることがより好ましく、0.5~10質量%であることが更に好ましい。増感剤は、1種単独で用いてもよいし、2種以上を併用してもよい。 When the curable resin composition of the present invention contains a sensitizer, 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.
〔連鎖移動剤〕
 本発明の硬化性樹脂組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版(高分子学会編、2005年)683-684頁に定義されている。連鎖移動剤としては、例えば、分子内にSH、PH、SiH、及びGeHを有する化合物群が用いられる。これらは、低活性のラジカルに水素を供与して、ラジカルを生成するか、若しくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。特に、チオール化合物を好ましく用いることができる。
[Chain transfer agent]
The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (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. In particular, thiol compounds can be preferably used.
 また、連鎖移動剤は、国際公開第2015/199219号の段落0152~0153に記載の化合物を用いることもできる。 Further, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.
 本発明の硬化性樹脂組成物が連鎖移動剤を有する場合、連鎖移動剤の含有量は、本発明の硬化性樹脂組成物の全固形分100質量部に対し、0.01~20質量部が好ましく、1~10質量部がより好ましく、1~5質量部が更に好ましい。連鎖移動剤は1種のみでもよいし、2種以上であってもよい。連鎖移動剤が2種以上の場合は、その合計が上記範囲であることが好ましい。 When the curable resin composition of the present invention has a chain transfer agent, 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. Preferably, 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 is preferably in the above range.
〔界面活性剤〕
 本発明の硬化性樹脂組成物には、塗布性をより向上させる観点から、界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種類の界面活性剤を使用できる。また、下記界面活性剤も好ましい。下記式中、主鎖の繰返し単位を示す括弧は各繰返し単位の含有量(モル%)を、側鎖の繰返し単位を示す括弧は各繰返し単位の繰り返し数をそれぞれ表す。
Figure JPOXMLDOC01-appb-C000067

 また、界面活性剤は、国際公開第2015/199219号の段落0159~0165に記載の化合物を用いることもできる。
 フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開2010-164965号公報の段落0050~0090および段落0289~0295に記載された化合物、例えばDIC(株)製のメガファックRS-101、RS-102、RS-718K等が挙げられる。
[Surfactant]
A surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferable. In the following formula, the parentheses indicating the repeating unit of the main chain indicate the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain indicate the number of repetitions of each repeating unit.
Figure JPOXMLDOC01-appb-C000067

Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
As the 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 thereof include 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.
 フッ素系界面活性剤中のフッ素含有率は、3~40質量%が好適であり、より好ましくは5~30質量%であり、特に好ましくは7~25質量%である。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性や省液性の点で効果的であり、組成物中における溶解性も良好である。 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 in the thickness of the coating film and liquid saving, and has good solubility in the composition.
 シリコーン系界面活性剤としては、例えば、トーレシリコーンDC3PA、トーレシリコーンSH7PA、トーレシリコーンDC11PA、トーレシリコーンSH21PA、トーレシリコーンSH28PA、トーレシリコーンSH29PA、トーレシリコーンSH30PA、トーレシリコーンSH8400(以上、東レ・ダウコーニング(株)製)、TSF-4440、TSF-4300、TSF-4445、TSF-4460、TSF-4452(以上、モメンティブ・パフォーマンス・マテリアルズ社製)、KP341、KF6001、KF6002(以上、信越シリコーン(株)製)、BYK307、BYK323、BYK330(以上、ビックケミー(株)製)等が挙げられる。 Examples of the silicone-based surfactant 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), KP341, KF6001, KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.
 炭化水素系界面活性剤としては、例えば、パイオニンA-76、ニューカルゲンFS-3PG、パイオニンB-709、パイオニンB-811-N、パイオニンD-1004、パイオニンD-3104、パイオニンD-3605、パイオニンD-6112、パイオニンD-2104-D、パイオニンD-212、パイオニンD-931、パイオニンD-941、パイオニンD-951、パイオニンE-5310、パイオニンP-1050-B、パイオニンP-1028-P、パイオニンP-4050-T等(以上、竹本油脂社製)、などが挙げられる。 Examples of the hydrocarbon-based surfactant 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. D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (all manufactured by Takemoto Oil & Fat Co., Ltd.) and the like can be mentioned.
 ノニオン型界面活性剤としては、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート(例えば、グリセロールプロポキシレート、グリセロールエトキシレート等)、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル、プルロニック(登録商標)L10、L31、L61、L62、10R5、17R2、25R2(BASF社製)、テトロニック304、701、704、901、904、150R1(BASF社製)、ソルスパース20000(日本ルーブリゾール(株)製)、NCW-101、NCW-1001、NCW-1002(和光純薬工業(株)製)、パイオニンD-6112、D-6112-W、D-6315(竹本油脂(株)製)、オルフィンE1010、サーフィノール104、400、440(日信化学工業(株)製)などが挙げられる。 Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic® L10, L31, L61, L62, 10R5, 17R2 , 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsparse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Manufactured by Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (Nisshin Chemical Industry Co., Ltd. (Nissin Chemical Industry Co., Ltd.) Made by Co., Ltd.).
 カチオン型界面活性剤として具体的には、オルガノシロキサンポリマーKP341(信越化学工業(株)製)、(メタ)アクリル酸系(共)重合体ポリフローNo.75、No.77、No.90、No.95(共栄社化学(株)製)、W001(裕商(株)製)等が挙げられる。 Specifically, as a cationic surfactant, 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.) and the like can be mentioned.
 アニオン型界面活性剤として具体的には、W004、W005、W017(裕商(株)製)、サンデットBL(三洋化成(株)製)等が挙げられる。 Specific examples of the anion-type surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
 本発明の硬化性樹脂組成物が界面活性剤を有する場合、界面活性剤の含有量は、本発明の硬化性樹脂組成物の全固形分に対して、0.001~2.0質量%であることが好ましく、より好ましくは0.005~1.0質量%である。界面活性剤は1種のみでもよいし、2種以上であってもよい。界面活性剤が2種以上の場合は、その合計が上記範囲であることが好ましい。 When the curable resin composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0% by mass based on 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 is preferably in the above range.
〔高級脂肪酸誘導体〕
 本発明の硬化性樹脂組成物は、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で硬化性樹脂組成物の表面に偏在させてもよい。
[Higher fatty acid derivative]
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.
 また、高級脂肪酸誘導体は、国際公開第2015/199219号の段落0155に記載の化合物を用いることもできる。 Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used.
 本発明の硬化性樹脂組成物が高級脂肪酸誘導体を有する場合、高級脂肪酸誘導体の含有量は、本発明の硬化性樹脂組成物の全固形分に対して、0.1~10質量%であることが好ましい。高級脂肪酸誘導体は1種のみでもよいし、2種以上であってもよい。高級脂肪酸誘導体が2種以上の場合は、その合計が上記範囲であることが好ましい。 When the curable resin composition of the present invention has a higher fatty acid derivative, 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 is preferably in the above range.
〔無機粒子〕
 本発明の樹脂組成物は、無機粒子を含んでもよい。無機粒子として、具体的には、炭酸カルシウム、リン酸カルシウム、シリカ、カオリン、タルク、二酸化チタン、アルミナ、硫酸バリウム、フッ化カルシウム、フッ化リチウム、ゼオライト、硫化モリブデン、ガラス等を含むことができる。
[Inorganic particles]
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.
 上記無機粒子の平均粒子径としては、0.01~2.0μmが好ましく、0.02~1.5μmがより好ましく、0.03~1.0μmがさらに好ましく、0.04~0.5μmが特に好ましい。
 上記平均粒子径の無機粒子を含有させることによって、硬化膜の機械特性と露光光の散乱抑制を両立することができる。
The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferable.
By containing the inorganic particles having the average particle size, it is possible to achieve both the mechanical properties of the cured film and the suppression of scattering of the exposure light.
〔紫外線吸収剤〕
 本発明の組成物は、紫外線吸収剤を含んでいてもよい。紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、トリアジン系などの紫外線吸収剤を使用することができる。
 サリシレート系紫外線吸収剤の例としては、フェニルサリシレート、p-オクチルフェニルサリシレート、p-t-ブチルフェニルサリシレートなどが挙げられ、ベンゾフェノン系紫外線吸収剤の例としては、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン、2,2’-ジヒドロキシ-4,4’-ジメトキシベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン、2,4-ジヒドロキシベンゾフェノン、2-ヒドロキシ-4-オクトキシベンゾフェノンなどが挙げられる。また、ベンゾトリアゾール系紫外線吸収剤の例としては、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-ブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-アミル-5’-イソブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-プロピルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2-[2’-ヒドロキシ-5’-(1,1,3,3-テトラメチル)フェニル]ベンゾトリアゾールなどが挙げられる。
[UV absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
Examples of salicylate-based ultraviolet absorbers include phenylsalicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like, and examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-. Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxyl-4-octoxybenzophenone and the like can be mentioned. Examples of benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3). '-Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5' -(1,1,3,3-tetramethyl) phenyl] benzotriazole and the like can be mentioned.
 置換アクリロニトリル系紫外線吸収剤の例としては、2-シアノ-3,3-ジフェニルアクリル酸エチル、2-シアノ-3,3-ジフェニルアクリル酸2-エチルヘキシルなどが挙げられる。さらに、トリアジン系紫外線吸収剤の例としては、2-[4-[(2-ヒドロキシ-3-ドデシルオキシプロピル)オキシ]-2-ヒドロキシフェニル]-4,6-ビス(2,4-ジメチルフェニル)-1,3,5-トリアジン、2-[4-[(2-ヒドロキシ-3-トリデシルオキシプロピル)オキシ]-2-ヒドロキシフェニル]-4,6-ビス(2,4-ジメチルフェニル)-1,3,5-トリアジン、2-(2,4-ジヒドロキシフェニル)-4,6-ビス(2,4-ジメチルフェニル)-1,3,5-トリアジンなどのモノ(ヒドロキシフェニル)トリアジン化合物;2,4-ビス(2-ヒドロキシ-4-プロピルオキシフェニル)-6-(2,4-ジメチルフェニル)-1,3,5-トリアジン、2,4-ビス(2-ヒドロキシ-3-メチル-4-プロピルオキシフェニル)-6-(4-メチルフェニル)-1,3,5-トリアジン、2,4-ビス(2-ヒドロキシ-3-メチル-4-ヘキシルオキシフェニル)-6-(2,4-ジメチルフェニル)-1,3,5-トリアジンなどのビス(ヒドロキシフェニル)トリアジン化合物;2,4-ビス(2-ヒドロキシ-4-ブトキシフェニル)-6-(2,4-ジブトキシフェニル)-1,3,5-トリアジン、2,4,6-トリス(2-ヒドロキシ-4-オクチルオキシフェニル)-1,3,5-トリアジン、2,4,6-トリス[2-ヒドロキシ-4-(3-ブトキシ-2-ヒドロキシプロピルオキシ)フェニル]-1,3,5-トリアジンなどのトリス(ヒドロキシフェニル)トリアジン化合物等が挙げられる。 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. Further, as an example of the triazine-based ultraviolet absorber, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl) -4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2) , 4-Dimethylphenyl) -1,3,5-Triazine and other bis (hydroxyphenyl) triazine compounds; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) )-1,3,5-Triazine, 2,4,6-Tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-Triazine, 2,4,6-Tris [2-Hydroxy-4 -(3-Butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-Triazine and other tris (hydroxyphenyl) triazine compounds and the like can be mentioned.
 本発明においては、前記各種の紫外線吸収剤は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
 本発明の組成物は、紫外線吸収剤を含んでも含まなくてもよいが、含む場合、紫外線吸収剤の含有量は、本発明の組成物の全固形分質量に対して、0.001質量%以上1質量%以下であることが好ましく、0.01質量%以上0.1質量%以下であることがより好ましい。
In the present invention, the 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.
〔有機チタン化合物〕 
 本実施形態の樹脂組成物は、有機チタン化合物を含有してもよい。樹脂組成物が有機チタン化合物を含有することにより、低温で硬化した場合であっても耐薬品性に優れる樹脂層を形成できる。
[Organic titanium compound]
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.
 使用可能な有機チタン化合物としては、チタン原子に有機基が共有結合又はイオン結合を介して結合しているものが挙げられる。
有機チタン化合物の具体例を、以下のI)~VII)に示す:
I)チタンキレート化合物:中でも、ネガ型感光性樹脂組成物の保存安定性がよく、良好な硬化パターンが得られることから、アルコキシ基を2個以上有するチタンキレート化合物がより好ましい。具体的な例は、チタニウムビス(トリエタノールアミン)ジイソプロポキサイド、チタニウムジ(n-ブトキサイド)ビス(2,4-ペンタンジオネート、チタニウムジイソプロポキサイドビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(テトラメチルヘプタンジオネート)、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)等である。
II)テトラアルコキシチタン化合物:例えば、チタニウムテトラ(n-ブトキサイド)、チタニウムテトラエトキサイド、チタニウムテトラ(2-エチルヘキソキサイド)、チタニウムテトライソブトキサイド、チタニウムテトライソプロポキサイド、チタニウムテトラメトキサイド、チタニウムテトラメトキシプロポキサイド、チタニウムテトラメチルフェノキサイド、チタニウムテトラ(n-ノニロキサイド)、チタニウムテトラ(n-プロポキサイド)、チタニウムテトラステアリロキサイド、チタニウムテトラキス[ビス{2,2-(アリロキシメチル)ブトキサイド}]等である。
III)チタノセン化合物:例えば、ペンタメチルシクロペンタジエニルチタニウムトリメトキサイド、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロフェニル)チタニウム、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)チタニウム等である。
IV)モノアルコキシチタン化合物:例えば、チタニウムトリス(ジオクチルホスフェート)イソプロポキサイド、チタニウムトリス(ドデシルベンゼンスルホネート)イソプロポキサイド等である。
V)チタニウムオキサイド化合物:例えば、チタニウムオキサイドビス(ペンタンジオネート)、チタニウムオキサイドビス(テトラメチルヘプタンジオネート)、フタロシアニンチタニウムオキサイド等である。
VI)チタニウムテトラアセチルアセトネート化合物:例えば、チタニウムテトラアセチルアセトネート等である。
VII)チタネートカップリング剤:例えば、イソプロピルトリドデシルベンゼンスルホニルチタネート等である。
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) diisopropoxiside, titanium di (n-butoxide) bis (2,4-pentanegenate, titanium diisopropoxiside bis (2,4-pentanegeonate)). , Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Titanium Alkoxy Titanium Compounds: For example, Titanium Tetra (n-Butoxide), Titanium Tetraethoxide, Titanium Tetra (2-ethylhexoxyside), 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.
III) Titanosen compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titaniumtris (dioctylphosphate) isopropoxyside, titaniumtris (dodecylbenzenesulfonate) isopropoxyside and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetonate compound: For example, titanium tetraacetylacetoneate and the like.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
 中でも、有機チタン化合物としては、上記I)チタンキレート化合物、II)テトラアルコキシチタン化合物、及びIII)チタノセン化合物から成る群から選ばれる少なくとも1種の化合物であることが、より良好な耐薬品性を奏するという観点から好ましい。特に、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)、チタニウムテトラ(n-ブトキサイド)、及びビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)チタニウムが好ましい。 Among them, as 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) titanosen compound has better chemical resistance. It is preferable from the viewpoint of playing. In particular, titanium diisopropoxyside bis (ethylacetacetate), titanium tetra (n-butoxide), and bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H)). -Pyrrole-1-yl) phenyl) titanium is preferred.
 有機チタン化合物を配合する場合、その配合量は、環化樹脂の前駆体100質量部に対し、0.05~10質量部であることが好ましく、より好ましくは0.1~2質量部である。配合量が0.05質量部以上である場合、得られる硬化パターンに良好な耐熱性及び耐薬品性が発現し、一方10質量部以下である場合、組成物の保存安定性に優れる。 When the organic titanium compound is blended, the blending amount thereof 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. .. When 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.
〔酸化防止剤〕
 本発明の組成物は、酸化防止剤を含んでいてもよい。添加剤として酸化防止剤を含有することで、硬化後の膜の伸度特性や、金属材料との密着性を向上させることができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。前述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-50F、アデカスタブ AO-60、アデカスタブ AO-60G、アデカスタブ AO-80、アデカスタブ AO-330(以上、(株)ADEKA製)などが挙げられる。また、酸化防止剤は、特許第6268967号公報の段落番号0023~0048に記載された化合物を使用することもできる。また、本発明の組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられる。潜在酸化防止剤の市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。好ましい酸化防止剤の例としては、2,2-チオビス(4-メチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチルフェノールおよび一般式(3)で表される化合物が挙げられる。
〔Antioxidant〕
The composition of the present invention may contain 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. Examples of the antioxidant include a phenol compound, a phosphite ester compound, a thioether compound and the like. As 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. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, Tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepine-6] -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available products of 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, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, the composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the 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. This includes compounds in which the protecting group is desorbed and functions as an antioxidant. 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). Examples of preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds represented by the general formula (3).
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
 一般式(3)中、R5は水素原子または炭素数2以上のアルキル基を表し、R6は炭素数2以上のアルキレン基を表す。R7は、炭素数2以上のアルキレン基、O原子、およびN原子のうち少なくともいずれかを含む1~4価の有機基を示す。kは1~4の整数を示す。 In the general formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and 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.
 一般式(3)で表される化合物は、樹脂の脂肪族基やフェノール性水酸基の酸化劣化を抑制する。また、金属材料への防錆作用により、金属酸化を抑制することができる。 The compound represented by the general formula (3) suppresses oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the resin. In addition, metal oxidation can be suppressed by the rust preventive action on the metal material.
 樹脂と金属材料に同時に作用できるため、kは2~4の整数がより好ましい。R7としては、アルキル基、シクロアルキル基、アルコキシ基、アルキルエーテル基、アルキルシリル基、アルコキシシリル基、アリール基、アリールエーテル基、カルボキシル基、カルボニル基、アリル基、ビニル基、複素環基、-O-、-NH-、-NHNH-、それらを組み合わせたものなどが挙げられ、さらに置換基を有していてもよい。この中でも、現像液への溶解性や金属密着性の点から、アルキルエーテル、-NH-を有することが好ましく、樹脂との相互作用と金属錯形成による金属密着性の点から-NH-がより好ましい。 Since it can act on the resin and the metal material at the same time, k is more preferably an integer of 2 to 4. Examples of 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. Among these, it is preferable to have 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 interaction with a resin and metal adhesion due to metal complex formation. preferable.
 下記一般式(3)で表される化合物は、例としては以下のものが挙げられるが、下記構造に限らない。 Examples of the compound represented by the following general formula (3) include the following, but the compound is not limited to the following structure.
Figure JPOXMLDOC01-appb-C000069
 
Figure JPOXMLDOC01-appb-C000069
 
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000072
 酸化防止剤の添加量は、樹脂に対し、0.1~10質量部が好ましく、0.5~5質量部がより好ましい。添加量が0.1質量部より少ない場合は、信頼性後の伸度特性や金属材料に対する密着性向上の効果が得られにくく、また10質量部より多い場合は、感光剤との相互作用により、樹脂組成物の感度低下を招く恐れがある。酸化防止剤は1種のみを用いてもよく、2種以上を用いてもよい。2種以上を用いる場合は、それらの合計量が上記範囲となることが好ましい。 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. When the addition amount is less than 0.1 part by mass, it is difficult to obtain the effect of improving the elongation property after reliability and the adhesion to the metal material, and when the addition amount is more than 10 parts by mass, it is due to the interaction with the photosensitizer. , There is a risk of reducing the sensitivity of the resin composition. Only one kind of antioxidant may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
<その他の含有物質についての制限>
 本発明の硬化性樹脂組成物の水分含有量は、塗布面性状の観点から、5質量%未満が好ましく、1質量%未満がより好ましく、0.6質量%未満が更に好ましい。水分の含有量を維持する方法としては、保管条件における湿度の調整、収容容器の空隙率低減などが挙げられる。
<Restrictions on other contained substances>
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, still 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.
 本発明の硬化性樹脂組成物の金属含有量は、絶縁性の観点から、5質量ppm(parts per million)未満が好ましく、1質量ppm未満がより好ましく、0.5質量ppm未満が更に好ましい。金属としては、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、クロム、ニッケルなどが挙げられる。金属を複数含む場合は、これらの金属の合計が上記範囲であることが好ましい。 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, still more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
 また、本発明の硬化性樹脂組成物に意図せずに含まれる金属不純物を低減する方法としては、本発明の硬化性樹脂組成物を構成する原料として金属含有量が少ない原料を選択する、本発明の硬化性樹脂組成物を構成する原料に対してフィルターろ過を行う、装置内をポリテトラフルオロエチレン等でライニングしてコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。 Further, as a method for reducing metal impurities unintentionally contained in the curable resin composition of the present invention, a raw material having a low metal content is selected as the 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 are mentioned. be able to.
 本発明の硬化性樹脂組成物は、半導体材料としての用途を考慮すると、ハロゲン原子の含有量が、配線腐食性の観点から、500質量ppm未満が好ましく、300質量ppm未満がより好ましく、200質量ppm未満が更に好ましい。中でも、ハロゲンイオンの状態で存在するものは、5質量ppm未満が好ましく、1質量ppm未満がより好ましく、0.5質量ppm未満が更に好ましい。ハロゲン原子としては、塩素原子及び臭素原子が挙げられる。塩素原子及び臭素原子、又は塩素イオン及び臭素イオンの合計がそれぞれ上記範囲であることが好ましい。
 ハロゲン原子の含有量を調節する方法としては、イオン交換処理などが好ましく挙げられる。
Considering the use as a semiconductor material, 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 by mass, 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. Examples of 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.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.
 本発明の硬化性樹脂組成物の収容容器としては従来公知の収容容器を用いることができる。また、収容容器としては、原材料や硬化性樹脂組成物中への不純物混入を抑制することを目的に、容器内壁を6種6層の樹脂で構成された多層ボトルや、6種の樹脂を7層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開2015-123351号公報に記載の容器が挙げられる。 A conventionally known storage container can be used as the storage container for the curable resin composition of the present invention. In addition, as the storage container, for the purpose of suppressing contamination of raw materials and curable resin composition with impurities, a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in JP-A-2015-123351.
<硬化性樹脂組成物の用途>
 本発明の硬化性樹脂組成物は、再配線層用層間絶縁膜の形成に用いられることが好ましい。
 また、その他、半導体デバイスの絶縁膜の形成、又は、ストレスバッファ膜の形成等にも用いることができる。
<Use of curable resin composition>
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.
<硬化性樹脂組成物の調製>
 本発明の硬化性樹脂組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。
<Preparation of curable resin composition>
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.
 また、硬化性樹脂組成物中のゴミや微粒子等の異物を除去する目的で、フィルターを用いたろ過を行うことが好ましい。フィルター孔径は、1μm以下が好ましく、0.5μm以下がより好ましく、0.1μm以下が更に好ましい。一方、生産性の観点では、5μm以下が好ましく、3μm以下がより好ましく、1μm以下が更に好ましい。フィルターの材質は、ポリテトラフルオロエチレン、ポリエチレン又はナイロンが好ましい。フィルターは、有機溶剤であらかじめ洗浄したものを用いてもよい。フィルターろ過工程では、複数種のフィルターを直列又は並列に接続して用いてもよい。複数種のフィルターを使用する場合は、孔径又は材質が異なるフィルターを組み合わせて使用してもよい。また、各種材料を複数回ろ過してもよい。複数回ろ過する場合は、循環ろ過であってもよい。また、加圧してろ過を行ってもよい。加圧してろ過を行う場合、加圧する圧力は0.05MPa以上0.3MPa以下が好ましい。。一方、生産性の観点では、0.01MPa以上1.0MPa以下が好ましく、0.03MPa以上0.9MPa以下がより好ましく、0.05MPa以上0.7MPa以下が更に好ましい。
 フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行ってもよい。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせてもよい。吸着材としては、公知の吸着材を用いることができる。例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材が挙げられる。
Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the curable resin composition. The filter hole diameter is preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, 5 μm or less is preferable, 3 μm or less is more preferable, and 1 μm 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 for use. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. In addition, various materials may be filtered a plurality of times. When filtering multiple times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less. .. On the other hand, from the viewpoint of productivity, 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.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
(樹脂膜、硬化膜、積層体、半導体デバイス、及びそれらの製造方法)
 次に、樹脂膜、硬化膜、積層体、半導体デバイス、及びそれらの製造方法について説明する。
(Resin film, cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, a resin film, a cured film, a laminate, a semiconductor device, and a method for manufacturing them will be described.
 本発明の硬化膜は、本発明の硬化性樹脂組成物、又は、本発明の樹脂膜を硬化してなる。本発明の硬化膜の膜厚は、例えば、0.5μm以上とすることができ、1μm以上とすることができる。また、上限値としては、100μm以下とすることができ、30μm以下とすることもできる。 The cured film of the present invention is obtained by curing the curable resin composition of the present invention or the resin film of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.
 本発明の硬化膜を2層以上、更には、3~7層積層して積層体としてもよい。本発明の積層体は、硬化膜を2層以上含み、上記硬化膜同士のいずれかの間に金属層を含む態様が好ましい。例えば、第一の硬化膜、金属層、第二の硬化膜の3つの層がこの順に積層された層構造を少なくとも含む積層体が好ましいものとして挙げられる。上記第一の硬化膜及び上記第二の硬化膜は、いずれも本発明の硬化膜であり、例えば、上記第一の硬化膜及び上記第二の硬化膜のいずれもが、本発明の硬化性樹脂組成物を硬化してなる膜である態様が好ましいものとして挙げられる。上記第一の硬化膜の形成に用いられる本発明の硬化性樹脂組成物と、上記第二の硬化膜の形成に用いられる本発明の硬化性樹脂組成物とは、組成が同一の組成物であってもよいし、組成が異なる組成物であってもよい。本発明の積層体における金属層は、再配線層などの金属配線として好ましく用いられる。 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. It is preferable that the laminated body of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, 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. An embodiment in which the resin composition is a cured film is preferable. 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. It may be present or it may be a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
 本発明の硬化膜の適用可能な分野としては、半導体デバイスの絶縁膜、再配線層用層間絶縁膜、ストレスバッファ膜などが挙げられる。そのほか、封止フィルム、基板材料(フレキシブルプリント基板のベースフィルムやカバーレイ、層間絶縁膜)、又は上記のような実装用途の絶縁膜をエッチングでパターン形成することなどが挙げられる。これらの用途については、例えば、サイエンス&テクノロジー(株)「ポリイミドの高機能化と応用技術」2008年4月、柿本雅明/監修、CMCテクニカルライブラリー「ポリイミド材料の基礎と開発」2011年11月発行、日本ポリイミド・芳香族系高分子研究会/編「最新ポリイミド 基礎と応用」エヌ・ティー・エス,2010年8月等を参照することができる。 Examples of the applicable field 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. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" November 2011 You can refer to "Latest Polyimide Basics and Applications", NTS, August 2010, etc., published by Japan Polyimide / Aromatic Polymer Research Association / ed.
 また、本発明における硬化膜は、オフセット版面又はスクリーン版面などの版面の製造、成形部品のエッチングへの使用、エレクトロニクス、特に、マイクロエレクトロニクスにおける保護ラッカー及び誘電層の製造などにも用いることもできる。 Further, the cured film in the present invention can also be used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, and manufacturing a protective lacquer and a dielectric layer in electronics, particularly microelectronics.
 本発明の硬化膜の製造方法(以下、単に「本発明の製造方法」ともいう。)は、本発明の硬化性樹脂組成物を基材に適用して膜(樹脂膜)を形成する膜形成工程を含むことが好ましい。
 本発明の硬化膜の製造方法は、上記膜形成工程、並びに、上記膜を露光する露光工程及び上記膜を現像する現像工程を含むことが好ましい。
 また、本発明の硬化膜の製造方法は、上記膜形成工程、及び、必要に応じて上記現像工程を含み、かつ、上記膜を50~450℃で加熱する加熱工程を含むことがより好ましい。
 具体的には、以下の(a)~(d)の工程を含むことも好ましい。
(a)硬化性樹脂組成物を基材に適用して膜(硬化性樹脂組成物層)を形成する膜形成工程
(b)膜形成工程の後、膜を露光する露光工程
(c)露光された上記膜を現像する現像工程
(d)現像された上記膜を50~450℃で加熱する加熱工程
 上記加熱工程において加熱することにより、露光で硬化した樹脂層を更に硬化させることができる。この加熱工程で、例えば上述の熱塩基発生剤が分解し、十分な硬化性が得られる。
The method for producing a cured film of the present invention (hereinafter, also simply referred to as “the method for producing the present invention”) is a film forming in which the curable resin composition of the present invention is applied to a substrate to form a film (resin film). It is preferable to include a step.
The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film.
Further, it is more preferable that the method for producing a cured film of the present invention includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C.
Specifically, it is also preferable to include the following steps (a) to (d).
(A) Film forming step of applying the curable resin composition to a substrate to form a film (curable resin composition layer) (b) After the film forming step, an exposure step of exposing the film (c) is exposed. Development step for developing the developed film (d) Heating step for heating the developed film at 50 to 450 ° C. By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed, and sufficient curability is obtained.
 本発明の好ましい実施形態に係る積層体の製造方法は、本発明の硬化膜の製造方法を含む。本実施形態の積層体の製造方法は、上記の硬化膜の製造方法に従って、硬化膜を形成後、更に、再度、(a)の工程、又は(a)~(c)の工程、又は(a)~(d)の工程を行う。特に、上記各工程を順に、複数回、例えば、2~5回(すなわち、合計で3~6回)行うことが好ましい。このように硬化膜を積層することにより、積層体とすることができる。本発明では特に硬化膜を設けた部分の上又は硬化膜の間、又はその両者に金属層を設けることが好ましい。なお、積層体の製造においては、(a)~(d)の工程をすべて繰り返す必要はなく、上記のとおり、少なくとも(a)、好ましくは(a)~(c)又は(a)~(d)の工程を複数回行うことで硬化膜の積層体を得ることができる。 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. In the method for producing the laminated body of the present embodiment, after forming the cured film according to the above-mentioned method for producing the cured film, the steps (a), the steps (a) to (c), or (a) are further performed. )-(D). In particular, it is preferable to perform each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d). ) Can be performed a plurality of times to obtain a laminated body of the cured film.
<膜形成工程(層形成工程)>
 本発明の好ましい実施形態に係る製造方法は、硬化性樹脂組成物を基材に適用して膜(層状)にする、膜形成工程(層形成工程)を含む。
<Film formation process (layer formation process)>
The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the curable resin composition is applied to a substrate to form a film (layered).
 基材の種類は、用途に応じて適宜定めることができるが、シリコン、窒化シリコン、ポリシリコン、酸化シリコン、アモルファスシリコンなどの半導体作製基材、石英、ガラス、光学フィルム、セラミック材料、蒸着膜、磁性膜、反射膜、Ni、Cu、Cr、Feなどの金属基材、紙、SOG(Spin On Glass)、TFT(薄膜トランジスタ)アレイ基材、プラズマディスプレイパネル(PDP)の電極板など特に制約されない。また、これらの基材には表面に密着層や酸化層などの層が設けられていてもよい。本発明では、特に、半導体作製基材が好ましく、シリコン基材、Cu基材およびモールド基材がより好ましい。
 また、これらの基材にはヘキサメチルジシラザン(HMDS)等による密着層や酸化層などの層が表面に設けられていてもよい。
 また、基材としては、例えば板状の基材(基板)が用いられる。
 基材の形状は特に限定されず、円形状であっても矩形状であってもよいが、矩形状であることが好ましい。
 基材のサイズとしては、円形状であれば、例えば直径が100~450mmであり、好ましくは200~450mmである。矩形状であれば、例えば短辺の長さが100~1000mmであり、好ましくは200~700mmである。
The type of substrate can be appropriately determined depending on the application, but semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin 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.
Further, 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 thereof.
Further, as the 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.
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.
 また、樹脂層の表面や金属層の表面に硬化性樹脂組成物層を形成する場合は、樹脂層や金属層が基材となる。 Further, when the curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes the base material.
 硬化性樹脂組成物を基材に適用する手段としては、塗布が好ましい。 Coating is preferable as a means for applying the curable resin composition to the base material.
 具体的には、適用する手段としては、ディップコート法、エアーナイフコート法、カーテンコート法、ワイヤーバーコート法、グラビアコート法、エクストルージョンコート法、スプレーコート法、スピンコート法、スリットコート法、及びインクジェット法などが例示される。硬化性樹脂組成物層の厚さの均一性の観点から、より好ましくはスピンコート法、スリットコート法、スプレーコート法、インクジェット法である。方法に応じて適切な固形分濃度や塗布条件を調整することで、所望の厚さの樹脂層を得ることができる。また、基材の形状によっても塗布方法を適宜選択でき、ウエハ等の円形基材であればスピンコート法やスプレーコート法、インクジェット法等が好ましく、矩形基材であればスリットコート法やスプレーコート法、インクジェット法等が好ましい。スピンコート法の場合は、例えば、500~2,000rpmの回転数で、10秒~1分程度適用することができる。
 また樹脂組成物の粘度や設定する膜厚によっては、300~3,500rpmの回転数で、10~180秒適用することも好ましい。また膜厚の均一性を得るために、複数の回転数を組み合わせて塗布することもできる。
 また、あらかじめ仮支持体上に上記付与方法によって付与して形成した塗膜を、基材上に転写する方法を適用することもできる。
 転写方法に関しては特開2006-023696号公報の段落0023、0036~0051や、特開2006-047592号公報の段落0096~0108に記載の作製方法を本発明においても好適に用いることができる。
 また、基材の端部において余分な膜の除去を行なう工程を行なってもよい。このような工程の例には、エッジビードリンス(EBR)、エアナイフ、バックリンスなどが挙げられる。
 また樹脂組成物を基材に塗布する前に基材を種々の溶剤を塗布し、基材の濡れ性を向上させた後に樹脂組成物を塗布するプリウェット工程を採用しても良い。
Specifically, 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. And 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. Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
Further, depending on the viscosity of the resin composition and the film thickness to be set, it is also preferable to apply the resin composition at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. Further, in order to obtain uniformity of the film thickness, it is also possible to apply a combination of a plurality of rotation speeds.
Further, it is also possible to apply a method of transferring a coating film previously applied onto a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0090 to 0108 of JP-A-2006-047592 can be suitably used in the present invention.
Further, a step of removing the excess film at the end portion of the base material may be performed. Examples of such a process include edge bead rinse (EBR), air knife, back rinse and the like.
Further, a pre-wet 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.
<乾燥工程>
 本発明の製造方法は、膜形成工程(層形成工程)の後に、溶剤を除去するために乾燥する工程を含んでいてもよい。好ましい乾燥温度は50~150℃で、70℃~130℃がより好ましく、90℃~110℃が更に好ましい。乾燥時間としては、30秒~20分が例示され、1分~10分が好ましく、3分~7分がより好ましい。
<Drying process>
The production method of the present invention may include a step of drying to remove the solvent after the film forming step (layer forming step). 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.
<露光工程>
 本発明の製造方法は、上記膜(硬化性樹脂組成物層)を露光する露光工程を含んでもよい。露光量は、硬化性樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長365nmでの露光エネルギー換算で100~10,000mJ/cm照射することが好ましく、200~8,000mJ/cm照射することがより好ましい。
<Exposure process>
The production method of the present invention may include an exposure step of exposing the film (curable resin composition layer). The exposure amount 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.
 露光波長は、190~1,000nmの範囲で適宜定めることができ、240~550nmが好ましい。 The exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
 露光波長は、光源との関係でいうと、(1)半導体レーザー(波長 830nm、532nm、488nm、405nm etc.)、(2)メタルハライドランプ、(3)高圧水銀灯、g線(波長 436nm)、h線(波長 405nm)、i線(波長 365nm)、ブロード(g,h,i線の3波長)、(4)エキシマレーザー、KrFエキシマレーザー(波長 248nm)、ArFエキシマレーザー(波長 193nm)、F2エキシマレーザー(波長 157nm)、(5)極端紫外線;EUV(波長 13.6nm)、(6)電子線、(7)YAGレーザーの第二高調波532nmで、第三高調波355nm、等が挙げられる。本発明の硬化性樹脂組成物については、特に高圧水銀灯による露光が好ましく、中でも、i線による露光が好ましい。これにより、特に高い露光感度が得られうる。
 また取り扱いと生産性の観点では、高圧水銀灯のブロード(g,h,i線の3波長)光源や半導体レーザー405nmも好適である。
The exposure wavelengths are as follows: (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. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. 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. As a result, particularly high exposure sensitivity can be obtained.
From the viewpoint of handling and productivity, a broad (three wavelengths of g, h, and i lines) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.
<現像工程>
 本発明の製造方法は、露光された膜(硬化性樹脂組成物層)に対して、現像を行う(上記膜を現像する)現像工程を含んでもよい。現像を行うことにより、ネガ型であれば露光されていない部分(非露光部)が、ポジ型であれば露光部が除去される。現像方法は、所望のパターンを形成できれば特に制限は無く、例えばノズルからの現像液の吐出、スプレー噴霧、基材の現像液浸漬などが挙げられ、ノズルからの吐出が好ましく利用される。現像工程には、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、現像液を超音波等で振動させる工程およびそれらを組み合わせた工程などが採用可能である。
<Development process>
The production method of the present invention may include a developing step of developing (developing the above-mentioned film) the exposed film (curable resin composition layer). By performing the development, the unexposed portion (non-exposed portion) is removed in the case of the negative type, and the exposed portion is removed in the case of the positive type. 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 substrate, and the like, and ejection from a nozzle is preferably used. The developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, a process in which the developer is vibrated by ultrasonic waves, and a combination thereof. Processes can be adopted.
 現像は現像液を用いて行う。
 現像液としては、特に限定されず公知の物を使用できるが、有機溶剤を含む現像液、又は、アルカリ水溶液を用いることができる。
Development is performed using a developer.
The developing solution is not particularly limited and a known one can be used, but a developing solution containing an organic solvent or an alkaline aqueous solution can be used.
 本発明では、現像液は、ClogP値が-1~5の有機溶剤を含むことが好ましく、ClogP値が0~3の有機溶剤を含むことがより好ましい。ClogP値は、ChemBioDrawにて構造式を入力して計算値として求めることができる。 In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
 現像液が有機溶剤を含む現像液である場合、有機溶剤は、エステル類として、例えば、酢酸エチル、酢酸-n-ブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ-ブチロラクトン、ε-カプロラクトン、δ-バレロラクトン、アルキルオキシ酢酸アルキル(例:アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル(例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等))、3-アルキルオキシプロピオン酸アルキルエステル類(例:3-アルキルオキシプロピオン酸メチル、3-アルキルオキシプロピオン酸エチル等(例えば、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル等))、2-アルキルオキシプロピオン酸アルキルエステル類(例:2-アルキルオキシプロピオン酸メチル、2-アルキルオキシプロピオン酸エチル、2-アルキルオキシプロピオン酸プロピル等(例えば、2-メトキシプロピオン酸メチル、2-メトキシプロピオン酸エチル、2-メトキシプロピオン酸プロピル、2-エトキシプロピオン酸メチル、2-エトキシプロピオン酸エチル))、2-アルキルオキシ-2-メチルプロピオン酸メチル及び2-アルキルオキシ-2-メチルプロピオン酸エチル(例えば、2-メトキシ-2-メチルプロピオン酸メチル、2-エトキシ-2-メチルプロピオン酸エチル等)、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、2-オキソブタン酸メチル、2-オキソブタン酸エチル等、並びに、エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等、並びに、ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、2-ヘプタノン、3-ヘプタノン、N-メチル-2-ピロリドン等、並びに、環式炭化水素類として、例えば、トルエン、キシレン、アニソール、リモネン等、スルホキシド類としてジメチルスルホキシドが好適に挙げられ、また、それらの有機溶剤の混合物も好適に挙げられる。 When the developing solution is a developing solution containing an organic solvent, the organic solvent may be, for example, as esters such as ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate. , Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (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.) , 3-Methylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, 2-alkyloxypropionate) Methyl, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -Ethyl ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2) -Ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol. Dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol mono As propyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as cyclic hydrocarbons, for example, toluene. , Xylene, anisole, limonene and the like, dimethyl sulfoxide is preferably mentioned as a sulfoxide, and a mixture of these organic solvents is also preferably mentioned.
 現像液が有機溶剤を含む現像液である場合、本発明では、特にシクロペンタノン、γ-ブチロラクトンが好ましく、シクロペンタノンがより好ましい。また現像液が有機溶剤を含む場合、有機溶剤は1種又は、2種以上を混合して使用することもできる。 When the developer is a developer containing an organic solvent, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable in the present invention. When the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more.
 現像液が有機溶剤を含む現像液である場合、現像液は、50質量%以上が有機溶剤であることが好ましく、70質量%以上が有機溶剤であることがより好ましく、90質量%以上が有機溶剤であることが更に好ましい。また、現像液は、100質量%が有機溶剤であってもよい。 When the developer is a developer containing an organic solvent, 50% by mass or more of the developer is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is organic. It is more preferably a solvent. Further, the developer may be 100% by mass of an organic solvent.
 現像液は、他の成分を更に含んでもよい。
 他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。
The developer may further contain other components.
Examples of other components include known surfactants and known defoaming agents.
 現像液がアルカリ水溶液である場合、アルカリ水溶液が含みうる塩基性化合物としては、TMAH(水酸化テトラメチルアンモニウムヒドロキシド)、KOH(水酸化カリウム)、炭酸ナトリウムなどが挙げられ、好ましくはTMAHである。現像液における塩基性化合物の含有量は、例えばTMAHを用いる場合、現像液全質量中0.01~10質量%が好ましく、0.1~5質量%がより好ましく、0.3~3質量%が更に好ましい。 When the developer is an alkaline aqueous solution, examples of the basic compound that the alkaline aqueous solution can contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate and the like, and TMAH is preferable. .. When TMAH is used, for example, 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.
〔現像液の供給方法〕
 現像液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材を現像液に浸漬する方法、基材上にノズルを用いて現像液を供給しパドル現像、または、現像液を連続供給する方法がある。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
 現像液の浸透性、非画像部の除去性、製造上の効率の観点から、現像液をストレートノズルで供給する方法、又はスプレーノズルにて連続供給する方法が好ましく、画像部への現像液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。
 また、現像液をストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去し、スピン乾燥後に再度ストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去する工程を採用してもよく、この工程を複数回繰り返しても良い。
 また現像工程における現像液の供給方法としては、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、基材上で現像液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。
[Method of supplying developer]
The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and a method of immersing the base material in the developer, a method of supplying the developer on the base material using a nozzle and 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 developing solution, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developing solution with a straight nozzle or the method of continuously supplying the developing solution with a spray nozzle is preferable. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable.
Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, or this step may be repeated a plurality of times.
The method of supplying the developer in the developing process includes a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a substantially stationary state on the substrate, and a process in which the developer is superposed on the substrate. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.
 現像時間としては、5秒~10分間が好ましく、10秒~5分がより好ましい。現像時の現像液の温度は、特に定めるものではないが、通常、10~45℃、好ましくは、20~40℃で行うことができる。 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 determined, but it can be usually 10 to 45 ° C, preferably 20 to 40 ° C.
 現像液を用いた処理の後、更に、リンスを行ってもよい。また、パターン上に接する現像液が乾燥しきらないうちにリンス液を供給するなどの方法を採用しても良い。リンスは、現像液とは異なる溶剤で行うことが好ましい。例えば、硬化性樹脂組成物に含まれる溶剤を用いてリンスすることができる。
 現像液が有機溶剤を含む現像液である場合、リンス液としては、PGMEA(プロピレングリコールモノエチルエーテルアセテート)、IPA(イソプロパノール)などが挙げられ、好ましくはPGMEAである。また、アルカリ水溶液を含む現像液による現像に対するリンス液としては、水が好ましい。
 リンス時間は、10秒~10分間が好ましく、20秒~5分間がより好ましく、5秒~1分が更に好ましい。リンス時のリンス液の温度は、特に定めるものではないが、好ましくは、10~45℃、より好ましくは、18℃~30℃で行うことができる。
After the treatment with the developer, further rinsing may be performed. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed using the solvent contained in the curable resin composition.
When the developer is a developer containing an organic solvent, examples of the rinse solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), and the like, preferably PGMEA. Further, water is preferable as the rinsing solution for development with a developing solution containing an alkaline aqueous solution.
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 determined, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
 リンス液が有機溶剤を含む場合の有機溶剤としては、エステル類として、例えば、酢酸エチル、酢酸-n-ブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ-ブチロラクトン、ε-カプロラクトン、δ-バレロラクトン、アルキルオキシ酢酸アルキル(例:アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル(例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等))、3-アルキルオキシプロピオン酸アルキルエステル類(例:3-アルキルオキシプロピオン酸メチル、3-アルキルオキシプロピオン酸エチル等(例えば、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル等))、2-アルキルオキシプロピオン酸アルキルエステル類(例:2-アルキルオキシプロピオン酸メチル、2-アルキルオキシプロピオン酸エチル、2-アルキルオキシプロピオン酸プロピル等(例えば、2-メトキシプロピオン酸メチル、2-メトキシプロピオン酸エチル、2-メトキシプロピオン酸プロピル、2-エトキシプロピオン酸メチル、2-エトキシプロピオン酸エチル))、2-アルキルオキシ-2-メチルプロピオン酸メチル及び2-アルキルオキシ-2-メチルプロピオン酸エチル(例えば、2-メトキシ-2-メチルプロピオン酸メチル、2-エトキシ-2-メチルプロピオン酸エチル等)、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、2-オキソブタン酸メチル、2-オキソブタン酸エチル等、並びに、エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル(PGME)、プロピレングリコールモノメチルエーテルアセテート(PGMEA)、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等、並びに、ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、2-ヘプタノン、3-ヘプタノン、N-メチル-2-ピロリドン等、並びに、芳香族炭化水素類として、例えば、トルエン、キシレン、アニソール、リモネン等、スルホキシド類としてジメチルスルホキシド、並びに、アルコール類として、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、ペンタノール、オクタノール、ジエチレングリコール、プロピレングリコール、メチルイソブチルカルビノール、トリエチレングリコール等、並びに、アミド類として、N-メチルピロリドン、N-エチルピロリドン、ジメチルホルムアミド等が好適に挙げられる。 When the rinsing solution contains an organic solvent, the ethers include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid). Ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), etc. Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, 2) -Ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropion) Ethyl propionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate). Ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran. , Ethyl Glycol Monomethyl Ether, Ethyl Glycol Monoethyl Ether, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Ethyl Glycol Monomethyl Ether (PGME), Ethyl Glycol Monomethyl Ether Acetate (PGMEA), Propylene glycol monoethyl ether acetate, propionate Lopyrene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons. For example, toluene, xylene, anisole, limonene and the like, dimethylsulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene as alcohols. Glycols and the like, and examples of the amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
 リンス液が有機溶剤を含む場合、有機溶剤は1種又は、2種以上を混合して使用することができる。本発明では特にシクロペンタノン、γ-ブチロラクトン、ジメチルスルホキシド、N-メチルピロリドン、シクロヘキサノン、PGMEA、PGMEが好ましく、シクロペンタノン、γ-ブチロラクトン、ジメチルスルホキシド、PGMEA、PGMEがより好ましく、シクロヘキサノン、PGMEAがさらに好ましい。 When the rinsing liquid contains an organic solvent, one type or a mixture of two or more types of organic solvent can be used. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are particularly preferable, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, PGME are more preferable, and cyclohexanone and PGMEA are preferable. More preferred.
 リンス液が有機溶剤を含む場合、リンス液は、50質量%以上が有機溶剤であることが好ましく、70質量%以上が有機溶剤であることがより好ましく、90質量%以上が有機溶剤であることが更に好ましい。また、リンス液は、100質量%が有機溶剤であってもよい。 When 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. Further, the rinse liquid may be 100% by mass of an organic solvent.
 リンス液は、他の成分を更に含んでもよい。
 他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。
The rinse solution may further contain other components.
Examples of other components include known surfactants and known defoaming agents.
〔リンス液の供給方法〕
 リンス液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材をリンス液に浸漬する方法、基材上にリンス液を液盛りにより供給する方法、基材にリンス液をシャワーで供給する方法、基材上にストレートノズル等の手段によりリンス液を連続供給する方法がある。
 リンス液の浸透性、非画像部の除去性、製造上の効率の観点から、リンス液をシャワーノズル、ストレートノズル、スプレーノズルなどで供給する方法があり、スプレーノズルにて連続供給する方法が好ましく、画像部へのリンス液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
 すなわち、リンス工程は、リンス液を上記露光後の膜に対してストレートノズルにより供給、又は、連続供給する工程であることが好ましく、リンス液をスプレーノズルにより供給する工程であることがより好ましい。
 またリンス工程におけるリンス液の供給方法としては、リンス液が連続的に基材に供給され続ける工程、基材上でリンス液が略静止状態で保たれる工程、基材上でリンス液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。
[Supplying method of rinse liquid]
The method of supplying the rinsing liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinsing liquid, the method of supplying the rinsing liquid on the base material by filling, and the method of supplying the rinsing liquid to the base material with a shower. There are a method of supplying the rinse liquid and a method of continuously supplying the rinse liquid onto the base material by means such as a straight nozzle.
From the viewpoint of the permeability of the rinse liquid, the removability of non-image areas, and the efficiency of manufacturing, there is a method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying the rinse liquid 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 film after exposure by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
Further, as a method of supplying the rinse liquid in the rinsing step, 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 a sonic or the like and a process of combining them can be adopted.
<加熱工程>
 本発明の製造方法は、現像された上記膜を50~450℃で加熱する工程(加熱工程)を含むことが好ましい。
 加熱工程は、膜形成工程(層形成工程)、乾燥工程、及び現像工程の後に含まれることが好ましい。加熱工程では、例えば上述の熱塩基発生剤が分解することにより塩基が発生し、特定樹脂である前駆体の環化反応が進行する。また、本発明の硬化性樹脂組成物は特定樹脂である前駆体以外のラジカル重合性化合物を含んでいてもよいが、未反応の特定樹脂である前駆体以外のラジカル重合性化合物の硬化などもこの工程で進行させることができる。加熱工程における層の加熱温度(最高加熱温度)としては、50℃以上であることが好ましく、80℃以上であることがより好ましく、140℃以上であることが更に好ましく、150℃以上であることが一層好ましく、160℃以上であることがより一層好ましく、170℃以上であることが更に一層好ましい。上限としては、500℃以下であることが好ましく、450℃以下であることがより好ましく、350℃以下であることが更に好ましく、250℃以下であることが一層好ましく、220℃以下であることがより一層好ましい。
<Heating process>
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. In the heating step, for example, the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the precursor, which is a specific resin, proceeds. Further, the curable resin composition of the present invention may contain a radically polymerizable compound other than the precursor which is a specific resin, but may also cure a radically polymerizable compound other than the precursor which is an unreacted specific resin. It can be advanced in this step. 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 even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
 加熱は、加熱開始時の温度から最高加熱温度まで1~12℃/分の昇温速度で行うことが好ましく、2~10℃/分がより好ましく、3~10℃/分が更に好ましい。昇温速度を1℃/分以上とすることにより、生産性を確保しつつ、アミンの過剰な揮発を防止することができ、昇温速度を12℃/分以下とすることにより、硬化膜の残存応力を緩和することができる。加えて、急速加熱可能なオーブンの場合、加熱開始時の温度から最高加熱温度まで1~8℃/秒の昇温速度で行うことが好ましく、2~7℃/秒がより好ましく、3~6℃/秒が更に好ましい。 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. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured membrane can be prevented from excessive volatilization. Residual stress can be relaxed. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out 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. ℃ / sec is more preferable.
 加熱開始時の温度は、20℃~150℃が好ましく、20℃~130℃がより好ましく、25℃~120℃が更に好ましい。加熱開始時の温度は、最高加熱温度まで加熱する工程を開始する際の温度のことをいう。例えば、硬化性樹脂組成物を基材の上に適用した後、乾燥させる場合、この乾燥後の膜(層)の温度であり、例えば、硬化性樹脂組成物に含まれる溶剤の沸点よりも、30~200℃低い温度から徐々に昇温させることが好ましい。 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. For example, when the curable resin composition is applied onto a substrate and then dried, 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.
 加熱時間(最高加熱温度での加熱時間)は、10~360分であることが好ましく、20~300分であることがより好ましく、30~240分であることが更に好ましい。 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.
 特に多層の積層体を形成する場合、硬化膜の層間の密着性の観点から、加熱温度は180℃~320℃で加熱することが好ましく、180℃~260℃で加熱することがより好ましい。その理由は定かではないが、この温度とすることで、層間の特定樹脂のエチニル基同士が架橋反応を進行しているためと考えられる。 Particularly when forming a multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between the layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.
 加熱は段階的に行ってもよい。例として、25℃から180℃まで3℃/分で昇温し、180℃にて60分保持し、180℃から200℃まで2℃/分で昇温し、200℃にて120分保持する、といった前処理工程を行ってもよい。前処理工程としての加熱温度は100~200℃が好ましく、110~190℃であることがより好ましく、120~185℃であることが更に好ましい。この前処理工程においては、米国特許第9159547号明細書に記載のように紫外線を照射しながら処理することも好ましい。このような前処理工程により膜の特性を向上させることが可能である。前処理工程は10秒間~2時間程度の短い時間で行うとよく、15秒~30分間がより好ましい。前処理は2段階以上のステップとしてもよく、例えば100~150℃の範囲で前処理工程1を行い、その後に150~200℃の範囲で前処理工程2を行ってもよい。 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 the temperature is kept at 200 ° C. for 120 minutes. , Such as a pretreatment step 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 perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step may be 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, for example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
 更に、加熱後冷却してもよく、この場合の冷却速度としては、1~5℃/分であることが好ましい。 Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
 加熱工程は、窒素、ヘリウム、アルゴンなどの不活性ガスを流す等により、低酸素濃度の雰囲気で行うことが特定樹脂の分解を防ぐ点で好ましい。酸素濃度は、50ppm(体積比)以下が好ましく、20ppm(体積比)以下がより好ましい。
 加熱手段としては、特に限定されないが、例えばホットプレート、赤外炉、電熱式オーブン、熱風式オーブンなどが挙げられる。
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.
<金属層形成工程>
 本発明の製造方法は、現像後の膜(硬化性樹脂組成物層)の表面に金属層を形成する金属層形成工程を含むことが好ましい。
<Metal layer forming process>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (curable resin composition layer).
 金属層としては、特に限定なく、既存の金属種を使用することができ、銅、アルミニウム、ニッケル、バナジウム、チタン、クロム、コバルト、金及びタングステンが例示され、銅、アルミニウム、及び、これらの金属を含む合金がより好ましく、銅が更に好ましい。 As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, and copper, aluminum, and these metals are exemplified. The alloy containing the above is more preferable, and copper is further preferable.
 金属層の形成方法は、特に限定なく、既存の方法を適用することができる。例えば、特開2007-157879号公報、特表2001-521288号公報、特開2004-214501号公報、特開2004-101850号公報に記載された方法を使用することができる。例えば、フォトリソグラフィ、リフトオフ、電解メッキ、無電解メッキ、エッチング、印刷、及びこれらを組み合わせた方法などが考えられる。より具体的には、スパッタリング、フォトリソグラフィ及びエッチングを組み合わせたパターニング方法、フォトリソグラフィと電解メッキを組み合わせたパターニング方法が挙げられる。 The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination method thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electrolytic plating can be mentioned.
 金属層の厚さとしては、最も厚肉部で、0.01~100μmが好ましく、0.1~50μmがより好ましく、1~10μmが更に好ましい。 The thickness of the metal layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, still more preferably 1 to 10 μm in the thickest portion.
<積層工程>
 本発明の製造方法は、更に、積層工程を含むことが好ましい。
<Laminating process>
The production method of the present invention preferably further includes a laminating step.
 積層工程とは、硬化膜(樹脂層)又は金属層の表面に、再度、(a)膜形成工程(層形成工程)、(b)露光工程、(c)現像工程、(d)加熱工程を、この順に行うことを含む一連の工程である。ただし、(a)の膜形成工程のみを繰り返す態様であってもよい。また、(d)加熱工程は積層の最後又は中間に一括して行う態様としてもよい。すなわち、(a)~(c)の工程を所定の回数繰り返し行い、その後に(d)の加熱をすることで、積層された硬化性樹脂組成物層を一括で硬化する態様としてもよい。また、(c)現像工程の後には(e)金属層形成工程を含んでもよく、このときにも都度(d)の加熱を行っても、所定回数積層させた後に一括して(d)の加熱を行ってもよい。積層工程には、更に、上記乾燥工程や加熱工程等を適宜含んでいてもよいことは言うまでもない。 In the laminating step, (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, it may be an embodiment in which 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 layer all at once. Further, the (c) developing step may include (e) a metal layer forming step, and even if the heating is performed each time (d), the (d) is collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step and the like as appropriate.
 積層工程後、更に積層工程を行う場合には、上記加熱工程後、上記露光工程後、又は、上記金属層形成工程後に、更に、表面活性化処理工程を行ってもよい。表面活性化処理としては、プラズマ処理が例示される。 When the laminating step is further performed, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. Plasma treatment is exemplified as the surface activation treatment.
 上記積層工程は、2~20回行うことが好ましく、2~5回行うことがより好ましく、3~5回行うことが更に好ましい。
 また、積層工程における各層は、組成、形状、膜厚等が同一の層であってもよいし、異なる層であってもよい。
The laminating step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even 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.
 例えば、樹脂層/金属層/樹脂層/金属層/樹脂層/金属層のような、樹脂層が3層以上7層以下の構成が好ましく、3層以上5層以下が更に好ましい。 For example, a structure such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferable, and the resin layer is preferably 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less.
 本発明では特に、金属層を設けた後、更に、上記金属層を覆うように、上記硬化性樹脂組成物の硬化膜(樹脂層)を形成する態様が好ましい。具体的には、(a)膜形成工程、(b)露光工程、(c)現像工程、(e)金属層形成工程、(d)加熱工程の順序で繰り返す態様、又は、(a)膜形成工程、(b)露光工程、(c)現像工程、(e)金属層形成工程の順序で繰り返し、最後又は中間に一括して(d)加熱工程を設ける態様が挙げられる。硬化性樹脂組成物層(樹脂層)を積層する積層工程と、金属層形成工程を交互に行うことにより、硬化性樹脂組成物層(樹脂層)と金属層を交互に積層することができる。 In the present invention, it is particularly preferable to form a cured film (resin layer) of the curable resin composition so as to cover the metal layer after the metal layer is provided. Specifically, an embodiment in which (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are repeated in this order, or (a) film forming. Examples thereof include an embodiment in which (b) an exposure step, (c) a development step, and (e) a metal layer forming step are repeated in this order, and (d) a heating step is collectively provided at the end or in the middle. By alternately performing the laminating step of laminating the curable resin composition layer (resin layer) and the metal layer forming step, the curable resin composition layer (resin layer) and the metal layer can be alternately laminated.
(表面活性化処理工程)  
 本発明の積層体の製造方法は、上記金属層および感光性樹脂組成物層の少なくとも一部を表面活性化処理する、表面活性化処理工程を含んでもよい。
 表面活性化処理工程は、通常、金属層形成工程の後に行うが、上記露光現像工程の後、感光性樹脂組成物層に表面活性化処理工程を行ってから、金属層形成工程を行ってもよい。
 表面活性化処理は、金属層の少なくとも一部のみに行ってもよいし、露光後の感光性樹脂組成物層の少なくとも一部のみに行ってもよいし、金属層および露光後の感光性樹脂組成物層の両方について、それぞれ、少なくとも一部に行ってもよい。表面活性化処理は、金属層の少なくとも一部について行うことが好ましく、金属層のうち、表面に感光性樹脂組成物層を形成する領域の一部または全部に表面活性化処理を行うことが好ましい。このように、金属層の表面に表面活性化処理を行うことにより、その表面に設けられる樹脂層との密着性を向上させることができる。
 また、表面活性化処理は、露光後の感光性樹脂組成物層(樹脂層)の一部または全部についても行うことが好ましい。このように、感光性樹脂組成物層の表面に表面活性化処理を行うことにより、表面活性化処理した表面に設けられる金属層や樹脂層との密着性を向上させることができる。
 表面活性化処理としては、具体的には、各種原料ガス(酸素、水素、アルゴン、窒素、窒素/水素混合ガス、アルゴン/酸素混合ガスなど)のプラズマ処理、コロナ放電処理、CF/O、NF/O、SF、NF、NF/Oによるエッチング処理、紫外線(UV)オゾン法による表面処理、塩酸水溶液に浸漬して酸化皮膜を除去した後にアミノ基とチオール基を少なくとも一種有する化合物を含む有機表面処理剤への浸漬処理、ブラシを用いた機械的な粗面化処理から選択され、プラズマ処理が好ましく、特に原料ガスに酸素を用いた酸素プラズマ処理が好ましい。コロナ放電処理の場合、エネルギーは、500~200,000J/mが好ましく、1000~100,000J/mがより好ましく、10,000~50,000J/mが最も好ましい。
(Surface activation treatment process)
The method for producing a laminate 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 activation treatment step is usually performed after the metal layer forming step, but after the exposure development step, the photosensitive resin composition layer may be subjected to the surface activation treatment step and then 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 that forms the photosensitive resin composition layer on the surface. .. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin layer provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure. As described above, by performing the surface activating treatment on the surface of the photosensitive resin composition layer, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activating treatment.
Specific examples of the surface activation treatment include plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, and CF 4 / O 2. Etching treatment with NF 3 / O 2 , SF 6 , NF 3 , NF 3 / O 2 , surface treatment with ultraviolet (UV) ozone method, soaking in a hydrochloric acid aqueous solution to remove the oxide film, and then removing amino and thiol groups. 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 plasma treatment is preferable, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. For corona discharge treatment, 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.
 本発明は、本発明の硬化膜又は積層体を含む半導体デバイスも開示する。本発明の硬化性樹脂組成物を再配線層用層間絶縁膜の形成に用いた半導体デバイスの具体例としては、特開2016-027357号公報の段落0213~0218の記載及び図1の記載を参酌でき、これらの内容は本明細書に組み込まれる。 The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As specific examples of 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 of JP-A-2016-0273557 and the description in FIG. 1 are referred to. Yes, these contents are incorporated herein.
 以下に実施例を挙げて本発明を更に具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。「部」、「%」は特に述べない限り、質量基準である。 The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.
<合成例MP-1:化合物MP-1の合成>
 撹拌機、コンデンサーを取りつけたフラスコ中で、1,2,4-トリアゾール(東京化成工業(株)製)7.25g(105ミリモル)、カレンズMOI(昭和電工(株)製)15.52g(100ミリモル)、ネオスタンU-600(日東化成(株)製)0.01g、をテトラヒドロフラン(東京化成工業(株)製)70mLに溶解し、25℃で1時間撹拌した。次いで、45℃で2時間撹拌した後、600mLの酢酸エチルに溶解し、分液ロートに移した。次いで、これを100mLの水で2回、150mLの飽和食塩水で2回洗浄し、硫酸ナトリウムで乾燥した。これをろ紙でろ過しながら1口フラスコに移し、エバポレーターで溶媒を除去し、MP-1を18g得た。MP-1の構造は、下記式(MP-1)で表される構造であると推定される。
Figure JPOXMLDOC01-appb-C000073
<Synthesis Example MP-1: Synthesis of Compound MP-1>
In a flask equipped with a stirrer and a condenser, 1,2,4-triazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 7.25 g (105 mmol), Karenz MOI (manufactured by Showa Denko Co., Ltd.) 15.52 g (100) Mt. mmol) and 0.01 g of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) were dissolved in 70 mL of tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred at 25 ° C. for 1 hour. Then, after stirring at 45 ° C. for 2 hours, it was dissolved in 600 mL of ethyl acetate and transferred to a separating funnel. It was then washed twice with 100 mL of water and twice with 150 mL of saturated brine and dried over sodium sulfate. This was transferred to a 1-necked flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 18 g of MP-1. The structure of MP-1 is presumed to be the structure represented by the following formula (MP-1).
Figure JPOXMLDOC01-appb-C000073
<合成例MP-2:化合物MP-2の合成>
 撹拌機、コンデンサーを取りつけたフラスコ中で、トリアゾール15.2g(0.22モル)を塩化メチレン150mLと混合し、10℃以下になるまで冷却した。続いて、メタクリル酸クロリド10.5g(0.1モル)を1時間かけて滴下し、20~25℃に昇温した。20~25℃で3時間撹拌した後、塩化メチレンを200mL加え、発生した塩をろ紙でろ過し、ろ液を回収した。ろ液を分液ロートに移し、水50mLで2回、150mLの飽和食塩水で2回洗浄し、硫酸ナトリウムで乾燥した。これをろ紙でろ過しながら1口フラスコに移し、エバポレーターで溶媒を除去し、MP-2を20g得た。MP-2の構造は、下記式(MP-2)で表される構造であると推定される。
Figure JPOXMLDOC01-appb-C000074
<Synthesis Example MP-2: Synthesis of Compound MP-2>
In a flask equipped with a stirrer and a condenser, 15.2 g (0.22 mol) of triazole was mixed with 150 mL of methylene chloride and cooled to 10 ° C. or lower. Subsequently, 10.5 g (0.1 mol) of methacrylic acid chloride was added dropwise over 1 hour, and the temperature was raised to 20 to 25 ° C. After stirring at 20 to 25 ° C. for 3 hours, 200 mL of methylene chloride was added, and the generated salt was filtered through a filter paper to recover the filtrate. The filtrate was transferred to a separating funnel, washed twice with 50 mL of water and twice with 150 mL of saturated brine, and dried over sodium sulfate. This was transferred to a 1-necked flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 20 g of MP-2. The structure of MP-2 is presumed to be the structure represented by the following formula (MP-2).
Figure JPOXMLDOC01-appb-C000074
<合成例MC-1:化合物MC-1の合成>
 撹拌機、コンデンサーを取りつけたフラスコ中で、無水コハク酸(東京化成工業(株)製)10.5g(0.105モル)をテトラヒドロフラン200mLと混合し、10℃以下になるまで冷却した。続いて、メタクリル酸2-ヒドロキシエチル(東京化成工業(株)製)13.g(0.1モル)を1時間かけて滴下し、20~25℃に昇温した。20~25℃で3時間撹拌した後、塩化メチレンを500mL加え、分液ロートに移し、水100mLで2回、150mLの飽和食塩水で2回洗浄し、硫酸ナトリウムで乾燥した。これをろ紙でろ過しながら1口フラスコに移し、エバポレーターで溶媒を除去し、MC-1を18g得た。MC-1の構造は、下記式(MC-1)で表される構造であると推定される。
Figure JPOXMLDOC01-appb-C000075
<Synthesis Example MC-1: Synthesis of Compound MC-1>
In a flask equipped with a stirrer and a condenser, 10.5 g (0.105 mol) of succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with 200 mL of tetrahydrofuran and cooled to 10 ° C. or lower. Subsequently, 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 13. g (0.1 mol) was added dropwise over 1 hour, and the temperature was raised to 20 to 25 ° C. After stirring at 20 to 25 ° C. for 3 hours, 500 mL of methylene chloride was added, the mixture was transferred to a separating funnel, washed twice with 100 mL of water and twice with 150 mL of saturated brine, and dried over sodium sulfate. This was transferred to a 1-necked flask while being filtered through a filter paper, and the solvent was removed by an evaporator to obtain 18 g of MC-1. The structure of MC-1 is presumed to be the structure represented by the following formula (MC-1).
Figure JPOXMLDOC01-appb-C000075
<合成例PC-1:化合物PC-1の合成>
 フラスコ(フラスコ1)に、プロピレングリコールモノメチルエーテルを20g添加し、窒素を流しながら、80℃に昇温し、攪拌した。
 次いで、別のフラスコ(フラスコ2)に、メタクリル酸3-(トリエトキシシリル)プロピル(東京化成工業(株)製)23.2g(80ミリモル)、メタクリル酸(東京化成工業(株)製)1.72g(20ミリモル)、重合開始剤V-601(富士フイルム和光(株)製)0.46gを添加し、プロピレングリコールモノメチルエーテル 38.1gに溶解させ、3時間かけて、フラスコ1に滴下した。次いで、85℃に昇温し、3時間攪拌した後、室温まで冷却し、PC-1溶液を得た。PC-1の構造は、下記式(PC-1)で表される構造であると推測される。下記式中、括弧の添字は各繰り返し単位の含有比(モル比)を表す。
 重量平均分子量(Mw)を測定したところ、23,100であった。
Figure JPOXMLDOC01-appb-C000076
<Synthesis example PC-1: Synthesis of compound PC-1>
20 g of propylene glycol monomethyl ether was added to the flask (flask 1), the temperature was raised to 80 ° C. while flowing nitrogen, and the mixture was stirred.
Next, in another flask (flask 2), 23.2 g (80 mmol) of 3- (triethoxysilyl) propyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1 .72 g (20 mmol) and 0.46 g of the polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were added, dissolved in 38.1 g of propylene glycol monomethyl ether, and added dropwise to flask 1 over 3 hours. .. Then, the temperature was raised to 85 ° C., the mixture was stirred for 3 hours, and then cooled to room temperature to obtain a PC-1 solution. The structure of PC-1 is presumed to be the structure represented by the following formula (PC-1). In the following formula, the parenthesized subscripts represent the content ratio (molar ratio) of each repeating unit.
The weight average molecular weight (Mw) was measured and found to be 23,100.
Figure JPOXMLDOC01-appb-C000076
<合成例PC-2~PC-5:化合物PC-2~PC-5の合成>
 合成例PC-1と同様の方法により、化合物PC-2~PC-5を合成した。
 PC-2~PC-5の推定される構造を、それぞれ、下記式(PC-2)~式(PC-5)に示す。下記式中、括弧の添字は各繰り返し単位の含有比(モル比)を表す。
 PC-2の重量平均分子量(Mw)は17,500、PC-3のMwは8,900、PC-4のMwは12,000、PC-5のMwは33,800であった。
Figure JPOXMLDOC01-appb-C000077
<Synthesis Example PC-2 to PC-5: Synthesis of Compounds PC-2 to PC-5>
Synthesis Example Compounds PC-2 to PC-5 were synthesized by the same method as PC-1.
The estimated structures of PC-2 to PC-5 are shown in the following equations (PC-2) to (PC-5), respectively. In the following formula, the parenthesized subscripts represent the content ratio (molar ratio) of each repeating unit.
The weight average molecular weight (Mw) of PC-2 was 17,500, the Mw of PC-3 was 8,900, the Mw of PC-4 was 12,000, and the Mw of PC-5 was 33,800.
Figure JPOXMLDOC01-appb-C000077
<合成例PB-1:化合物PB-1の合成>
 フラスコ(フラスコ1)に、プロピレングリコールモノメチルエーテルを7.5g添加し、窒素を流しながら、80℃に昇温し、撹拌した。
 次いで、別のフラスコ(フラスコ2)に、2-イソプロピル-2-オキサゾリン(アルドリッチ(株)製)7.78g(70ミリモル)、MP-2(上記合成品) 2.74g(20ミリモル)、メタクリル酸アリル(東京化成工業(株)製)1.26g(10ミリモル)、重合開始剤V-601(富士フイルム和光(株)製)0.55gを添加し、プロピレングリコールモノメチルエーテル20gに溶解させ、3時間かけて、フラスコ1に滴下した。次いで、85℃に昇温し、3時間撹拌した後、室温まで冷却し、PB-1溶液を得た。
 PB-1の構造は、下記式(PB-1)で表される構造であると推定される。下記式中、括弧の添字は各繰り返し単位の含有比(モル比)を表す。
 重量平均分子量(Mw)を測定したところ、1,6900であった。
Figure JPOXMLDOC01-appb-C000078
<Synthesis Example PB-1: Synthesis of Compound PB-1>
7.5 g of propylene glycol monomethyl ether was added to the flask (flask 1), the temperature was raised to 80 ° C. while flowing nitrogen, and the mixture was stirred.
Then, in another flask (flask 2), 2-isopropyl-2-oxazoline (manufactured by Aldrich Co., Ltd.) 7.78 g (70 mmol), MP-2 (the above synthetic product) 2.74 g (20 mmol), methacryl. 1.26 g (10 mmol) of allyl acid acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.55 g of the polymerization initiator V-601 (manufactured by Fujifilm Wako Co., Ltd.) were added and dissolved in 20 g of propylene glycol monomethyl ether. It was added dropwise to flask 1 over 3 hours. Then, the temperature was raised to 85 ° C., the mixture was stirred for 3 hours, and then cooled to room temperature to obtain a PB-1 solution.
The structure of PB-1 is presumed to be the structure represented by the following formula (PB-1). In the following formula, the parenthesized subscripts represent the content ratio (molar ratio) of each repeating unit.
The weight average molecular weight (Mw) was measured and found to be 1,6900.
Figure JPOXMLDOC01-appb-C000078
<合成例PB-2~PB-3、PB-5~PB-6:化合物PB-2~PB-3、PB-5~PB-6の合成>
 合成例PB-1と同様の方法により、化合物PB-2~PB-3、PB-5~PB-6を合成した。
 PB-2のMwは9,800、PB-3のMwは12,500、PB-5のMwは25,800、PB-6のMwは18,700であった。
Figure JPOXMLDOC01-appb-C000079
<Synthesis Examples PB-2 to PB-3, PB-5 to PB-6: Synthesis of Compounds PB-2 to PB-3 and PB-5 to PB-6>
Synthesis Example Compounds PB-2 to PB-3 and PB-5 to PB-6 were synthesized by the same method as PB-1.
The Mw of PB-2 was 9,800, the Mw of PB-3 was 12,500, the Mw of PB-5 was 25,800, and the Mw of PB-6 was 18,700.
Figure JPOXMLDOC01-appb-C000079
<合成例C-1:化合物C-1の合成>
 フラスコに、無水マレイン酸(東京化成工業(株)製)9.81g(100ミリモル)をテトラヒドロフラン80gに溶解し、0℃~10℃に冷却した。
 次いで、3-アミノプロピルトリエトキシシラン(東京化成工業(株)製))22.1g(100ミリモル)を1時間かけて、上記フラスコに滴下した。次いで、25℃に昇温し、3時間攪拌した。上記溶液を一口フラスコに移し、エバポレーターで溶媒を除去し、化合物C-1を30g得た。
<Synthesis Example C-1: Synthesis of Compound C-1>
In a flask, 9.81 g (100 mmol) of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80 g of tetrahydrofuran and cooled to 0 ° C to 10 ° C.
Then, 22.1 g (100 mmol) of 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 1 hour. Then, the temperature was raised to 25 ° C., and the mixture was stirred for 3 hours. The above solution was transferred to a bite-sized flask, and the solvent was removed by an evaporator to obtain 30 g of compound C-1.
<合成例C-2~C-3:化合物C-2~C-3の合成>
 化合物C-1と同様の方法で、化合物C-2、化合物C-3を合成した。
 なお、化合物C-2は、無水マレイン酸の代わりに、無水フタル酸を使用した。
 化合物C-3は、無水マレイン酸の代わりに、無水コハク酸を使用した。
<Synthesis Examples C-2 to C-3: Synthesis of Compounds C-2 to C-3>
Compound C-2 and compound C-3 were synthesized in the same manner as in compound C-1.
As compound C-2, phthalic anhydride was used instead of maleic anhydride.
For compound C-3, succinic anhydride was used instead of maleic anhydride.
<合成例C-4:化合物C-4の合成>
 フラスコに、p-アミノ安息香酸(東京化成工業(株)製)13.7g(100ミリモル)をテトラヒドロフラン140gに溶解し、0℃~10℃に冷却した。
 次いで、イソシアン酸3-(トリエトキシシリル)プロピル(東京化成工業(株)製))24.7g(100ミリモル)を1時間かけて、上記フラスコに滴下した。次いで、25℃に昇温し、3時間攪拌した。上記溶液を一口フラスコに移し、エバポレーターで溶媒を除去し、化合物C-4を37g得た。
<Synthesis Example C-4: Synthesis of Compound C-4>
In a flask, 13.7 g (100 mmol) of p-aminobenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 140 g of tetrahydrofuran and cooled to 0 ° C to 10 ° C.
Then, 24.7 g (100 mmol) of 3- (triethoxysilyl) propyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 1 hour. Then, the temperature was raised to 25 ° C., and the mixture was stirred for 3 hours. The above solution was transferred to a bite-sized flask, and the solvent was removed by an evaporator to obtain 37 g of compound C-4.
<合成例C-5:化合物C-5の合成>
 フラスコに、4-ヒドロキシメチル安息香酸(東京化成工業(株)製)15.2g(100ミリモル)、ネオスタンU-600(日東化成(株)製)0.1gをテトラヒドロフラン150gに溶解した。
 次いで、イソシアン酸3-(トリエトキシシリル)プロピル(東京化成工業(株)製))24.7g(100ミリモル)を1時間かけて、上記フラスコに滴下した。次いで、40℃に昇温し、5時間攪拌した。上記溶液を分液ロートに移し、酢酸エチル800mLで希釈した。これを水100mL、飽和食塩水100mLで洗浄した後、硫酸マグネシウムで乾燥し、ろ紙でろ過しながら一口フラスコに移した。エバポレーターで溶媒を除去し、化合物C-5を30g得た。
<Synthesis Example C-5: Synthesis of Compound C-5>
In a flask, 15.2 g (100 mmol) of 4-hydroxymethylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.1 g of Neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) were dissolved in 150 g of tetrahydrofuran.
Then, 24.7 g (100 mmol) of 3- (triethoxysilyl) propyl isocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 1 hour. Then, the temperature was raised to 40 ° C., and the mixture was stirred for 5 hours. The above solution was transferred to a separating funnel and diluted with 800 mL of ethyl acetate. This was washed with 100 mL of water and 100 mL of saturated brine, dried over magnesium sulfate, and transferred to a bite-sized flask while being filtered through a filter paper. The solvent was removed by an evaporator to obtain 30 g of compound C-5.
<合成例C-6:化合物C-6の合成>
 フラスコにN-メチル-2-ピロリドン(NMP)を46.0g、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物(東京化成工業(株)製)4.84g(15mmol)、3-アミノプロピルトリエトキシシラン(東京化成工業(株)製)6.64g(30mmol)を入れ、25℃で、5時間撹拌し、C-6のNMP20質量%溶液を得た。
<Synthesis Example C-6: Synthesis of Compound C-6>
46.0 g of N-methyl-2-pyrrolidone (NMP), 3,3', 4,4'-benzophenone tetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.84 g (15 mmol), in a flask. 6.64 g (30 mmol) of 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25 ° C. for 5 hours to obtain a 20% by mass NMP solution of C-6.
<合成例A-1:2,2’-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン、4,4’-オキシジベンゾイルクロリドからのポリベンゾオキサゾール前駆体A-1の合成>
 2,2’-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン28.0g(76.4ミリモル)をN-メチルピロリドン200gに撹拌溶解した。続いて、ピリジン12.1g(153ミリモル)を加え、温度を-10~0℃に保ちながら、N-メチルピロリドン75gに4,4’-オキシジベンゾイルクロリド20.7g(70.1ミリモル)を溶解させた溶液を1時間かけて滴下した。30分間撹拌した後、塩化アセチル1.00g(12.7ミリモル)を加え、さらに60分間撹拌した。次いで、6リットルの水の中でポリベンゾオキサゾール前駆体樹脂を沈殿させ、水-ポリベンゾオキサゾール前駆体樹脂混合物を500rpmの速度で15分間撹拌した。ポリベンゾオキサゾール前駆体樹脂を濾過して除き、6リットルの水の中で再度30分間撹拌し再び濾過した。次いで、得られたポリベンゾオキサゾール前駆体樹脂を減圧下で、45℃で3日間乾燥し、ポリベンゾオキサゾール前駆体A-1を得た。このポリベンゾオキサゾール前駆体A-1は、Mw=21500、Mn=9500であった。A-1におけるカルボキシ基の含有量は、0.002mmol/gであった。
 ポリベンゾオキサゾール前駆体A-1の構造は、下記式(A-1)で表される構造であると推測される。
Figure JPOXMLDOC01-appb-C000080
<Synthesis Example A-1: Synthesis of polybenzoxazole precursor A-1 from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxydibenzoyl chloride>
28.0 g (76.4 mmol) of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 200 g of N-methylpyrrolidone by stirring. Subsequently, 12.1 g (153 mmol) of pyridine was added, and 20.7 g (70.1 mmol) of 4,4'-oxydibenzoyl chloride was added to 75 g of N-methylpyrrolidone while keeping the temperature at -10 to 0 ° C. The dissolved solution was added dropwise over 1 hour. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was further stirred for 60 minutes. The polybenzoxazole precursor resin was then precipitated in 6 liters of water and the water-polybenzoxazole precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes. The polybenzoxazole precursor resin was filtered off, stirred again in 6 liters of water for 30 minutes and filtered again. Then, the obtained polybenzoxazole precursor resin was dried under reduced pressure at 45 ° C. for 3 days to obtain a polybenzoxazole precursor A-1. This polybenzoxazole precursor A-1 had Mw = 21500 and Mn = 9500. The content of the carboxy group in A-1 was 0.002 mmol / g.
The structure of the polybenzoxazole precursor A-1 is presumed to be the structure represented by the following formula (A-1).
Figure JPOXMLDOC01-appb-C000080
<合成例A-2:ピロメリット酸二無水物、4,4’-ジアミノジフェニルエーテル及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-2:ラジカル重合性基を有するポリイミド前駆体)の合成>
 14.06g(64.5ミリモル)のピロメリット酸二無水物(140℃で12時間乾燥したもの)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、100gのダイグライム(ジエチレングリコールジメチルエーテル)を混合し、60℃の温度で18時間撹拌して、ピロメリット酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOClにより塩素化した後、合成例A-5と同様の方法で4,4’-ジアミノジフェニルエーテルでポリイミド前駆体に変換し、合成例A-5と同様の方法でポリイミド前駆体A―2を得た。このポリイミド前駆体A―2の重量平均分子量は、21,000であった。A-2におけるカルボキシ基の含有量は、0.35mmol/gであった。
 ポリイミド前駆体A-2の構造は、下記式(A-2)で表される構造であると推測される。
Figure JPOXMLDOC01-appb-C000081
<Synthesis Example A-2: Synthesis of polyimide precursor (A-2: polyimide precursor having radical polymerizable group) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate>
14.06 g (64.5 mmol) of pyromellitic acid dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone. 20.4 g (258 mmol) of pyridine and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCL 2 and then converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, and in the same manner as in Synthesis Example A-5. Polyimide precursor A-2 was obtained. The weight average molecular weight of this polyimide precursor A-2 was 21,000. The content of the carboxy group in A-2 was 0.35 mmol / g.
The structure of the polyimide precursor A-2 is presumed to be the structure represented by the following formula (A-2).
Figure JPOXMLDOC01-appb-C000081
<合成例A-3:4,4’-オキシジフタル酸二無水物、4,4’-ジアミノジフェニルエーテル及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-3:ラジカル重合性基を有するポリイミド前駆体)の合成>
 20.0g(64.5ミリモル)の4,4’-オキシジフタル酸二無水物(140℃で12時間乾燥したもの)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、100gのダイグライムとを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOClにより塩素化した後、合成例A-5と同様の方法で4,4’-ジアミノジフェニルエーテルでポリイミド前駆体に変換し、合成例A-5と同様の方法でポリイミド前駆体A-3を得た。このポリイミド前駆体A-3の重量平均分子量は、19,600であった。A-3におけるカルボキシ基の含有量は、0.25mmol/gであった。
 ポリイミド前駆体A-3の構造は、下記式(A-3)で表される構造であると推測される。
Figure JPOXMLDOC01-appb-C000082
<Synthesis Example A-3: Polyimide precursor from 4,4'-oxydiphthalic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (A-3: Polyimide precursor having a radically polymerizable group) ) Synthesis>
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic acid dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g. Hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to give a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethylmethacrylate. Manufactured. Next, the obtained diester was chlorinated with SOCL 2 and then converted into a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-5, and in the same manner as in Synthesis Example A-5. Polyimide precursor A-3 was obtained. The weight average molecular weight of this polyimide precursor A-3 was 19,600. The content of the carboxy group in A-3 was 0.25 mmol / g.
The structure of the polyimide precursor A-3 is presumed to be the structure represented by the following formula (A-3).
Figure JPOXMLDOC01-appb-C000082
<合成例A-4:4,4’-オキシジフタル酸二無水物、4,4’-ジアミノ-2,2’-ジメチルビフェニル(オルトトリジン)及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-4:ラジカル重合性基を有するポリイミド前駆体)の合成>
 20.0g(64.5ミリモル)の4,4’-オキシジフタル酸二無水物(140℃で12時間乾燥したもの)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、100gのダイグライムとを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOClにより塩素化した後、合成例A-5と同様の方法で4,4’-ジアミノ-2,2’-ジメチルビフェニルでポリイミド前駆体に変換し、合成例A-5と同様の方法でポリイミド前駆体A-4を得た。このポリイミド前駆体A-4の重量平均分子量は、23,500であった。A-4におけるカルボキシ基の含有量は、0.21mmol/gであった。
 ポリイミド前駆体A-4の構造は、下記式(A-4)で表される構造であると推測される。
Figure JPOXMLDOC01-appb-C000083
<Synthesis Example A-4: Polyimide precursor from 4,4'-oxydiphthalic acid dianhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotridin) and 2-hydroxyethylmethacrylate (A-4) : Synthesis of polyimide precursor with radically polymerizable group)>
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic acid dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g. Hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to give a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethylmethacrylate. Manufactured. Next, the obtained diester was chlorinated with SOCL 2 , and then converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example A-5, and synthesized Example A. Polyimide precursor A-4 was obtained in the same manner as in −5. The weight average molecular weight of this polyimide precursor A-4 was 23,500. The content of the carboxy group in A-4 was 0.21 mmol / g.
The structure of the polyimide precursor A-4 is presumed to be the structure represented by the following formula (A-4).
Figure JPOXMLDOC01-appb-C000083
<合成例A-5:オキシジフタル酸二無水物、4,4’-ビフタル酸無水物、2-ヒドロキシエチルメタクリレート及び4,4’-ジアミノジフェニルエーテルからのポリイミド前駆体樹脂A-5の合成>
 撹拌機、コンデンサー及び内部温度計を取りつけた平底ジョイントを備えた乾燥反応器中で水分を除去しながら、4,4’-ビフタル酸無水物 9.49g(32.25ミリモル)、オキシジフタル酸二無水物 10.0g(32.25ミリモル)をジグリム 140mL中に懸濁させた。2-ヒドロキシエチルメタクリレート 16.8g(129ミリモル)、ヒドロキノン 0.05g、純水 0.05g及びピリジン 10.7g(135ミリモル)を続いて添加し、60℃の温度で18時間撹拌した。次いで、混合物を-20℃まで冷却した後、塩化チオニル 16.1g(135.5ミリモル)を90分かけて滴下した。ピリジニウムヒドロクロリドの白色沈澱が得られた。次いで、混合物を室温まで温め、2時間撹拌した後、ピリジン 9.7g(123ミリモル)及びN-メチルピロリドン(NMP) 25mLを添加し、透明溶液を得た。次いで、得られた透明溶液に、4,4’-ジアミノジフェニルエーテル 11.8g(58.7ミリモル)をNMP 100mL中に溶解させたものを、1時間かけて滴下により添加した。次いで、メタノール 5.6g(17.5ミリモル)と3,5-ジ-tert-ブチル-4-ヒドロキシトルエン 0.05gを加え、混合物を2時間撹拌した。次いで、4リットルの水の中でポリイミド前駆体樹脂を沈殿させ、水-ポリイミド前駆体樹脂混合物を500rpmの速度で15分間撹拌した。ポリイミド前駆体樹脂を濾過して取得し、4リットルの水の中で再度30分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体樹脂を減圧下、45℃で3日間乾燥し、ポリイミド前駆体A-5を得た。得られたポリイミド前駆体A-5の重量平均分子量は23,800、数平均分子量は10,400であった。A-5におけるカルボキシ基の含有量は、0.19mmol/gであった。
 ポリイミド前駆体A-5の構造は、下記式(A-5)で表される構造であると推測される。
Figure JPOXMLDOC01-appb-C000084
<Synthesis Example A-5: Synthesis of polyimide precursor resin A-5 from oxydiphthalic acid dianhydride, 4,4'-biphthalic acid anhydride, 2-hydroxyethyl methacrylate and 4,4'-diaminodiphenyl ether>
9.49 g (32.25 mmol) of 4,4'-biphthalic acid anhydride, oxydiphthalic acid dianhydride while removing water in a drying reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. 10.0 g (32.25 mmol) of the product was suspended in 140 mL of diglyme. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water and 10.7 g (135 mmol) of pyridine were subsequently added and stirred at a temperature of 60 ° C. for 18 hours. The mixture was then cooled to −20 ° C. and then 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature and stirred for 2 hours before adding 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) to give a clear solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added to the obtained transparent solution by dropping over 1 hour. Then 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 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 4 liters of water for 30 minutes, and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 3 days to obtain a polyimide precursor A-5. The obtained polyimide precursor A-5 had a weight average molecular weight of 23,800 and a number average molecular weight of 10,400. The content of the carboxy group in A-5 was 0.19 mmol / g.
The structure of the polyimide precursor A-5 is presumed to be the structure represented by the following formula (A-5).
Figure JPOXMLDOC01-appb-C000084
<合成例A-6:4,4’-オキシジフタル二酸無水物、4,4’-ジアミノジフェニルエーテル、及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体A-6の合成>
 4,4’-オキシジフタル酸二無水物(ODPA)155.1gをセパラブルフラスコに入れ、2-ヒドロキシエチルメタクリレート(HEMA)134.0g及びγ-ブチロラクトン400mlを加えた。室温下で撹拌しながら、ピリジン79.1gを加えることにより、反応混合物を得た。反応による発熱の終了後、室温まで放冷し、更に16時間静置した。
 次に、氷冷下において、反応混合物に、ジシクロヘキシルカルボジイミド(DCC)206.3gをγ-ブチロラクトン180mlに溶解した溶液を、撹拌しながら40分かけて加えた。続いて、4,4’-ジアミノジフェニルエーテル93.0gをγ-ブチロラクトン350mlに懸濁した懸濁液を、撹拌しながら60分かけて加えた。更に室温で2時間撹拌した後、エチルアルコール30mlを加えて1時間撹拌した。その後、γ-ブチロラクトン400mlを加えた。反応混合物に生じた沈殿物を、ろ過により取り除き、反応液を得た。
 得られた反応液を3リットルのエチルアルコールに加えて、粗ポリマーからなる沈殿物を生成した。生成した粗ポリマーを濾取し、テトラヒドロフラン1.5リットルに溶解して粗ポリマー溶液を得た。得られた粗ポリマー溶液を28リットルの水に滴下してポリマーを沈殿させ、得られた沈殿物を濾取した後に真空乾燥することにより、粉末状のポリイミド前駆体A-6を得た。このポリイミド前駆体A-6の重量平均分子量(Mw)を測定したところ、24,000であった。A-6におけるカルボキシ基の含有量は、0.11mmol/gであった。
<Synthesis Example A-6: Synthesis of Polyimide Precursor A-6 from 4,4'-oxydiphthaldiate anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate>
155.1 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine while stirring at room temperature. After the exotherm by the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.
Next, under ice-cooling, a solution prepared by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour. Then, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate consisting of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polyimide precursor A-6. The weight average molecular weight (Mw) of this polyimide precursor A-6 was measured and found to be 24,000. The content of the carboxy group in A-6 was 0.11 mmol / g.
<合成例A-7:3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、4,4’-ジアミノジフェニルエーテル、及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体A-7の合成>
 合成例6において、4,4’-オキシジフタル酸二無水物155.1gに代えて、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物147.1gを用いた以外は、合成例6に記載の方法と同様にして反応を行うことにより、ポリマーA-7を得た。このポリマーA-7の重量平均分子量(Mw)を測定したところ、22,900であった。A-7におけるカルボキシ基の含有量は、0.15mmol/gであった。
<Synthesis Example A-7: Synthesis of polyimide precursor A-7 from 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate>
Synthesis Example 6 except that 147.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride. Polymer A-7 was obtained by carrying out the reaction in the same manner as described in 6. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 22,900. The content of the carboxy group in A-7 was 0.15 mmol / g.
<合成例PBI-1:ポリイミドPBI-1の合成>
 コンデンサー及び撹拌機を取り付けたフラスコ中で、水分を除去しながら、4,4’-(ヘキサフルオロイソプロピリデン)ジフタル酸無水物(東京化成工業(株)製)22.2g(50ミリモル)、2,2,6,6-テトラメチルピペリジン1-オキシル フリーラジカル(東京化成品工業(株)製)0.02gをN-メチルピロリドン(NMP)100.0gに溶解した。次いで、後述するジアミン(AA-1)11.9g(45ミリモル)を添加し、25℃で3時間撹拌し、45℃で更に3時間撹拌した。次いで、ピリジン15.8g(200ミリモル)、無水酢酸12.8g(125ミリモル)、N-メチルピロリドン(NMP)50gを添加し、80℃で、3時間撹拌し、N-メチルピロリドン(NMP)50gを加え、希釈した。
 この反応液を、1リットルのメタノールの中で沈殿させ、3000rpmの速度で15分間撹拌した。樹脂を濾過して除き、1リットルのメタノールの中で再度30分間撹拌し再び濾過した。得られた樹脂を減圧下で、40℃で1日乾燥し、ポリイミドPBI-1を得た。PBI-1の分子量は、Mw=19,000、Mn=8,100であった。
 ポリイミドPBI-1の構造は下記式(PBI-1)により表される構造であると推測される。PBI-1におけるカルボキシ基の含有量は、0.21mmol/gであった。
Figure JPOXMLDOC01-appb-C000085
<Synthesis Example PBI-1: Synthesis of Polyimide PBI-1>
In a flask equipped with a condenser and a stirrer, while removing water, 4,4'-(hexafluoroisopropyridene) diphthalic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 22.2 g (50 mmol), 2 , 2,6,6-Tetramethylpiperidin 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.02 g was dissolved in 100.0 g of N-methylpyrrolidone (NMP). Then, 11.9 g (45 mmol) of diamine (AA-1) described later was added, and the mixture was stirred at 25 ° C. for 3 hours and further at 45 ° C. for 3 hours. Then, 15.8 g (200 mmol) of pyridine, 12.8 g (125 mmol) of acetic anhydride, and 50 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80 ° C. for 3 hours, and 50 g of N-methylpyrrolidone (NMP) was added. Was added and diluted.
The reaction was precipitated in 1 liter of methanol and stirred at a rate of 3000 rpm for 15 minutes. The resin was filtered off, 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 to obtain polyimide PBI-1. The molecular weight of PBI-1 was Mw = 19,000 and Mn = 8,100.
It is presumed that the structure of polyimide PBI-1 is a structure represented by the following formula (PBI-1). The content of the carboxy group in PBI-1 was 0.21 mmol / g.
Figure JPOXMLDOC01-appb-C000085
<合成例AA-1:ジアミンAA-1の合成>
 コンデンサー及び撹拌機を取り付けたフラスコ中で、メタクリル酸2-ヒドロキシエチル(富士フイルム和光純薬(株)製)26.0g(0.2モル)、脱水ピリジン(富士フイルム和光純薬(株)製)17.4g(0.22モル)を78gの酢酸エチルに溶解し、5℃以下に冷却した。次いで、3,5-ジニトロベンゾイルクロリド(東京化成工業(株)製)48.4g(0.21モル)を145gの酢酸エチルに溶解し、この溶液を滴下ロートを使い、1時間かけてフラスコ中に滴下した。滴下終了後、10℃以下で30分撹拌し、25℃に昇温し、3時間撹拌した。次いで、反応液を酢酸エチル(CHCOOEt)600mLで希釈し、分液ロートに移し、水300mL、飽和重曹水300mL、希塩酸300mL、飽和食塩水300mLで順に洗浄した。分液洗浄後、硫酸マグネシウム30gで乾燥後、エバポレーターを用いて濃縮、真空乾燥し、ジニトロ体(A-1)を61.0g得た。
 コンデンサー及び撹拌機を取り付けたフラスコに、還元鉄(富士フイルム和光純薬(株)製)27.9g(500ミリモル)、塩化アンモニウム(富士フイルム和光純薬(株)製)5.9g(110ミリモル)、酢酸(富士フイルム和光純薬(株)製)3.0g(50ミリモル)、2,2,6,6-テトラメチルピペリジン 1-オキシル フリーラジカル(東京化成工業(株)製)0.03gを秤り取り、イソプロピルアルコール(IPA)200mL、純水30mLを添加し、撹拌した。
 次いで、上記ジニトロ体(A-1)16.2gを少量ずつ1時間かけて添加し、30分撹拌した。次に、外温を85℃に昇温し、2時間撹拌し、25℃以下に冷却した後、セライト(登録商標)を使用してろ過した。ろ液をロータリーエバポレーターで濃縮し、酢酸エチル800mLに溶解した。これを分液ロートに移し、飽和重曹水300mLで2回洗浄し、水300mL、飽和食塩水300mLで順に洗浄した。分液洗浄後、硫酸マグネシウム30gで乾燥後、エバポレーターを用いて濃縮、真空乾燥し、ジアミン(AA-1)を11.0g得た。
Figure JPOXMLDOC01-appb-C000086
<Synthesis Example AA-1: Synthesis of Diamine AA-1>
2-Hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 26.0 g (0.2 mol), dehydrated pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) in a flask equipped with a condenser and a stirrer. ) 17.4 g (0.22 mol) was dissolved in 78 g of ethyl acetate and cooled to 5 ° C. or lower. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate, and this solution was dissolved in a flask over 1 hour using a dropping funnel. Dropped into. After completion of the dropping, the mixture was stirred at 10 ° C. or lower for 30 minutes, heated to 25 ° C., and stirred for 3 hours. Then, the 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 300 mL of saturated brine in that order. After liquid separation washing, drying with 30 g of magnesium sulfate, concentration using an evaporator, and vacuum drying were performed to obtain 61.0 g of a dinitro compound (A-1).
27.9 g (500 mmol) of reduced iron (manufactured by Wako Pure Chemical Industries, Ltd.) and 5.9 g (110 mmol) of ammonium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) in a flask equipped with a condenser and a stirrer. ), Acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) 3.0 g (50 mmol), 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.03 g Was weighed, 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added, and the mixture was stirred.
Then, 16.2 g of the dinitro compound (A-1) was added little by little over 1 hour, and the mixture was stirred for 30 minutes. Next, the outside temperature was raised to 85 ° C., the mixture was stirred for 2 hours, cooled to 25 ° C. or lower, and then filtered using Cerite (registered trademark). The filtrate was concentrated on a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separating funnel, washed twice with 300 mL of saturated aqueous sodium hydrogen carbonate, and then washed with 300 mL of water and 300 mL of saturated brine in that order. After liquid separation washing, drying with 30 g of magnesium sulfate, concentration using an evaporator, and vacuum drying were performed to obtain 11.0 g of diamine (AA-1).
Figure JPOXMLDOC01-appb-C000086
<実施例及び比較例>
 各実施例において、それぞれ、下記表に記載の成分を混合し、各硬化性樹脂組成物を得た。また、各比較例において、それぞれ、下記表に記載の成分を混合し、各比較用組成物を得た。
 具体的には、表に記載の溶剤以外の成分の含有量は、表の各「添加量」の欄に記載の量(質量部)とした。
 得られた硬化性樹脂組成物及び比較用組成物を、細孔の幅が0.8μmのポリテトラフルオロエチレン製フィルターを通して加圧ろ過した。
 また、表中、「-」の記載は該当する成分を組成物が含有していないことを示している。 
<Examples and comparative examples>
In each example, the components listed in the table below were mixed to obtain each curable resin composition. Further, in each comparative example, the components listed in the following table were mixed to obtain each comparative composition.
Specifically, the content of the components other than the solvent described in the table is the amount (parts by mass) described in each "addition amount" column of the table.
The obtained curable resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
Further, in the table, the description of "-" indicates that the composition does not contain the corresponding component.
Figure JPOXMLDOC01-appb-T000087
Figure JPOXMLDOC01-appb-T000087
Figure JPOXMLDOC01-appb-T000088
Figure JPOXMLDOC01-appb-T000088
 表に記載した各成分の詳細は下記の通りである。 The details of each component listed in the table are as follows.
〔樹脂〕
・A-1~A-7、PBI-1:上述の合成例で合成したポリベンゾオキサゾール前駆体A-1、ポリイミド前駆体A-2~A-7、ポリイミドPBI-1
〔resin〕
A-1 to A-7, PBI-1: Polybenzoxazole precursor A-1, polyimide precursors A-2 to A-7, polyimide PBI-1 synthesized in the above synthesis example.
〔オキサゾリン基を有する化合物〕
・B-1~B-6:下記構造の化合物、B-1、B-2、B-4及びB-5は東京化成工業(株)製であり、B-3及びB-6はAldrich社製である。
・PB-1~PB-3、PB-5~PB-6:上述の合成例で合成したPB-1~PB-3、PB-5~PB-6
・PB-4:エポクロスRPSー1005(日本触媒(株)製)
 なお、PB-1~PB-6はオキサゾリン基を含む繰り返し単位を有する樹脂である。
Figure JPOXMLDOC01-appb-C000089
[Compound having an oxazoline group]
B-1 to B-6: Compounds having the following structures, B-1, B-2, B-4 and B-5, are manufactured by Tokyo Chemical Industry Co., Ltd., and B-3 and B-6 are manufactured by Aldrich. Made of.
PB-1 to PB-3, PB-5 to PB-6: PB-1 to PB-3 and PB-5 to PB-6 synthesized in the above synthesis example.
・ PB-4: Epocross RPS-1005 (manufactured by Nippon Shokubai Co., Ltd.)
In addition, PB-1 to PB-6 are resins having a repeating unit containing an oxazoline group.
Figure JPOXMLDOC01-appb-C000089
〔酸基及びアルコキシシリル基を有する化合物〕
・C-1~C-6:上述の合成例で合成したC-1~C-6
・PC-1~PC-5:上述の合成例で合成したPC-1~PC-5
 なお、PC-1~PC-5は酸基を含む繰り返し単位及びアルコキシシリル基を含む繰り返し単位を有する樹脂である。
 C-1~C-6の構造は、下記式(C-1)~式(C-6)で表される構造であると推定される。
 また、式(PC-1)~式(PC-5)中、括弧の添字は書く繰り返し単位の含有比(モル比)を表す。
Figure JPOXMLDOC01-appb-C000090
[Compound having an acid group and an alkoxysilyl group]
C-1 to C-6: C-1 to C-6 synthesized in the above synthesis example.
-PC-1 to PC-5: PC-1 to PC-5 synthesized in the above synthesis example.
PC-1 to PC-5 are resins having a repeating unit containing an acid group and a repeating unit containing an alkoxysilyl group.
The structures of C-1 to C-6 are presumed to be the structures represented by the following formulas (C-1) to (C-6).
Further, in the formulas (PC-1) to (PC-5), the subscripts in parentheses represent the content ratio (molar ratio) of the repeating unit to be written.
Figure JPOXMLDOC01-appb-C000090
〔塩基発生剤〕
・D-1~D-3:下記構造の化合物
・D-4:WPBG-27 (富士フイルム和光純薬(株))
Figure JPOXMLDOC01-appb-C000091
[Base generator]
-D-1 to D-3: Compounds with the following structure-D-4: WPBG-27 (Fuji Film Wako Pure Chemical Industries, Ltd.)
Figure JPOXMLDOC01-appb-C000091
〔光重合開始剤(いずれも商品名)〕
・OXE-01:IRGACURE OXE 01(BASF社製)
・OXE-02:IRGACURE OXE 02(BASF社製)
[Photopolymerization initiator (both are trade names)]
・ OXE-01: IRGACURE OXE 01 (manufactured by BASF)
OXE-02: IRGACURE OXE 02 (manufactured by BASF)
〔重合性化合物(いずれも商品名)〕
・SR-209:SR-209(サートマー社製)
・SR-231:SR-231(サートマー社製)
・SR-239:SR-239(サートマー社製)
・A-DPH  :ジペンタエリスリトールヘキサアクリレート(新中村化学工業(株)製)
[Polymerizable compounds (both trade names)]
-SR-209: SR-209 (manufactured by Sartmer)
-SR-231: SR-231 (manufactured by Sartmer)
-SR-239: SR-239 (manufactured by Sartmer)
-A-DPH: Dipentaerythritol hexaacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
〔重合禁止剤〕
・G-1:1,4-ベンゾキノン
・G-2:4-メトキシフェノール
・G-3:1,4-ジヒドロキシベンゼン
・G-4:下記構造の化合物
Figure JPOXMLDOC01-appb-C000092
[Polymerization inhibitor]
G-1: 1,4-benzoquinone, G-2: 4-methoxyphenol, G-3: 1,4-dihydroxybenzene, G-4: a compound having the following structure
Figure JPOXMLDOC01-appb-C000092
〔アゾール基を有する化合物(アゾール基を有する他の化合物)〕
・H-1~H-3:下記構造の化合物
Figure JPOXMLDOC01-appb-C000093
[Compounds having an azole group (other compounds having an azole group)]
-H-1 to H-3: Compounds having the following structure
Figure JPOXMLDOC01-appb-C000093
〔その他の添加剤〕
・Iー1:N-フェニルジエタノールアミン(東京化成工業(株)製)
[Other additives]
・ I-1: N-Phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
〔溶剤〕
・DMSO:ジメチルスルホキシド
・GBL:γ-ブチロラクトン
・NMP:N-メチルピロリドン
 表中、「DMSO/GBL」の記載はDMSOとGBLを80:20の混合比(質量比)で混合したものを用いたことを示している。
〔solvent〕
-DMSO: dimethyl sulfoxide-GBL: γ-butyrolactone-NMP: N-methylpyrrolidone In the table, "DMSO / GBL" is a mixture of DMSO and GBL at a mixing ratio (mass ratio) of 80:20. It is shown that.
<評価>
〔銅密着性の評価〕
 上記ろ過後の各硬化性樹脂組成物又は比較用組成物を、銅基板上にスピンコート法により層状に適用して、硬化性樹脂組成物層を形成した。得られた硬化性樹脂組成物層を適用した銅基板をホットプレート上で、100℃で5分間乾燥し、銅基板上に20μmの厚さの均一な硬化性樹脂組成物層とした。銅基板上の硬化性樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cmの露光エネルギーで100μm四方のフォトマスクを使用して露光し、その後シクロペンタノンで60秒間現像して、100μm四方形の樹脂層を得た。さらに、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表中の「硬化温度(℃)」の欄に記載の温度に達した後、この温度を3時間維持し樹脂膜2を得た。
 ただし、塩基発生剤としてI-4を用いた例においては、上記「硬化温度(℃)」の欄に記載の温度に達した後、3時間加熱しながら500mJ/cmの露光量でパターンの全面にi線露光を行った。
 銅基板上の100μm四方形の樹脂膜2に対して、25℃、65%相対湿度(RH)の環境下にて、ボンドテスター(XYZTEC社製、CondorSigma)を用いて、せん断力を測定した。せん断力が大きければ大きいほど密着力が大きく、金属と硬化膜との密着性に優れるといえ、好ましい結果となる。
 評価は下記評価基準に従って行い、評価結果は表中の「銅密着性」の欄に記載した。
―評価基準―
A:せん断力が40gfを超えた
B:せん断力が35gfを超えて40gf以下
C:せん断力が30gfを超えて35gf以下
D:せん断力が25gfを超えて30gf以下
E:せん断力が25gf以下
 1gfは9.80665×10-3Nである。
<Evaluation>
[Evaluation of copper adhesion]
Each of the curable resin compositions or comparative compositions after filtration was applied in layers on a copper substrate by a spin coating method to form a curable resin composition layer. The copper substrate to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform curable resin composition layer having a thickness of 20 μm on the copper substrate. The curable resin composition layer on the copper substrate was exposed using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ / cm 2 using a 100 μm square photomask, followed by cyclopentanone for 60 seconds. Development was performed to obtain a 100 μm square resin layer. Further, the temperature is raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching the temperature described in the column of "curing temperature (° C.)" in the table, this temperature is maintained for 3 hours to form a resin film. I got 2.
However, in the example in which I-4 was used as the base generator, after reaching the temperature described in the above "curing temperature (° C.)" column, the pattern was heated at an exposure amount of 500 mJ / cm 2 while heating for 3 hours. The entire surface was exposed to i-line.
Shear force was measured on a 100 μm square resin film 2 on a copper substrate in an environment of 25 ° C. and 65% relative humidity (RH) using a bond tester (CondorSigma, manufactured by XYZTEC). It can be said that the larger the shearing force, the larger the adhesion force and the excellent adhesion between the metal and the cured film, which is a preferable result.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Copper adhesion" column in the table.
-Evaluation criteria-
A: Shear force exceeds 40 gf B: Shear force exceeds 35 gf and 40 gf or less C: Shear force exceeds 30 gf and 35 gf or less D: Shear force exceeds 25 gf and 30 gf or less E: Shear force exceeds 25 gf 1 gf Is 9.80665 × 10 -3 N.
〔耐薬品性(膜変化率)の評価〕
 各実施例及び比較例において、それぞれ、硬化性樹脂組成物又は比較用組成物をシリコンウェハ上にスピンコート法により適用し、硬化性樹脂組成物層を形成した。得られた硬化性樹脂組成物層を適用したシリコンウェハをホットプレート上で、100℃で5分間乾燥し、シリコンウェハ上に15μmの均一な厚さの硬化性樹脂組成物層を形成した。シリコンウェハ上の硬化性樹脂組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cmの露光エネルギーでi線露光し、露光した硬化性樹脂組成物層(樹脂層)を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表中の「硬化温度(℃)」の欄に記載の温度で3時間加熱して、硬化性樹脂組成物層の硬化層(樹脂層)を得た。
 得られた樹脂層について下記の薬液に下記の条件で浸漬し、溶解速度を算定した。
 薬液:ジメチルスルホキシド(DMSO)と25質量%のテトラメチルアンモニウムヒドロキシド(TMAH)水溶液の90:10(質量比)の混合物
評価条件:樹脂層を上記薬液に75℃で15分間浸漬して前後の膜厚を比較し、溶解速度(nm/分)を算出した。膜厚は、エリプソメーター(Foothill社製KT-22)で塗布面10点において膜厚測定を実施し、その算術平均値として求めた。
 評価は下記評価基準に従って行い、評価結果は表の「耐薬品性」の欄に記載した。溶解速度の値が小さいほど、得られる硬化膜(樹脂層)は耐薬品性に優れるといえる。
-評価基準-
 A:溶解速度が200nm/分未満であった。
 B:溶解速度が200nm/分以上300nm/分未満であった。
 C:溶解速度が300nm/分以上400nm/分未満であった。
 D:溶解速度が400nm/分以上であった。
[Evaluation of chemical resistance (membrane change rate)]
In each Example and Comparative Example, a curable resin composition or a comparative composition was applied onto 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 μm on the silicon wafer. The curable resin composition layer on the silicon wafer was exposed to i-line with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed curable resin composition layer (resin layer) was subjected to i-line exposure. Under a nitrogen atmosphere, the temperature is raised at a heating rate of 10 ° C./min, and the temperature is heated at the temperature described in the column of "curing temperature (° C.)" in the table for 3 hours to cure the cured resin composition layer. (Resin layer) was obtained.
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 dimethylsulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio) Evaluation conditions: Immerse the resin layer in the above chemical solution at 75 ° C. for 15 minutes before and after. The film thicknesses were compared and the dissolution rate (nm / min) was calculated. The film thickness was measured at 10 points on the coated surface with an ellipsometer (KT-22 manufactured by Foothill), and the film thickness was determined as the arithmetic mean value.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Chemical resistance" column of the table. It can be said that the smaller the value of the dissolution rate, the better the chemical resistance of the obtained cured film (resin layer).
-Evaluation criteria-
A: The dissolution rate was less than 200 nm / min.
B: The dissolution rate was 200 nm / min or more and less than 300 nm / min.
C: The dissolution rate was 300 nm / min or more and less than 400 nm / min.
D: The dissolution rate was 400 nm / min or more.
 以上の結果から、本発明の硬化性樹脂組成物によれば、金属密着性(銅密着性)に優れた硬化膜が得られることがわかる。
 比較例1~3に係る比較用組成物は、オキサゾリン基を有する化合物を含まない。このような比較用組成物によれば、金属密着性(銅密着性)に劣ることがわかる。
From the above results, it can be seen that according to the curable resin composition of the present invention, a cured film having excellent metal adhesion (copper adhesion) can be obtained.
The comparative compositions according to Comparative Examples 1 to 3 do not contain a compound having an oxazoline group. It can be seen that such a comparative composition is inferior in metal adhesion (copper adhesion).
<実施例101>
 実施例1において使用した硬化性樹脂組成物を、表面に銅薄層が形成された樹脂基材の銅薄層の表面にスピンコート法により層状に適用して、100℃で4分間乾燥し、膜厚20μmの硬化性樹脂組成物層を形成した後、ステッパー((株)ニコン製、NSR1505 i6)を用いて露光した。露光はマスク(パターンが1:1ラインアンドスペースであり、線幅が10μmであるバイナリマスク)を介して、波長365nmで行った。露光後、100℃で4分間加熱した。上記加熱後、シクロヘキサノンで2分間現像し、PGMEAで30秒間リンスし、層のパターンを得た。
 次いで、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、230℃で3時間維持して、再配線層用層間絶縁膜を形成した。この再配線層用層間絶縁膜は、絶縁性に優れていた。
 また、これらの再配線層用層間絶縁膜を使用して半導体デバイスを製造したところ、問題なく動作することを確認した。
<Example 101>
The curable resin composition used in Example 1 was applied in a layered manner on the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 4 minutes. After forming a curable resin composition layer having a thickness of 20 μm, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 μm) at a wavelength of 365 nm. After the exposure, it was heated at 100 ° C. for 4 minutes. After the above heating, it was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
Next, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating property.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Claims (15)

  1.  ポリイミド前駆体、ポリベンゾオキサゾール前駆体、ポリイミド及びポリベンゾオキサゾールよりなる群から選ばれた少なくとも1種の樹脂、
     オキサゾリン基を有する化合物、並びに、
     酸基及びアルコキシシリル基を含む化合物を含む、
     硬化性樹脂組成物。
    At least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimides and polybenzoxazoles,
    Compounds having an oxazoline group, as well as
    Includes compounds containing acid and alkoxysilyl groups,
    Curable resin composition.
  2.  前記樹脂におけるカルボキシ基の含有量が、1.0mmol/g以下である、請求項1に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1, wherein the content of the carboxy group in the resin is 1.0 mmol / g or less.
  3.  前記オキサゾリン基を有する化合物が、構造中にオキサゾリン基を2個以上含む化合物である、請求項1又は2に記載の硬化性樹脂組成物。 The curable resin composition according to claim 1 or 2, wherein the compound having an oxazoline group is a compound containing two or more oxazoline groups in its structure.
  4.  前記オキサゾリン基を有する化合物が、アルコキシシリル基、ラジカル重合性基及びアゾール基よりなる群から選ばれた少なくとも1種を含む、請求項1~3のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 3, wherein the compound having an oxazoline group contains at least one selected from the group consisting of an alkoxysilyl group, a radically polymerizable group and an azole group. ..
  5.  前記オキサゾリン基を有する化合物が樹脂である、請求項1~4のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 4, wherein the compound having an oxazoline group is a resin.
  6.  前記酸基及びアルコキシシリル基を含む化合物が、樹脂である、請求項1~5のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 5, wherein the compound containing the acid group and the alkoxysilyl group is a resin.
  7.  前記酸基及びアルコキシシリル基を含む化合物が、ラジカル重合性基及びアゾール基よりなる群から選ばれた少なくとも1種の基を含む、請求項1~6のいずれか1項に記載の硬化性樹脂組成物。 The curable resin according to any one of claims 1 to 6, wherein the compound containing an acid group and an alkoxysilyl group contains at least one group selected from the group consisting of a radically polymerizable group and an azole group. Composition.
  8.  熱塩基発生剤、光塩基発生剤、及び、オニウム塩よりなる群から選ばれた少なくとも1種の化合物を含む、請求項1~7のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 7, which comprises at least one compound selected from the group consisting of a thermal base generator, a photobase generator, and an onium salt.
  9.  再配線層用層間絶縁膜の形成に用いられる、請求項1~8のいずれか1項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 8, which is used for forming an interlayer insulating film for a rewiring layer.
  10.  請求項1~9のいずれか1項に記載の硬化性樹脂組成物を硬化してなる硬化膜。 A cured film obtained by curing the curable resin composition according to any one of claims 1 to 9.
  11.  請求項10に記載の硬化膜を2層以上含み、前記硬化膜同士のいずれかの間に金属層を含む積層体。 A laminate containing two or more layers of the cured film according to claim 10 and containing a metal layer between any of the cured films.
  12.  請求項1~9のいずれか1項に記載の硬化性樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。 A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of claims 1 to 9 to a substrate to form a film.
  13.  前記膜を露光する露光工程及び前記膜を現像する現像工程を含む、請求項12に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 12, further comprising an exposure step for exposing the film and a developing step for developing the film.
  14.  前記膜を、50~450℃で加熱する加熱工程を含む、請求項12又は13に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 12, which comprises a heating step of heating the film at 50 to 450 ° C.
  15.  請求項10に記載の硬化膜又は請求項11に記載の積層体を含む、半導体デバイス。 A semiconductor device comprising the cured film according to claim 10 or the laminate according to claim 11.
PCT/JP2021/021069 2020-06-03 2021-06-02 Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device WO2021246459A1 (en)

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