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WO2024181276A1 - Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, and semiconductor device - Google Patents

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

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Publication number
WO2024181276A1
WO2024181276A1 PCT/JP2024/006352 JP2024006352W WO2024181276A1 WO 2024181276 A1 WO2024181276 A1 WO 2024181276A1 JP 2024006352 W JP2024006352 W JP 2024006352W WO 2024181276 A1 WO2024181276 A1 WO 2024181276A1
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WO
WIPO (PCT)
Prior art keywords
group
formula
resin composition
compound
cured product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/006352
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French (fr)
Japanese (ja)
Inventor
大輔 浅川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to CN202480015588.XA priority Critical patent/CN120917095A/en
Priority to JP2025503827A priority patent/JPWO2024181276A1/ja
Priority to KR1020257028611A priority patent/KR20250142370A/en
Publication of WO2024181276A1 publication Critical patent/WO2024181276A1/en
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • 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
    • G03F7/0755Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14Polymers provided for in subclass C08G
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14Polymers provided for in subclass C08G
    • C08F290/145Polyamides; Polyesteramides; Polyimides
    • 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
    • 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
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/544Silicon-containing compounds containing nitrogen
    • 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
    • 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
    • G03F7/039Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/16Coating processes; Apparatus therefor
    • G03F7/168Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC

Definitions

  • the present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device.
  • resin materials produced from resin compositions containing resins are being used in various fields.
  • cyclized resins such as polyimide are used in various applications because of their excellent heat resistance and insulating properties.
  • the applications are not particularly limited, but for example, in the case of semiconductor devices for mounting, they can be used as insulating films, sealing materials, or protective films. They are also used as base films or coverlays for flexible substrates.
  • the cyclized resin such as a polyimide
  • a resin composition that includes the cyclized resin or a precursor of the cyclized resin, such as a polyimide precursor.
  • a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate.
  • the precursor of the cyclized resin, such as a polyimide precursor is cyclized, for example, by heating, and becomes a cyclized resin, such as a polyimide, in the cured product.
  • the resin composition can be applied by a known coating method, etc., it can be said to have excellent adaptability in manufacturing, for example, high degree of freedom in designing the shape, size, application position, etc. of the resin composition when applied.
  • cyclized resins such as polyimide
  • industrial application development of the above-mentioned resin composition is expected to continue.
  • resin materials are required to have excellent adhesion to substrates, and various methods for improving adhesion to substrates have been investigated.
  • Patent Document 1 describes a curable resin composition containing at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor, and a photobase generator having an alkoxysilyl group.
  • Patent Document 2 describes a negative type photosensitive resin composition containing the following components: (A) a polyimide precursor; (B) a photopolymerization initiator; (C) a silane coupling agent having a specific structure; and (D) an organic solvent containing at least one selected from the group consisting of ⁇ -butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ⁇ -caprolactone.
  • the present invention aims to provide a resin composition that can give a cured product that has excellent adhesion to a substrate, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product.
  • R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different
  • R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different, at least two of R 1 and R 2 may be bonded to form a ring structure
  • n represents an integer of 1 to 3
  • m represents an integer of 1 or more
  • R 3 represents an m-valent organic group.
  • R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different
  • R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different
  • at least two of R 1 and R 2 may be bonded to form a ring structure
  • n represents an integer of 1 to 3
  • L represents a divalent linking group
  • R 4 represents a hydrogen atom or a monovalent organic group.
  • R 3 in the above formula (A1-1) is a group represented by the following formula (R3-1):
  • L 31 each independently represents a divalent linking group
  • R 31 each independently represents an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or a group represented by *-C( ⁇ O)R 32 -#
  • * represents a bonding site to the nitrogen atom in formula (R3-1)
  • # represents a bonding site to L 32 in formula (R3-1)
  • R 32 represents an organic group
  • m represents an integer of 1 or more, when m is 1, L 32 represents a hydrogen atom or a substituent, and when m is 2 or more, L 32 represents a single bond or an m-valent linking group
  • * represents a bonding site to the silicon
  • R 21 is an organic group having an HSP value of 17.0 to 27.0 MPa 1/2 , and when there is a plurality of R 21 , they may be the same or different
  • R 22 is a hydrogen atom or any organic group not corresponding to the above R 21 , and when there is a plurality of R 22 , they may be the same or different, at least two of R 21 and R 22 may be bonded to form a ring structure
  • n represents an integer of 1 to 3
  • m represents an integer of 1 or more
  • R 23 represents an m-valent organic group.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the resin is a polyimide or a polyimide precursor.
  • ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the resin is a polyimide.
  • ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, further comprising a photopolymerization initiator.
  • ⁇ 9> The resin composition according to ⁇ 8>, further comprising a sensitizer.
  • ⁇ 10> The resin composition according to any one of ⁇ 1> to ⁇ 9>, further comprising a compound having a urea bond.
  • ⁇ 11> The resin composition according to any one of ⁇ 1> to ⁇ 10>, further comprising a polymerizable compound having at least one of a urea bond and a urethane bond.
  • ⁇ 12> The resin composition according to any one of ⁇ 1> to ⁇ 11>, further comprising a solvent having at least one of an amide bond or a hydroxyl group.
  • ⁇ 13> The resin composition according to any one of ⁇ 1> to ⁇ 12>, which is used for forming an interlayer insulating film for a redistribution layer.
  • ⁇ 14> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 13>.
  • ⁇ 15> A laminate comprising two or more layers made of the cured product according to ⁇ 14>, and a metal layer between any two adjacent layers made of the cured product.
  • ⁇ 16> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 13> onto a substrate to form a film.
  • the method for producing a cured product according to ⁇ 16> comprising: an exposure step of selectively exposing the film to light; and a development step of developing the film with a developer to form a pattern.
  • a method for producing a cured product according to ⁇ 16> or ⁇ 17> comprising a heating step of heating the film at 50 to 450° C.
  • a method for producing a laminate comprising the method for producing a cured product according to any one of ⁇ 16> to ⁇ 18>.
  • a method for producing a semiconductor device comprising the method for producing a cured product according to any one of ⁇ 16> to ⁇ 18>.
  • a semiconductor device comprising the cured product according to ⁇ 14>.
  • the present invention provides a resin composition that can produce a cured product that has excellent adhesion to a substrate, a cured product obtained by curing the resin composition, a laminate that includes the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device that includes the method for producing the cured product, and a semiconductor device that includes the cured product.
  • a numerical range expressed using the symbol "to” means a range that includes the numerical values before and after "to” as the lower limit and upper limit, respectively.
  • the term “process” includes not only an independent process but also a process that cannot be clearly distinguished from other processes, so long as the process can achieve its intended effect.
  • groups (atomic groups) when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups).
  • an "alkyl group” encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
  • exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
  • (meth)acrylate means both or either of “acrylate” and “methacrylate”
  • (meth)acrylic means both or either of “acrylic” and “methacrylic”
  • (meth)acryloyl means both or either of “acryloyl” and “methacryloyl”.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the total solid content refers to the total mass of all components of the composition excluding the solvent
  • the solid content concentration refers to the mass percentage of the 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 values measured using gel permeation chromatography (GPC) method, and are defined as polystyrene equivalent values, unless otherwise specified.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series as columns.
  • these molecular weights are measured using THF (tetrahydrofuran) as an eluent.
  • THF tetrahydrofuran
  • NMP N-methyl-2-pyrrolidone
  • detection in GPC measurement is performed using a UV (ultraviolet) light detector with a wavelength of 254 nm.
  • a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer.
  • the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as “upper”, and the opposite direction is referred to as "lower”. Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper” direction in this specification may be different from the vertical upward direction.
  • the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component.
  • the content of each component in the composition means the total content of all compounds corresponding to that component.
  • the temperature is 23° C.
  • the pressure is 101,325 Pa (1 atm)
  • the relative humidity is 50% RH.
  • combinations of preferred aspects are more preferred aspects.
  • the resin composition according to the first aspect of the present invention contains at least one resin selected from the group consisting of cyclized resins and precursors thereof, and a compound A represented by formula (A1-1).
  • the resin composition according to the second aspect of the present invention (hereinafter, also simply referred to as the “second resin composition”) comprises at least one resin selected from the group consisting of cyclized resins and precursors thereof, It contains a compound A represented by formula (A2-1).
  • the first resin composition and the second resin composition will be collectively referred to simply as the "resin composition”.
  • the compound A contained in the first resin composition and represented by formula (A1-1) will also be referred to as the "first compound A”.
  • the compound A contained in the second resin composition and represented by formula (A2-1) is also referred to as the "second compound A”.
  • compound A when simply described as “compound A”, it refers to both the first compound A and the second compound A.
  • the resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent.
  • the resin composition of the present invention can be used, for example, to form an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer.
  • the resin composition of the present invention may be used to form a photosensitive film to be subjected to positive development, or may be used to form a photosensitive film to be subjected to negative development.
  • negative development refers to a development in which the non-exposed areas are removed by development during exposure and development
  • positive development refers to a development in which the exposed areas are removed by development.
  • the exposure method, the developer, and the development method for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the production method of the cured product described later can be used.
  • a cured product having excellent adhesion to a substrate can be obtained.
  • the mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.
  • Silane coupling agents have been used in resin compositions for the purpose of improving adhesion to substrates, etc. These silane coupling agents have a simple unsubstituted trialkoxysilyl structure such as a trimethoxysilyl group.
  • at least one alkoxy group in the trialkoxysilyl structure is substituted with an organic group having at least one atom selected from oxygen atom, nitrogen atom and sulfur atom.It has been found that this improves the adhesion of the cured film to the substrate after heat resistance test compared with the case of using the conventional product.
  • the mechanism by which the above effect is obtained is not clear, but is presumed to be as follows.
  • the introduction of a highly polar heteroatom into the hydrophobic alkoxysilyl group improves the interaction between the silane coupling agent and the metal substrate, and it is believed that the silane coupling agent is unevenly distributed near the substrate when the film is cured. As a result, the sol-gel reaction proceeds more efficiently on the substrate surface than with conventional products, which is believed to improve the adhesion of the cured film to the substrate.
  • at least one alkoxy group in the trialkoxysilyl structure is substituted with an organic group having an HSP value of 17.0 to 27.0 MPa 1/2 . This has been found to improve the adhesion of the cured film to the substrate after heat resistance testing compared to the case where a conventional product is used.
  • Patent Documents 1 and 2 do not describe the first compound A and the second compound A.
  • the resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.
  • the cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.
  • the term "main chain” refers to the relatively longest bonding chain in a resin molecule, and the term “side chain” refers to any other bonding chain.
  • the cyclized resin include polyimide, polybenzoxazole, and polyamideimide.
  • the precursor of a cyclized resin refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a cyclized resin.
  • a resin that undergoes a change in chemical structure due to heat to become a cyclized resin is preferred, and a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a cyclized resin is more preferred.
  • the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor. That is, the resin composition preferably contains, as the specific resin, at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor.
  • the resin composition preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide.
  • the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
  • the resin composition of the present invention preferably contains a radical polymerization initiator, more preferably contains a radical polymerization initiator and a radical crosslinking agent. If necessary, it can further contain a sensitizer.
  • a negative photosensitive film is formed from such a resin composition.
  • the specific resin may also have a polarity conversion group such as an acid-decomposable group.
  • the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive or negative photosensitive film is formed.
  • the polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2).
  • A1 and A2 each independently represent an oxygen atom or -NRz-
  • R111 represents a divalent organic group
  • R115 represents a tetravalent organic group
  • R113 and R114 each independently represent a hydrogen atom or a monovalent organic group
  • Rz represents a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 each independently represent an oxygen atom or —NR z —, and preferably an oxygen atom.
  • Rz represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.
  • R 111 in 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.
  • a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred.
  • the linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom.
  • R 111 in formula (2) examples include groups represented by -Ar- and -Ar-L-Ar-, and a group represented by -Ar-L-Ar- is preferred.
  • Ar is each independently an aromatic group
  • L is a single bond, 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.
  • the preferred ranges of these are as described above.
  • R 111 is preferably derived from a diamine.
  • the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
  • R 111 is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms.
  • the linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom
  • the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom.
  • groups containing an aromatic group include the following.
  • * represents a bonding site with other structures.
  • diamines 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'-diaminodiphen
  • diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017/038598.
  • diamines having two or more alkylene glycol units in the main chain are also preferably used.
  • diamines having two or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of WO 2017/038598.
  • R 111 is preferably represented by -Ar-L-Ar-.
  • each Ar is independently an aromatic group
  • 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 preferably a phenylene group
  • L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 -.
  • 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). In particular, from the viewpoints of i-line transmittance and ease of availability, R 111 is more preferably a divalent organic group represented by formula (61). Equation (51) In formula (51), R 50 to R 57 each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group, at least one of R 50 to R 57 represents a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2).
  • Examples of the monovalent organic group for R 50 to R 57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).
  • R 58 and R 59 each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in formula (2).
  • Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.
  • R 111 is also preferably a group represented by the following formula (71): In the above embodiment, R 111 is more preferably a group represented by the following formula (72).
  • a 1 to A 3 each independently represent a single bond or a divalent linking group
  • * represents a bonding site with the nitrogen atom in formula (2)
  • each of the four benzene rings described in formula (71) may have a hydrogen atom substituted by a substituent.
  • a bond that crosses an edge of a ring structure is meant to replace any of the hydrogen atoms in that ring structure.
  • * represents a bonding site with the nitrogen atom in formula (2).
  • a 1 to A 3 are preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, -S-, -S( ⁇ O) 2 -, -NHC( ⁇ O)-, or a group consisting of a combination of two or more of these, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, or a group consisting of a combination of two or more of these, and further preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-.
  • a 1 and A 3 are preferably —O—.
  • A2 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom.
  • a 1 and A 3 are —O— and A 2 is —C(CH 3 ) 2 — is also one of the preferred embodiments of the present invention.
  • the number of carbon atoms in the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 4.
  • aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom include -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 - and the like, with -C(CH 3 ) 2 - being preferred.
  • substituents on the four benzene rings shown in formula (71) include a fluorine atom and a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom.
  • An embodiment in which all of the four benzene rings in formula (71) are unsubstituted is also one of the preferred embodiments of the present invention.
  • R 111 is also preferably a group represented by the following formula (81): In the above embodiment, R 111 is more preferably a group represented by the following formula (82).
  • A1 and A2 each independently represent a single bond or a divalent linking group, * represents a bonding site with the nitrogen atom in formula (2), and each of the three benzene rings depicted in formula (81) may have a hydrogen atom substituted with a substituent.
  • * represents a bonding site with the nitrogen atom in formula (2).
  • a 1 and A 2 are each preferably independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, -S-, -S( ⁇ O) 2 -, -NHC( ⁇ O)-, or a group consisting of a combination of two or more of these, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, or a group consisting of a combination of two or more of these, further preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-, and particularly preferably -C(CH 3 ) 2 -.
  • R 115 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.
  • each * independently represents a bonding site to another structure.
  • R 112 is a single bond or a divalent linking group and is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -, -NHCO-, and a combination thereof, more preferably a single bond, or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO 2 -, and still more preferably a divalent group selected from the group consisting of -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -O-, -CO-, -S-, and -SO 2 -.
  • R 115 is also preferably a group represented by the following formula (7): In the above embodiment, R 115 is more preferably a group represented by the following formula (7-2).
  • a 1 to A 3 each independently represent a single bond or a divalent linking group
  • * represents a bonding site with the carbonyl group in formula (2)
  • each of the four benzene rings described in formula (7) may have a hydrogen atom substituted by a substituent.
  • * represents a bonding site with the carbonyl group in formula (2).
  • preferred embodiments of A 1 to A 3 and the substituent on the benzene ring are the same as the preferred embodiments of A 1 to A 3 and the substituent on the benzene ring in formula (7-1) described above.
  • R 115 include tetracarboxylic acid residues remaining after removal of anhydride groups from tetracarboxylic dianhydride.
  • the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue or two or more types of tetracarboxylic dianhydride residues as the structure corresponding to R 115 .
  • the tetracarboxylic dianhydride is preferably represented by the following formula (O).
  • R 115 represents a tetravalent organic group.
  • the preferred range of R 115 is the same as that of R 115 in formula (2), and the preferred range is also the same.
  • tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl methane tetracarboxylic dianhydride, 2 ,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxy
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.
  • R 111 and R 115 may have an OH group. More specifically, R 111 may be a residue of a bisaminophenol derivative.
  • R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
  • the polymerizable group is a group capable of crosslinking by the action of heat, radicals, etc., and is preferably a radical polymerizable group.
  • the polymerizable group examples 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 an amino group.
  • a group having an ethylenically unsaturated bond is preferable.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.
  • R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
  • * represents a bonding site with another structure.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
  • R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CH 2 CH(OH)CH 2 -, and polyalkyleneoxy groups, of which alkylene groups such as ethylene group and propylene group, -CH 2 CH(OH)CH 2 -, cyclohexyl group, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy groups are even more preferred.
  • alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-but
  • the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating.
  • the number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent, when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.
  • the alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom.
  • the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.
  • the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.
  • the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiment of the number of repetitions of the ethyleneoxy group in these groups is as described above.
  • the polyimide precursor when R 113 is a hydrogen atom or when R 114 is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond.
  • a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.
  • R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group.
  • the acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred.
  • the acid-decomposable group examples include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
  • the polyimide precursor has fluorine atoms in its structure.
  • the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and 20% by mass or less.
  • the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
  • Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine.
  • the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
  • a 1 and A 2 represent an oxygen atom
  • R 111 and R 112 each independently represent a divalent organic group
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group
  • at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.
  • a 1 , A 2 , R 111 , R 113 and R 114 each independently have the same meaning as A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and the preferred range is also the same.
  • R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.
  • the polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2).
  • the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).
  • One embodiment of the polyimide precursor of the present invention is one in which the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units.
  • the total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000.
  • the number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
  • the polyimide precursor has a molecular weight dispersity of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the dispersity of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.
  • the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as one resin are each within the above ranges.
  • the polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide that is soluble in a developer containing an organic solvent as a main component.
  • the alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C., and from the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferable, and a polyimide that dissolves at 1.0 g or more is more preferable.
  • the upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less.
  • the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.
  • the polyimide contains fluorine atoms.
  • the fluorine atom is preferably contained, for example, in R 132 in the repeating unit represented by formula (4) described later or in R 131 in the repeating unit represented by formula (4) described later, and more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by formula (4) described later or in R 131 in the repeating unit represented by formula (4) described later.
  • the amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.
  • the polyimide contains a silicon atom.
  • the silicon atom is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and more preferably contained in R 131 in the repeating unit represented by formula (4) described later as an organically modified (poly)siloxane structure described later.
  • the silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
  • the amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass % or more and 20 mass % or less.
  • the polyimide preferably has an ethylenically unsaturated bond.
  • the polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in the side chain.
  • the ethylenically unsaturated bond is preferably radically polymerizable.
  • the ethylenically unsaturated bond is preferably contained in R 132 or R 131 in the repeating unit represented by formula (4) described below, and more preferably contained in R 132 or R 131 as a group having an ethylenically unsaturated bond.
  • the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described below, and more preferably contained in R 131 as a group having an ethylenically unsaturated bond.
  • the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).
  • R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
  • R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -C( ⁇ O)O-, -O(C ⁇ O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions in the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group consisting of a combination of two or more of these.
  • the alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, and alkylene groups represented by a combination thereof.
  • the alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.
  • R 21 is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by 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 in which two or more of these are bonded together;
  • X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ⁇ represents a bonding site with the oxygen atom to which R21 in formula (IV) is bonded.
  • formulas (R1) to (R3) preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L are the same as the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as R 21 in formula (IV).
  • X is preferably an oxygen atom.
  • * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
  • the structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).
  • the structure represented by formula (R2) can be 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 formula (R3) can be obtained, for example, by reacting 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, etc.).
  • * represents a bonding site with another structure, and is preferably a bonding site with the main chain of the polyimide.
  • the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.
  • the polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
  • the polymerizable group other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
  • the polymerizable group other than the group having an ethylenically unsaturated bond is preferably included in, for example, R 131 in the repeating unit represented by formula (4) described below.
  • the amount of polymerizable groups other than groups having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.
  • the polyimide may have a polarity 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 preferred embodiments are also the same.
  • the polarity conversion group is contained, for example, in R 131 and R 132 in the repeating unit represented by formula (4) described later, or at the terminal of the polyimide.
  • the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
  • 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 from 1 to 35 mgKOH/g, more preferably from 2 to 30 mgKOH/g, and even more preferably from 5 to 20 mgKOH/g.
  • the acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
  • the acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability.
  • pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa.
  • pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified.
  • ACD/ChemSketch registered trademark
  • pKa the value listed in "Revised 5th Edition Chemistry Handbook: Basics" compiled by the Chemical Society of Japan may be referred to.
  • the acid group is a polyacid, such as phosphoric acid
  • the pKa is the first dissociation constant.
  • the polyimide preferably contains at least one type 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 on a side chain.
  • the phenolic hydroxy group is preferably contained in, for example, R 132 or R 131 in the repeating unit represented by formula (4) described below.
  • the amount of the phenolic hydroxy group relative 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 polymeric compound having an imide structure, but it is preferable that the polyimide contains a repeating unit represented by the following formula (4).
  • R 131 represents a divalent organic group
  • R 132 represents a tetravalent organic group.
  • the polymerizable group may be located 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).
  • Formula (4-2) In formula (4-2), at least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are as defined in formula (4).
  • R 131 represents a divalent organic group.
  • the divalent organic group include the same as those of R 111 in formula (2), and the preferred range is also the same.
  • R 131 may be a diamine residue remaining after removal of the amino group of the diamine.
  • the diamine may be an aliphatic, cycloaliphatic or aromatic diamine. Specific examples include the example of R 111 in the formula (2) of the polyimide precursor.
  • R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.
  • Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.
  • R 132 represents a tetravalent organic group.
  • examples of the tetravalent organic group include the same as those of R 115 in formula (2), and the preferred range is also the same.
  • the four bonds of the tetravalent organic group exemplified as R 115 bond to the four —C( ⁇ O)— portions in formula (4) to form a condensed ring.
  • R 132 may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride.
  • a specific example is 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 has an OH group. More specifically, preferred examples of R 131 include 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), and more preferred examples of R 132 include the above (DAA-1) to (DAA-5).
  • the polyimide has fluorine atoms in its structure.
  • 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.
  • diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.
  • the main chain ends of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
  • a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
  • monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amino
  • the imidization rate of the polyimide (also referred to as the "ring closure rate") is preferably 70% or more, and more preferably 80% or more. It is more preferable that the content is 90% or more. There is no particular upper limit to the imidization rate, and it is sufficient if it is 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 at about 1377 cm ⁇ 1 , which is an absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350° C.
  • the polyimide may contain repeating units represented by the above formula (4) in which all of the repeating units have the same combination of R 131 and R 132 , or may contain repeating units represented by the above formula (4) containing two or more different combinations of R 131 and R 132.
  • the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Examples of other types of repeating units include the repeating units represented by the above formula (2).
  • Polyimides can be synthesized, for example, by reacting tetracarboxylic dianhydride with diamine (partially substituted with a terminal blocking agent that is a monoamine) at low temperature, by reacting tetracarboxylic dianhydride (partially substituted with a terminal blocking agent that is an acid anhydride, monoacid chloride compound, or monoactive ester compound) with diamine at low temperature, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine) in the presence of a condensing agent, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine), or by using a method in which a polyimide precursor is obtained and then completely
  • the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties (e.g., breaking elongation), the weight average molecular weight is particularly preferably 15,000 or more.
  • the number average molecular weight (Mn) of the polyimide is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000.
  • the polyimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the polyimide molecular weight dispersity is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimides as one resin are each within the above ranges.
  • polybenzoxazole precursor includes the compounds described in paragraphs 0073 to 0095 of WO 2022/145355. The above descriptions are incorporated herein by reference.
  • polybenzoxazole examples include compounds described in paragraphs 0096 to 0103 of WO 2022/145355. The above descriptions are incorporated herein by reference.
  • polyamide-imide precursor examples include compounds described in paragraphs 0104 to 0119 of WO 2022/145355. The above descriptions are incorporated herein by reference.
  • polyamide-imide examples include the compounds described in paragraphs 0120 to 0133 of WO 2022/145355. The above descriptions are incorporated herein by reference.
  • polyimide precursor or the like is produced, for example, by the method described in paragraphs 0134 to 0136 of WO 2022/145355. The above description is incorporated herein by reference.
  • the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition.
  • the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition.
  • the resin composition of the present invention may contain only one specific resin, or may contain two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.
  • the resin composition of the present invention contains at least two types of resins.
  • the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resins described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins.
  • the resin composition of the present invention contains two or more specific resins, it preferably contains, for example, two or more polyimide precursors having different dianhydride-derived structures (R 115 in the above formula (2)).
  • the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, simply referred to as "another resin").
  • other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
  • phenol resins polyamides
  • epoxy resins polysiloxanes
  • resins containing a siloxane structure resins containing a siloxane structure
  • (meth)acrylic resins eth)acrylamide resins
  • urethane resins urethane resins
  • butyral resins ethyral resins
  • styryl resins polyether resins
  • polyester resins polyester resins.
  • the coatability of the resin composition and the solvent resistance of the pattern (cured product) can be improved.
  • the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition.
  • the content of the other resins is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, even more preferably 60 mass% or less, and even more preferably 50 mass% or less, based on the total solid content of the resin composition.
  • 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, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition.
  • the lower limit of the content is not particularly limited, and may be 0% by mass or more.
  • the resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.
  • the first resin composition of the present invention contains a first compound A.
  • the first compound A is a compound represented by formula (A1-1).
  • R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different
  • R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different, at least two of R 1 and R 2 may be bonded to form a ring structure
  • n represents an integer of 1 to 3
  • m represents an integer of 1 or more
  • R 3 represents an m-valent organic group.
  • R 1 is preferably an organic group having at least one atom selected from an oxygen atom and a nitrogen atom.
  • R 1 has an oxygen atom and a nitrogen atom is also one of the preferred embodiments of the present invention.
  • R 1 preferably contains an amino group or an ester bond.
  • the above R N represents a hydrogen atom or a hydrocarbon group in which the hydrogen atom may be substituted with a substituent.
  • the above substituent includes a hydroxy group, an alkoxy group, a halogen atom, etc., and is preferably a hydroxy group.
  • the above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
  • the saturated aliphatic hydrocarbon group is preferably a hydrocarbon group having 2 to 10 carbon atoms, and more preferably a hydrocarbon group having 2 to 4 carbon atoms.
  • substituent include a hydroxy group, an alkoxy group, a halogen atom, a polymerizable group, and the like, and a hydroxy group is preferred.
  • Examples of the polymerizable group include a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, and the like.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 carbon atoms.
  • examples of the substituent include an alkyl group, a hydroxy group, an alkoxy group, a halogen atom, a polymerizable group, etc., and a hydroxy group is preferred.
  • Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, etc.
  • the orientation of the ester bond is not particularly limited, but it is preferable that the carbon atom included in the ester bond faces the silicon atom in formula (A1-1).
  • the substituent in the substituted amino group may be an alkyl group in which the hydrogen atom may be substituted with a substituent, or an aryl group in which the hydrogen atom may be substituted with a substituent.
  • the substituent in the alkyl group in which the hydrogen atom is substituted may be a hydroxyl group, an alkoxyl group, a halogen atom, etc., and preferably a hydroxyl group.
  • the substituent in the aryl group in which the hydrogen atom is substituted may be a hydroxyl group, an alkoxyl group, a halogen atom, etc.
  • R 1 is preferably a group represented by the following formula (R-1), formula (R-2) or formula (R-3).
  • L 5 R1 represents a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-
  • R 5 R1 and R 5 R2 each independently represent a hydrocarbon group in which a hydrogen atom may be substituted with a substituent
  • * represents a bonding site with the oxygen atom in formula (A1-1).
  • L R1 represents a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-
  • R R3 represents a hydrogen atom or a hydrocarbon group in which the hydrogen atom may be substituted with a substituent
  • * represents the bonding site with the oxygen atom in formula (A1-1).
  • L 1 R1 represents a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-
  • R 4 R4 and R 5 represent hydrogen atoms or hydrocarbon groups in which the hydrogen atoms may be substituted with substituents
  • R 6 represents a hydrocarbon group in which the hydrogen atoms may be substituted with substituents
  • * represents the bonding site with the oxygen atom in formula (A1-1).
  • L 1 R1 is preferably an alkylene group or an alkyleneoxyalkylene group, more preferably an alkylene group.
  • the number of carbon atoms in the hydrocarbon group (preferably an alkylene group) in L 1 R1 is preferably 2 to 10, more preferably 2 to 4, and even more preferably 2 or 3.
  • R 1 R1 and R 2 R2 each independently represent an alkyl group in which a hydrogen atom may be substituted with a substituent, or an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
  • the alkyl group is preferably an alkyl group having 2 to 10 carbon atoms, and more preferably an alkyl group having 2 to 4 carbon atoms.
  • examples of the substituent include a hydroxy group, an alkoxy group, a halogen atom, etc., and a hydroxy group is preferred.
  • examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, etc.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a phenyl group.
  • examples of the substituent include an alkyl group, a hydroxy group, an alkoxy group, a halogen atom, a polymerizable group, etc., and a hydroxy group is preferred.
  • examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, etc.
  • R 1 R1 is a hydroxyalkyl group and R 2 R2 is an aromatic hydrocarbon group is also one of the preferred embodiments of the present invention.
  • R 1 R1 is a hydroxyethyl group and R 2 R2 is a phenyl group.
  • L 3 R1 preferred embodiments of L 3 R1 are the same as the preferred embodiments of L 3 R1 in formula (R-1) described above.
  • R 1 R3 when R 1 R3 is a hydrocarbon group in which a hydrogen atom may be substituted with a substituent, the preferred embodiments are the same as the preferred embodiments of R 1 R1 in formula (R-1) described above.
  • an embodiment in which L 1 R1 is an alkylene group and R 1 R3 is a hydrogen atom or an unsubstituted alkyl group is also one of the preferred embodiments of the present invention.
  • L 1 R1 is a trimethylene group and R 1 R3 is a hydrogen atom, a methyl group or an ethyl group.
  • R 1 R4 and R 1 R5 are preferably a hydrogen atom or an alkyl group whose hydrogen atom may be substituted with a substituent.
  • the number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 2 to 4.
  • substituent include a hydroxy group, an alkoxy group, and a halogen atom, and a hydroxy group is preferred.
  • R 1 and R 6 are preferably an alkyl group in which the hydrogen atom may be substituted with a substituent.
  • the number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 2 to 4.
  • substituent include a hydroxy group, an alkoxy group, and a halogen atom, and a hydroxy group is preferred.
  • Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, and a trialkoxysilyl group.
  • L 1 R1 is an alkylene group or an alkyleneoxyalkylene group
  • R 1 R4 is a hydrogen atom or a hydroxyalkyl group
  • R 5 is a hydrogen atom
  • R 6 is an alkyl group in which a hydrogen atom is substituted with a polymerizable group is also one of the preferred embodiments of the present invention.
  • L 1 R1 is an ethylene group or an ethyleneoxyethylene group
  • R 1 R4 is a hydrogen atom or a hydroxyethyl group
  • R 5 is a hydrogen atom
  • R 6 is a (meth)acryloyloxyethyl group
  • R 1 in formula (A1-1) Specific examples of R 1 in formula (A1-1) are described below, but the present invention is not limited thereto.
  • * represents a bonding site with an oxygen atom in formula (A1-1).
  • HSP value described below (the total HSP value described below when * is replaced with a hydrogen atom) is described as HSP.
  • R 2 is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, and still more preferably a methyl group or an ethyl group.
  • HSP values described below total HSP values described below when * is replaced with a hydrogen atom
  • the ring structure formed by combining at least two of R 1 and R 2 is preferably a ring structure containing a nitrogen atom as a ring member. Specifically, it is preferably a ring structure containing a structure represented by the following formula (R-4) or formula (R-5).
  • R-4 L1R2 and L1R3 each independently represent a hydrocarbon group in which a hydrogen atom may be substituted with a substituent
  • R2R7 represents a hydrocarbon group in which a hydrogen atom may be substituted with a substituent
  • L1R4 and L1R5 each independently represent a hydrocarbon group in which a hydrogen atom may be substituted with a substituent
  • R1R8 represents a hydrogen atom or a hydrocarbon group in which a hydrogen atom may be substituted with a substituent
  • R1R9 represents a hydrocarbon group in which a hydrogen atom may be substituted with a substituent
  • * each represents a bonding site to the oxygen atom in formula (A1-1).
  • L 1 R2 and L 1 R3 are each preferably independently an alkylene group.
  • the alkylene group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and further preferably an ethylene group.
  • preferred embodiments of R 1 R7 are the same as the preferred embodiments of R 1 R1 in formula (R-1) above.
  • it is preferable that each * is bonded to the oxygen atom in formula (A1-1) via a single bond without a linking group.
  • preferred embodiments of L 1 R4 and L 1 R5 are the same as the preferred embodiments of L 1 R2 and L 1 R3 in formula (R-4) above, respectively.
  • preferred embodiments of R 1 R8 are the same as preferred embodiments of R 1 R5 in formula (R-3) above.
  • preferred embodiments of R 1 R9 are the same as preferred embodiments of R 1 R6 in formula (R-3) above.
  • each * is bonded to the oxygen atom in formula (A1-1) via a single bond without a linking group.
  • n is preferably 1 or 2.
  • an embodiment in which n is 1 is also one of the preferred embodiments of the present invention.
  • m is preferably an integer of 1 to 3, and more preferably 1 or 2.
  • m is also one of the preferred embodiments of the present invention.
  • R3 represents an m-valent organic group.
  • R N represents a hydrogen atom or a hydrocarbon group in which the hydrogen atom may be substituted with a substituent, preferably a hydrogen atom. Examples of the substituent include a hydroxyl group, an alkoxy group, and a halogen atom.
  • the above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
  • the saturated aliphatic hydrocarbon group is preferably a hydrocarbon group having 2 to 10 carbon atoms, and more preferably a hydrocarbon group having 2 to 4 carbon atoms.
  • substituent include a hydroxy group, an alkoxy group, a halogen atom, and a polymerizable group.
  • Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, and a trialkoxysilyl group.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 carbon atoms.
  • examples of the substituent include a carboxy group, an alkyl group, a hydroxy group, an alkoxy group, a halogen atom, and a polymerizable group.
  • Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, and a trialkoxysilyl group.
  • R 3 is preferably a group represented by the following formula (R3-1).
  • L 31 each independently represents a divalent linking group
  • R 31 each independently represents a divalent linking group
  • m represents an integer of 1 or more, when m is 1
  • L 32 represents a hydrogen atom or a substituent, when m is 2 or more
  • L 32 represents an m-valent linking group
  • * represents a bonding site to the silicon atom in formula (A1-1).
  • L31 is preferably an alkylene group which may be substituted with a hydrogen atom.
  • the number of carbon atoms in the alkylene group is preferably 2 to 10, and more preferably 2 to 4.
  • the hydrocarbon group represented by R31 is preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or an aliphatic unsaturated hydrocarbon group in which a hydrogen atom may be substituted with a substituent, and more preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
  • the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms in which a hydrogen atom may be substituted with a substituent, and more preferably a phenylene group in which a hydrogen atom may be substituted with a substituent.
  • Examples of the substituent in the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent include a carboxy group, a hydroxy group, an alkyl group, an alkoxy group, a halogen atom, etc., and a carboxy group is preferred.
  • Examples of the aliphatic unsaturated hydrocarbon group in which a hydrogen atom may be substituted with a substituent include an ethylene group.
  • R32 represents an organic group, and is preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent. Preferred aspects of this aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent are the same as the preferred aspects of the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent when R31 is a hydrocarbon group.
  • n is the same number as m in formula (A1-1).
  • L 32 represents a hydrogen atom or a substituent, preferably a hydrogen atom or a carboxy group.
  • substituents may be used within the range in which the effects of the present invention can be obtained.
  • R3 in formula (A1-1) Specific examples of R3 in formula (A1-1) are shown below, but the present invention is not limited to these.
  • * represents the bonding site to the silicon atom in formula (A1-1).
  • the first compound A is preferably a compound represented by the following formula (A1-2).
  • R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different
  • R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different, at least two of R 1 and R 2 may be bonded to form a ring structure
  • n represents an integer of 1 to 3
  • L represents a divalent linking group
  • R 4 represents a hydrogen atom or a monovalent organic group.
  • R 1 , R 2 and n are the same as the preferred embodiments of R 1 , R 2 and n in formula (A1-1) described above.
  • L is preferably an alkylene group which may be substituted with a hydrogen atom.
  • the number of carbon atoms in the alkylene group is preferably 2 to 10, and more preferably 2 to 4.
  • the hydrocarbon group represented by R 4 is preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or an aliphatic unsaturated hydrocarbon group in which a hydrogen atom may be substituted with a substituent, and more preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
  • the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms in which a hydrogen atom may be substituted with a substituent, and more preferably a phenylene group in which a hydrogen atom may be substituted with a substituent.
  • Examples of the substituent in the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent include a carboxy group, a hydroxy group, an alkyl group, an alkoxy group, a halogen atom, etc., and a carboxy group is preferred.
  • Examples of the aliphatic unsaturated hydrocarbon group in which a hydrogen atom may be substituted with a substituent include an ethylene group.
  • R33 represents an organic group, and is preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
  • Preferred aspects of this aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent are the same as the preferred aspects of the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent when R4 is a hydrocarbon group.
  • the second resin composition of the present invention contains a second compound A.
  • the second compound A is a compound represented by formula (A2-1).
  • R 21 is an organic group having an HSP value of 17.0 to 27.0 MPa 1/2 , and when there is a plurality of R 21 , they may be the same or different, R 22 is a hydrogen atom or any organic group not corresponding to the above R 21 , and when there is a plurality of R 22 , they may be the same or different, at least two of R 21 and R 22 may be bonded to form a ring structure, n represents an integer of 1 to 3, m represents an integer of 1 or more, and R 23 represents an m-valent organic group.
  • R 21 is preferably an organic group having an HSP value of 17.0 to 25.0 MPa 1/2 , and more preferably an organic group having an HSP value of 17.5 to 24.5 MPa 1/2 .
  • the SP values of R21 and R22 described later were calculated by calculating three components (dD, dP, dH) using the calculation software HSPiP (version 4.1.07) for a structure in which the bond with oxygen of R21 or R22 was replaced with hydrogen, and the total HSP derived by the following formula was used as the HSP value.
  • totalHSP(MPa 1/2 ) (dD 2 +dP 2 +dH 2 ) 1/2
  • R 22 is a hydrogen atom or any organic group other than the above R 21 , and is preferably any organic group other than the above R 21 .
  • the arbitrary organic group not corresponding to R 21 is an organic group having an HSP value of less than 17.0 MPa 1/2 or an HSP value of more than 27.0 MPa 1/2 , and preferably an HSP value of less than 17.0 MPa 1/2 .
  • the second compound A is preferably a compound represented by the following formula (A2-2).
  • R 21 is an organic group having an HSP value of 17.0 to 27.0 MPa 1/2
  • R 21 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, when there is a plurality of R 21 , they may be the same or different
  • R 22 is a hydrogen atom or any organic group not corresponding to the above R 21 , when there is a plurality of R 22 , they may be the same or different
  • at least two of R 21 and R 22 may be bonded to form a ring structure
  • n represents an integer of 1 to 3
  • L represents a divalent linking group
  • R 24 represents a hydrogen atom or a monovalent organic group.
  • R 21 and R 22 are the same as the preferred embodiments of R 21 and R 22 in formula (1-2).
  • the preferred embodiments of n, L and R 24 are the same as the preferred embodiments of n, L and R 24 in formula (1-2).
  • the molecular weight of compound A is preferably 300-1,500, more preferably 320-1,000, and even more preferably 350-800.
  • Compound A is synthesized, for example, by reacting a corresponding alcohol compound with a trialkoxysilyl compound under anhydrous conditions and in the presence of a strong acid such as hydrochloric acid to carry out an alkoxy exchange reaction.
  • a strong acid such as hydrochloric acid
  • compound A may be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.
  • Specific examples of compound A include, but are not limited to, the compounds used in the examples described below.
  • the content of compound A relative to the total solid content of the resin composition of the present invention is preferably 0.02 to 10 mass%.
  • the lower limit is more preferably 0.05 mass% or more, even more preferably 0.10 mass% or more, and particularly preferably 0.20 mass% or more.
  • the upper limit is more preferably 8 mass% or less, even more preferably 4 mass% or less, and particularly preferably 2 mass% or less.
  • an embodiment in which the content is 0.5 mass% or less is also one of the preferred embodiments of the present invention.
  • Compound A may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.
  • the resin composition of the present invention may contain compound X1.
  • Compound X1 is a compound having at least one structure selected from the group consisting of a 1,3-dicarbonyl structure and a ⁇ -hydroxycarbonyl structure, and having a molecular weight of 1,000 or less.
  • the 1,3-dicarbonyl structure refers to a structure represented by the following formula (DC-1)
  • the ⁇ -hydroxycarbonyl structure refers to a structure represented by the following formula (HC-1).
  • * and # each represent a bonding site with another structure.
  • * is preferably a bonding site with a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • # is preferably a bonding site with a hydrogen atom or a carbon atom.
  • the structure represented by the above formula (DC-1) may be an enol type as represented by the following formula (DC-2).
  • the structure represented by the above formula (HC-1) may be an enol type as represented by the following formula (HC-2).
  • * and # each represent a bonding site with another structure. * is preferably a bonding site with a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom.
  • # is preferably a bonding site with a hydrogen atom or a carbon atom.
  • compound X1 does not contain a metal atom in the structure.
  • the metal atom in this case does not include a metalloid atom such as silica.
  • the compound X1 is not coordinated to a metal atom in the resin composition.
  • the molecular weight of compound X1 is 1,000 or less, preferably 100 to 500, more preferably 100 to 400, even more preferably 100 to 350, particularly preferably 100 to 300, and even more preferably 100 to 250.
  • Specific examples of compound X1 include, but are not limited to, compounds having the following structures:
  • the content of compound X1 relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 30 mass%.
  • the lower limit is more preferably 0.02 mass% or more, even more preferably 0.05 mass% or more, and particularly preferably 0.10 mass% or more.
  • the upper limit is more preferably 20 mass% or less, even more preferably 10 mass% or less, and particularly preferably 5 mass% or less.
  • an embodiment in which the content is 1 mass% or less is also one of the preferred embodiments of the present invention.
  • Compound X1 may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.
  • Compound X2 is a compound represented by the following formula (B-1).
  • R B1 represents a tertiary alkyl group
  • R B2 each independently represents a hydrogen atom or an organic group.
  • R B1 represents a tertiary alkyl group and is preferably a group represented by the following formula (B1-1), and more preferably a t-butyl group.
  • R B3 each independently represents an alkyl group, and * represents a bonding site to the benzene ring in formula (B-1).
  • R B3 are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • the alkyl group is preferably a linear alkyl group.
  • R B2 when R B2 is an organic group, R B2 is preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and a ring structure.
  • the hydrocarbon group is preferably an aliphatic saturated hydrocarbon group or a group represented by a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
  • the ring structure may be either an aromatic ring structure or an aliphatic ring structure, but is preferably an aliphatic ring structure, and more preferably an isocyanuric ring structure.
  • the molecular weight of compound X2 is preferably 100 to 2000, more preferably 150 to 1000, and even more preferably 200 to 800.
  • the compound represented by formula (B-1) include, but are not limited to, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N, N'-Hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, ethylene bis(oxyethylene)bis[3-(oxy
  • the content of compound X2 relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 5 mass %.
  • the lower limit is more preferably 0.2 mass % or more, and even more preferably 0.3 mass % or more.
  • the upper limit is more preferably 3 mass % or less, and even more preferably 1 mass % or less.
  • Compound X2 may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains a compound represented by the following formula (X-3).
  • R 1 X1 represents a hydrogen atom or an alkyl group
  • n is an integer of 1 to 10.
  • R X1 is preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, still more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.
  • compound X3 include 4-hydroxybutyric acid, methyl 4-hydroxybutyrate, ethyl 4-hydroxybutyrate, propyl 4-hydroxybutyrate, isopropyl 4-hydroxybutyrate, butyl 4-hydroxybutyrate, pentyl 4-hydroxybutyrate, hexyl 4-hydroxybutyrate, heptyl 4-hydroxybutyrate, octyl 4-hydroxybutyrate, nonyl 4-hydroxybutyrate, and decyl 4-hydroxybutyrate.
  • the content of compound X3 is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the specific resin.
  • the resin composition of the present invention may contain a compound containing a Group 4 element.
  • the compound containing a Group 4 element is preferably a compound containing titanium, zirconium or hafnium, and more preferably a compound containing titanium.
  • the compound containing a Group 4 element is preferably an organometallic complex, and more preferably an organotitanium complex.
  • titanium-containing compounds are shown below in I) to VII):
  • I) Titanium chelate compounds include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
  • Tetraalkoxytitanium compounds For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl)butoxide ⁇ ], etc.
  • Titanocene compounds For example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.
  • Monoalkoxytitanium compounds For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.
  • Titanium oxide compounds For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.
  • Titanium tetraacetylacetonate compounds For example, titanium tetraacetylacetonate, etc.
  • Titanate coupling agents For example, isopropyl tridodecylbenzenesulfonyl titanate, etc.
  • the titanium-containing compound is preferably at least one compound selected from the group consisting of the above I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance.
  • titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis( ⁇ 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.
  • the content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin.
  • the content is 0.05 parts by mass or more, the heat resistance and chemical resistance are improved, and when it is 10 parts by mass or less, the storage stability is improved.
  • the resin composition of the present invention preferably contains a polymerizable compound.
  • the resin composition of the present invention preferably further contains a polymerizable compound having at least one of a urea bond and a urethane bond.
  • the resin composition of the present invention preferably further contains a radical crosslinking agent having at least one of a urea bond and a urethane bond, which will be described later, as the polymerizable compound having at least one of a urea bond and a urethane bond.
  • the polymerizable compound may include a radical crosslinking agent or other crosslinking agents.
  • the resin composition of the present invention preferably contains a radical crosslinking agent.
  • the radical crosslinking agent is a compound having a radical polymerizable group.
  • the radical polymerizable group is preferably a group containing an ethylenically unsaturated bond.
  • Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
  • a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.
  • the radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds.
  • the radical crosslinking agent may have three or more ethylenically unsaturated bonds.
  • a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is even more preferable.
  • the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the above-mentioned compound having three or more ethylenically unsaturated bonds.
  • the molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
  • radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds.
  • unsaturated carboxylic acids e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters and amides preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds
  • amides of unsaturated carboxylic acids and polyvalent amine compounds amides of unsaturated carboxylic acids and polyvalent amine compounds.
  • addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sul
  • addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable.
  • the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
  • Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • radical crosslinking agents other than those mentioned above include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • the radical crosslinking agent is preferably dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), or a
  • radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates with four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers.
  • SR-494 a tetrafunctional acrylate with four ethyleneoxy chains
  • SR-209, 231, and 239 which are difunctional methacrylates with four ethyleneoxy chains (all manufactured by Sartomer Corporation)
  • DPCA-60 a hexafunctional acrylate with six pentyleneoxy chains
  • TPA-330 a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.)
  • Examples include UAS-10 and UAB-140 (all manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corp.).
  • radical crosslinking agents urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also suitable.
  • radical crosslinking agents compounds having an amino structure or sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, can also be used.
  • the radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group.
  • the radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride.
  • a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol.
  • examples of commercially available products include polybasic acid modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.
  • the acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, more preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, the agent has excellent handling properties during manufacturing and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.
  • the radical crosslinking agent a radical crosslinking agent having at least one bond selected from the group consisting of a urea bond and a urethane bond (hereinafter, also referred to as "crosslinking agent U") is also preferred.
  • a urethane bond is a bond represented by *--O--C(.dbd.O)-- NR.sub.N --*, where R.sub.N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom.
  • R.sub.N represents a hydrogen atom or a monovalent organic group
  • * represents a bonding site with a carbon atom.
  • the crosslinking agent U may have only one urea bond or one urethane bond, may have one or more urea bonds and one or more urethane bonds, may have no urethane bonds but two or more urea bonds, or may have no urea bonds but two or more urethane bonds.
  • the total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
  • the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
  • the number of urethane bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
  • the radical polymerizable group in the crosslinking agent U is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. Of these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred.
  • the crosslinking agent U has two or more radically polymerizable groups, the structures of the respective radically polymerizable groups may be the same or different.
  • the number of radical polymerizable groups in the crosslinking agent U may be only one or may be two or more, and is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
  • the radically polymerizable group value (mass of compound per mole of radically polymerizable group) in the crosslinking agent U is preferably 150 to 400 g/mol.
  • the lower limit of the radically polymerizable group value is more preferably 200 g/mol or more, even more preferably 210 g/mol or more, still more preferably 220 g/mol or more, even more preferably 230 g/mol or more, still more preferably 240 g/mol or more, and particularly preferably 250 g/mol or more.
  • the upper limit of the radically polymerizable group value is more preferably 350 g/mol or less, further preferably 330 g/mol or less, and particularly preferably 300 g/mol or less.
  • the polymerizable group value of the crosslinking agent U is preferably from 210 to 400 g/mol, and more preferably from 220 to 400 g/mol.
  • the crosslinking agent U preferably has a structure represented by the following formula (U-1).
  • R U1 is a hydrogen atom or a monovalent organic group
  • A is -O- or -NR N -
  • R N is a hydrogen atom or a monovalent organic group
  • Z U1 is an m-valent organic group
  • Z U2 is an (n+1)-valent organic group
  • X is a radical polymerizable group
  • n is an integer of 1 or more
  • m is an integer of 1 or more.
  • R U1 is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
  • R 3 N is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
  • the above-mentioned hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms.
  • the above-mentioned hydrocarbon group includes a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
  • R N represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.
  • the hydrocarbon group includes the same as those exemplified for ZU1 , and preferred embodiments are also the same.
  • X is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group.
  • a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferable, and a (meth)acryloxy group is more preferable.
  • n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.
  • m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.
  • the cross-linking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group.
  • the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group.
  • the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, still more preferably an ethyleneoxy group or a propyleneoxy group, and particularly preferably an ethylene group.
  • the alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U. In this case, the number of repetitions of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6.
  • R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.
  • the crosslinking agent U may have, in the molecule, two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (when a polyalkyleneoxy group is formed, the group is a polyalkyleneoxy group), an amide group, and a cyano group.
  • the hydroxy group, alkyleneoxy group, amide group and cyano group may be present at any position of the crosslinking agent U. From the viewpoint of chemical resistance, however, it is also preferable that the crosslinking agent U is such that at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, amide group and cyano group and at least one radical polymerizable group contained in the crosslinking agent U are linked via a linking group containing a urea bond or a urethane bond (hereinafter, also referred to as "linking group L2-1").
  • the crosslinking agent U contains only one radically polymerizable group
  • the radically polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").
  • the crosslinking agent U contains an alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2
  • the structure bonded to the side of the alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof.
  • hydrocarbon group a hydrocarbon group having 20 or less carbon atoms is preferable, a hydrocarbon group having 18 or less carbon atoms is more preferable, and a hydrocarbon group having 16 or less carbon atoms is even more preferable.
  • hydrocarbon group a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond thereof can be mentioned.
  • a preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking agent U described above.
  • the structure bonded to the side of the amide group opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof.
  • the hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms.
  • examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by bonds thereof.
  • a preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking agent U described above.
  • the carbon atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2.
  • the crosslinking agent U has a hydroxy group.
  • the crosslinking agent U preferably contains an aromatic group.
  • the aromatic group is preferably directly bonded to a urea bond or a urethane bond contained in the crosslinking agent U.
  • the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.
  • the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure.
  • the aromatic heterocyclic group is preferably a 5-membered or 6-membered aromatic heterocyclic group.
  • aromatic heterocyclic ring in such an aromatic heterocyclic group examples include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be further condensed with other rings, such as indole and benzimidazole.
  • the heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the aromatic group is preferably contained in a linking group that links two or more radically polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radically polymerizable group contained in the crosslinking agent U.
  • the number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10.
  • the crosslinking agent U contains two or more urea bonds or urethane bonds in total, when it contains two or more radically polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radically polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond or urethane bond and the radically polymerizable group may be within the above range.
  • the "number of atoms (linking chain length) between a urea bond or a urethane bond and a polymerizable group” refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked that links these objects with the shortest length (minimum number of atoms).
  • the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.
  • the crosslinking agent U is a compound having a structure that does not have an axis of symmetry.
  • the fact that the crosslinking agent U does not have an axis of symmetry means that the compound is a bilaterally asymmetric compound that does not have an axis that would produce an identical molecule to the original molecule by rotating the entire compound.
  • the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that since the crosslinking agent U does not have an axis of symmetry, aggregation of the crosslinking agents U within the composition film is suppressed.
  • the molecular weight of the crosslinking agent U is preferably 100-2,000, more preferably 150-1500, and even more preferably 200-900.
  • the method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a compound having a radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxy group or an amino group.
  • crosslinking agent U Specific examples of the crosslinking agent U are shown below, but the crosslinking agent U is not limited thereto.
  • a difunctional methacrylate or acrylate for the resin composition.
  • the compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexyl 1,5-dimethylphenyl ...
  • PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain.
  • a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent.
  • the monofunctional radical crosslinking agent a compound having a boiling point of 100° C. or more under normal pressure is also preferred in order to suppress volatilization before exposure.
  • the difunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
  • the content of the radical crosslinking agent is preferably more than 0 mass% and not more than 60 mass% based on the total solid content of the resin composition.
  • the lower limit is more preferably 5 mass% or more.
  • the upper limit is more preferably 50 mass% or less, and even more preferably 30 mass% or less.
  • the radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
  • the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photoacid generator or photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof.
  • the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
  • Other cross-linking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022/145355, the disclosures of which are incorporated herein by reference.
  • the resin composition of the present invention preferably contains a polymerization initiator.
  • the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • the photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.
  • the photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm).
  • the molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles
  • oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, ⁇ -aminoketone compounds such as aminoacetophenones, ⁇ -hydroxyketone compounds such as hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc.
  • ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference.
  • Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd.
  • Nippon Kayaku Co., Ltd. is also preferably used.
  • hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.
  • ⁇ -Hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).
  • Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.
  • aminoacetophenone initiator acylphosphine oxide initiator, and metallocene compound
  • aminoacetophenone initiator acylphosphine oxide initiator, and metallocene compound
  • the compounds described in paragraphs 0161 to 0163 of WO 2021/112189 can also be suitably used.
  • the contents of this specification are incorporated herein.
  • an oxime compound is more preferably used as a photoradical polymerization initiator.
  • an oxime compound By using an oxime compound, it becomes possible to more effectively improve the exposure latitude.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.
  • oxime compounds include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, the compounds described in JP-A-2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.
  • Preferred oxime compounds include, for example, compounds having the following structure, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one.
  • an oxime compound as a photoradical polymerization initiator.
  • oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemistry Co., Ltd.), and SpeedCure PDO (SARTOMER Also usable are oxime compounds having the following structure:
  • an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of WO 2021/112189 an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, or an oxime compound having a fluorine atom can be used.
  • oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group-containing substituent bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of WO 2021/020359 can also be used. The contents of these compounds are incorporated herein by reference.
  • an oxime compound having an aromatic ring group Ar OX1 in which an electron-withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
  • the electron-withdrawing group of the aromatic ring group Ar OX1 includes an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
  • the benzoyl group may have a substituent.
  • the substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group, and further preferably an alkoxy group, an alkyl
  • the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), and more preferably the compound represented by the formula (OX2).
  • R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group; R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl
  • R X12 is an electron-withdrawing group
  • R X10 , R X11 , R X13 and R X14 are each a hydrogen atom.
  • oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.
  • oxime compounds include oxime compounds having specific substituents as disclosed in JP 2007-269779 A and oxime compounds having thioaryl groups as disclosed in JP 2009-191061 A, the contents of which are incorporated herein by reference.
  • the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.
  • the photoradical polymerization initiator is a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound.
  • At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound is more preferred, and a metallocene compound or an oxime compound is even more preferred.
  • a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
  • two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity.
  • crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time, and improving the stability of the resin composition over time.
  • bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015/004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017/033680, paragraphs 0039 to 0055; compound (E) and compound (G) described in WO-T-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Publication No.
  • the content is preferably 0.1 to 30 mass% based on the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking caused by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.
  • the resin composition may contain a sensitizer.
  • the sensitizer absorbs specific active radiation and becomes electronically excited.
  • the sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur.
  • the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and are decomposed to generate a radical, an acid, or a base.
  • Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based compounds, and the like.
  • sensitizer examples include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, and p-dimethylaminobenzylidene indanone.
  • the content of the sensitizer is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %.
  • the sensitizer may be used alone or in combination of two or more types.
  • the resin composition of the present invention may contain a chain transfer agent.
  • the chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684.
  • Examples of the chain transfer agent include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization.
  • RAFT Reversible Addition Fragmentation Chain Transfer
  • chain transfer agent may be the compound described in paragraphs 0152 to 0153 of WO 2015/199219, the contents of which are incorporated herein by reference.
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total solid content of the resin composition.
  • the chain transfer agent may be one type or two or more types. When there are two or more types of chain transfer agents, the total is preferably within the above range.
  • the resin composition of the present invention contains two or more types of polymerization initiators.
  • the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.
  • the content of the thermal polymerization initiator is preferably 20 to 70 mass%, and more preferably 30 to 60 mass%, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.
  • the content of the photoacid generator is preferably 20 to 70 mass%, and more preferably 30 to 60 mass%, relative to the total content of the photopolymerization initiator and the photoacid generator.
  • thermal polymerization initiator examples include a thermal radical polymerization initiator.
  • a thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be promoted, so that the solvent resistance can be further improved.
  • thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A, the contents of which are incorporated herein by reference.
  • thermal polymerization initiator When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%.
  • the resin composition may contain only one type of thermal polymerization initiator, or may contain two or more types. When two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention may contain a base generator.
  • the base generator is a compound that can generate a base by physical or chemical action.
  • Preferred base generators include thermal base generators and photobase generators.
  • the resin composition preferably contains a base generator.
  • the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, and the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package can be improved.
  • the base generator may be an ionic base generator or a nonionic base generator.
  • Examples of the base generated from the base generator include secondary amines and tertiary amines.
  • the base generator is not particularly limited, and a known base generator can be used.
  • Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, ⁇ -lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds.
  • Specific examples of the non-ionic base generator include the compounds described in paragraphs 0249 to 0275 of WO 2022/145355. The above descriptions are incorporated herein by
  • Base generators include, but are not limited to, the following compounds:
  • the molecular weight of the nonionic 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.
  • Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018/038002.
  • ammonium salts include, but are not limited to, the following compounds:
  • iminium salts include, but are not limited to, the following compounds:
  • the base generator is preferably an amine in which the amino group is protected by a t-butoxycarbonyl group, from the viewpoints of storage stability and generating a base by deprotection during curing.
  • Amine compounds protected by a t-butoxycarbonyl group include, for example, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, Diol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-
  • the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition.
  • the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
  • the upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
  • the base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains a solvent.
  • the resin composition of the present invention preferably contains a solvent having at least one of an amide bond or a hydroxyl group as a solvent. Such a solvent has excellent solubility for compound A and can suppress aggregation of these compounds.
  • the solvent may be any known solvent.
  • 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.
  • Esters for example, 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, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -valerolactone, alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (for example,
  • alkyloxypropionic acid alkyl esters include alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc.
  • Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene 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 dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, di
  • ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.
  • cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.
  • dimethyl sulfoxide is preferred.
  • amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.
  • ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.
  • 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, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.
  • An embodiment in which toluene is further added to these combined solvents in an amount of about 1 to 10% by mass based on the total mass of the solvent is also one of the preferred embodiments of the present invention.
  • an embodiment containing ⁇ -valerolactone as a solvent is one of the preferred embodiments of the present invention.
  • the content of ⁇ -valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
  • the upper limit of the content is not particularly limited and may be 100% by mass.
  • the content may be determined taking into consideration the solubility of components such as a specific resin contained in the resin composition, and the like.
  • the solvent preferably contains 60 to 90% by mass of ⁇ -valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of ⁇ -valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of ⁇ -valerolactone and 15 to 25% by mass of dimethyl sulfoxide, relative to the total mass of the solvent.
  • the content of the solvent is preferably an amount that results in a total solids concentration of the resin composition of the present invention of 5 to 80 mass%, more preferably an amount that results in a total solids concentration of 5 to 75 mass%, even more preferably an amount that results in a total solids concentration of 10 to 70 mass%, and even more preferably an amount that results in a total solids concentration of 20 to 70 mass%.
  • the content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method. When two or more types of solvents are contained, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc.
  • the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a ⁇ -ketoester compound, and an amino compound.
  • the compound corresponding to the above-mentioned compound A does not correspond to the metal adhesion improver and the silane coupling agent referred to here.
  • silane coupling agent examples include the compounds described in paragraph 0316 of International Publication No. 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein. 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. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group. In addition, the following R includes a structure derived from a blocking agent in a blocked isocyanate group.
  • the blocking agent may be selected according to the desorption temperature, and examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds.
  • examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds.
  • caprolactam and the like are preferred.
  • Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-
  • the silane include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(a
  • an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
  • examples of such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1).
  • R 1 S1 represents a monovalent organic group
  • R 1 S2 represents a hydrogen atom, a hydroxyl group or an alkoxy group
  • n represents an integer of 0 to 2.
  • R S1 is preferably a structure containing a polymerizable group.
  • Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group.
  • R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
  • n represents an integer of 0 to 2, and is preferably 1.
  • n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and further preferably that n is 1 in at least two.
  • oligomer type compounds commercially available products can be used, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Aluminum-based adhesion promoter examples include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.
  • metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By making the content equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer will be good, and by making the content equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern will be good. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.
  • the resin composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively suppressed.
  • the migration inhibitor referred to here does not include compounds corresponding to the above-mentioned compound X1 or compound X2.
  • the migration inhibitor examples include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds.
  • a heterocycle pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring
  • triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole
  • tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.
  • Ion trapping agents that capture anions such as halogen ions can also be used as migration inhibitors.
  • Other migration inhibitors that can be used include the rust inhibitors described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compounds described in paragraph 0052 of JP 2011-059656 A, the compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520 A, and the compounds described in paragraph 0166 of WO 2015/199219 A, the contents of which are incorporated herein by reference.
  • migration inhibitors include the following compounds:
  • the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %, based on the total solid content of the resin composition.
  • the migration inhibitor may be one type or two or more types. When two or more types of migration inhibitors are used, it is preferable that the total is within the above range.
  • the resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.
  • a polymerization inhibitor such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.
  • the polymerization inhibitor referred to here does not include compounds corresponding to the above-mentioned compound X1 or compound X2.
  • polymerization inhibitor examples include the compounds described in paragraph 0310 of WO 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc.
  • the contents of this document are incorporated herein by reference.
  • the content of the polymerization inhibitor is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %.
  • the polymerization inhibitor may be one type or two or more types. When two or more types of polymerization inhibitors are used, it is preferable that the total is within the above range.
  • the resin composition of the present invention may contain at least one compound selected from the group consisting of a compound having a urea bond (urea compound), a compound having a carbodiimide structure (carbodiimide compound), and a compound having an isourea bond (isourea compound) (hereinafter also referred to as a "urea compound, etc.”).
  • urea compound a compound having a urea bond
  • carbodiimide compound a compound having a carbodiimide structure
  • isourea compound hereinafter also referred to as a "urea compound, etc.”
  • the resin composition of the present invention further contains a compound having a urea bond.
  • the urea compounds and the like referred to here do not include the above-mentioned compound A, the above-mentioned polymerizable compounds, and compounds corresponding to silane coupling agents.
  • Examples of the urea compound include the compound represented by the following formula (UR-1), examples of the carbodiimide compound include the compound represented by the following formula (UR-2), and examples of the isourea compound include the compound represented by the following formula (UR-3).
  • R 11 and R 12 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent
  • R 21 and R 22 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent
  • R 31 and R 32 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent
  • R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
  • R 11 and R 12 each independently represent preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having at least one substituent selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, and a quaternary ammonium group, as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
  • the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms for R 11 and R 12 is preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms, and still more preferably an ethyl group, an isopropyl group, a t-butyl group, or a cyclohexyl group.
  • R 11 and R 12 may each independently be an aliphatic hydrocarbon group having 2 to 7 carbon atoms and having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group.
  • the aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more of the above-mentioned substituents, but it is also preferable that the aliphatic hydrocarbon group has only one of the above-mentioned substituents.
  • R 21 and R 22 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
  • R 21 and R 22 are preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
  • R 21 and R 22 preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R 21 and R 22 are the same as those described above for R 11 and R 12 , respectively.
  • R 31 and R 32 are preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
  • preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R 31 and R 32 are the same as those described above for R 11 and R 12 , respectively.
  • R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and even more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • R 33 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group, and more preferably an ethyl group.
  • urea compounds include, but are not limited to, dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea.
  • the total content of the urea compounds and the like is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and even more preferably 1.0 to 6.0 parts by mass, per 100 parts by mass of the specific resin.
  • the urea compounds and the like may be used alone or in combination of two or more. When two or more bases are used in combination in the base-containing treatment liquid, it is preferable that the total content thereof is within the above range.
  • the resin composition of the present invention also preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.
  • a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.
  • the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022/202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of which are incorporated herein by reference.
  • the content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.
  • the resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained.
  • additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained.
  • auxiliaries e.g., defoamers, flame retardants, etc.
  • the viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and even more preferably 2,500 mm 2 /s to 8,000 mm 2 /s. If it is within the above range, it is easy to obtain a coating film with high uniformity.
  • the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If the water content is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.
  • the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
  • metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, it is preferable that the total of these metals is within the above range.
  • methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention, lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.
  • the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion.
  • those present in the form 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.
  • Halogen atoms include chlorine atoms and bromine atoms.It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range.
  • a preferred method for adjusting the content of halogen atoms is ion exchange treatment.
  • a conventionally known container can be used as the container for the resin composition of the present invention.
  • the container it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure of six types of resin, in order to prevent impurities from being mixed into the raw materials or the resin composition of the present invention.
  • An example of such a container is the container described in JP 2015-123351 A.
  • a cured product of the resin composition By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
  • the cured product of the present invention is a cured product obtained by curing a resin composition.
  • the resin composition is preferably cured by heating, and the heating temperature is more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C.
  • the form of the cured product of the resin composition is not particularly limited, and can be selected according to the application, such as a film, a rod, a sphere, or a pellet.
  • the cured product is preferably a film.
  • the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function.
  • the film thickness of the cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
  • the shrinkage percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
  • the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
  • the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
  • the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.
  • the resin composition of the present invention can be prepared by mixing the above-mentioned components.
  • the resin composition can be prepared, for example, by the method described in paragraphs 0283 to 0284 of WO 2022/210532. The descriptions therein are incorporated herein by reference.
  • the method for producing a cured product of the present invention preferably includes a film formation step of applying the resin composition onto a substrate to form a film. It is more preferable that the method for producing a cured product includes the above-mentioned film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern.
  • the method for producing a cured product includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step.
  • the method for producing a cured product preferably includes the film-forming step and a step of heating the film (heating step).
  • the heating step is preferably a heating step in which the film is heated at 50 to 450°C.
  • the method for producing a cured product of the present invention may further include the steps described in WO 2022/210532, such as a drying step, a post-exposure heating step, a post-development exposure step, and a metal layer forming step.
  • a drying step such as a drying step, a post-exposure heating step, a post-development exposure step, and a metal layer forming step.
  • Each step in the method for producing a cured product of the present invention can be carried out in the same manner as each step described in paragraphs 0285 to 0325 of WO 2022/210532. These descriptions are incorporated herein by reference.
  • Examples of the field of application of the method for producing the cured product of the present invention or the cured product include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc.
  • Other examples include etching patterns of sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or insulating films for mounting applications such as those described above.
  • the method for producing the cured product of the present invention or the cured product of the present invention can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, and for producing protective lacquers and dielectric layers in electronics, especially microelectronics.
  • the laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention.
  • the laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers.
  • at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.
  • the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention multiple times.
  • the laminate of the present invention preferably includes two or more layers made of a cured product, and includes a metal layer between any two of the layers made of the cured product.
  • the metal layer is preferably formed by the metal layer forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer made of a cured product between the steps for producing a cured product which are performed multiple times.
  • a preferred embodiment of the metal layer forming step is as described above.
  • a laminate including at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order can be mentioned as a preferred example.
  • the layer made of the first cured product and the layer made of the second cured product are preferably layers made of the cured product of the present invention.
  • the resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions.
  • the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
  • the method for producing the laminate of the present invention preferably includes a lamination step.
  • the lamination process is a series of processes including performing at least one of (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) a heating process and a post-development exposure process again on the surface of the pattern (resin layer) or metal layer in this order.
  • at least one of (a) the film formation process and (d) the heating process and the post-development exposure process may be repeated.
  • a metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying process and the like as appropriate.
  • a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step.
  • An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.
  • the lamination step is preferably carried out 2 to 20 times, and more preferably 2 to 9 times.
  • a structure of 2 to 20 resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred.
  • the layers may be the same or different in composition, shape, film thickness, etc.
  • a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.
  • a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.
  • the following may be repeated in this order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step; or (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step.
  • the method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
  • the surface activation treatment step is usually carried out after the metal layer formation step, but after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be subjected to a surface activation treatment step before the metal layer formation step is carried out.
  • the surface activation treatment may be performed on at least a part of the metal layer, or on at least a part of the resin composition layer after exposure, or on at least a part of both the metal layer and the resin composition layer after exposure.
  • 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 area of the metal layer on which the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface can be improved. It is preferable to perform the surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface that has been surface-activated.
  • the resin composition layer when performing negative development, etc., when the resin composition layer is cured, it is less likely to be damaged by the surface treatment, and the adhesion is likely to be improved.
  • the surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • the present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention.
  • the present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product or the method for producing the laminate of the present invention.
  • semiconductor devices using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer the descriptions in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357 can be referred to, and the contents of these are incorporated herein by reference.
  • Resin 2A was a structure represented by the following formula (P-2):
  • the molecular weight of Resin 2A was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000.
  • the Mw of resin 3 was 20,000
  • the Mw of resin 4 was 20,000
  • the Mw of resin 5 was 20,000
  • the Mw of resin 6 was 20,000
  • the Mw of resin 7 was 20,000
  • the Mw of resin 8 was 20,000
  • the Mw of resin 9 was 20,000
  • the Mw of resin 12 was 20,000
  • the Mw of resin 13 was 20,000
  • the Mw of resin 14 was 20,000
  • the Mw of resin 15 was 20,000. It was confirmed by 1 H-NMR that the structures of resins 3 to 9 and resins 12 to 15 were structures represented by the following formulas (P-3) to (P-9) and formulas (P-12) to (P-15), respectively.
  • Synthesis Example 10 Synthesis of polyimide (resin 10) In a flask equipped with a condenser and a stirrer, 18.0 g (40.5 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP) while removing moisture. Then, 7.95 g (39.7 mmol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 3 hours, and further stirred at 45°C for 3 hours.
  • NMP N-methylpyrrolidone
  • the molecular weight of resin 10 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 20,000. It was confirmed by 1 H-NMR that the structure of resin 10 was a structure represented by the following formula (P-10).
  • Examples and Comparative Examples> In each of the examples, the components shown in the following table were mixed to obtain a resin composition. In each of the comparative examples, the components shown in the following table were mixed to obtain a comparative composition. Specifically, the content (blended amount) of each component shown in the table other than the solvent is the amount (parts by mass) shown in the "parts by mass” column of each column in the table. The contents (amounts) of the solvents were set so that the solids concentration of the composition was the value (mass %) of "Solids concentration” in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvents was the ratio shown in the "Ratio" column in the table. The obtained resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter having a pore width of 0.8 ⁇ m. In the table, "-" indicates that the composition does not contain the corresponding component.
  • Resins 1 to 15 Resins 1 to 15 obtained by the above synthesis examples
  • C-1 to C-23 Compounds having the following structure: C-1 to C-23 are compounds corresponding to compound A (wherein, in the structural formula, Me represents a methyl group, and Et represents an ethyl group).
  • CR-1 A compound having the following structure. CR-1 is a compound that does not fall under Compound A (however, in the structural formula, Et represents an ethyl group).
  • CX-1 to CX-4 Compounds having the following structures. CX-1 to CX-4 are compounds that do not fall under compound A (however, in the structural formulas, Me represents a methyl group and Et represents an ethyl group).
  • E-1 to E-6, E-9, E-11 to E-19 Compounds having the following structures
  • E-7 Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid
  • E-8 The following synthetic product
  • NMP N-methyl-2-pyrrolidone
  • EL Ethyl lactate
  • DMSO Dimethyl sulfoxide
  • GBL ⁇ -butyrolactone
  • GVL ⁇ -valerolactone
  • MDMPA 3-methoxy-N,N-dimethylpropanamide
  • Toluene Toluene
  • the resin composition layer or the comparative composition layer on the copper substrate was exposed to light with an exposure wavelength (nm) shown in the "Exposure wavelength (nm)" column of the table using a stepper as a light source and an exposure energy of 500 mJ/ cm2 , and using a photomask with a 100 ⁇ m square unmasked portion formed therein in the examples marked with "CP” in the “Developer” column of the table, and using a photomask with a 100 ⁇ m square masked portion formed therein in the examples marked with "T” in the "Developer” column of the table.
  • the resin composition layer or the comparative composition layer on the copper substrate was subjected to laser direct imaging exposure in an area of 100 ⁇ m square with light of the exposure wavelength (nm) shown in the "Exposure wavelength (nm)” column in the table, using a direct exposure device (Adtec DE-6UH III) as a light source with an exposure energy of 500 mJ/cm2, without using a photomask. Thereafter, the resin layer was developed for 60 seconds with the developer shown in the "Developer” column in the table.
  • "CP” in the table means cyclopentanone
  • "T” in the table means a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.
  • the temperature was increased at a rate of 10°C/min in a nitrogen atmosphere, and after reaching the temperature given in the "Cure temperature (°C)” column in the table, the above temperature was maintained for the time given in the "Cure time (min)” column in the table to obtain a cured product.
  • the resin film obtained in each Example was heated at a heating rate of 10°C/min in a nitrogen atmosphere using an infrared lamp heating device (Advance Riko Co., Ltd., RTP-6).
  • the cured product formed from the resin composition of the present invention which contains a compound corresponding to compound A, has excellent substrate adhesion after high-temperature storage tests.
  • the comparative composition according to Comparative Example 1 does not contain a compound corresponding to compound A. It is clear that the cured product formed from such a comparative composition has poor substrate adhesion after a high-temperature storage test.
  • Example 201 The resin composition used in Example 1 was applied in a layer form by spin coating on the surface of the thin copper layer of the resin substrate on which the thin copper layer was formed, and dried at 100° C. for 5 minutes to form a photosensitive film with a thickness of 20 ⁇ m, which was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line and space pattern and a line width of 10 ⁇ m). After the exposure, the layer was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
  • the temperature was increased at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 180 minutes to form an interlayer insulating film for a rewiring layer.
  • This interlayer insulating film for a rewiring layer had excellent insulating properties. Furthermore, when a semiconductor device was manufactured using this interlayer insulating film for redistribution layers, it was confirmed that the device operated without any problems.

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Abstract

Provided is a resin composition containing: at least one resin selected from the group consisting of cyclized resins and precursors thereof; and a compound A represented by formula (A1-1). Also provided are a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device. In formula (A1-1), R1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, R2 is a hydrogen atom or an arbitrary organic group, at least two from among R1 and R2 may be bonded to form a ring structure, n represents an integer of 1-3, m represents an integer of 1 or more, and R3 represents an m-valent organic group.

Description

樹脂組成物、硬化物、積層体、硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、及び、半導体デバイスResin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, and semiconductor device

 本発明は、樹脂組成物、硬化物、積層体、硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、及び、半導体デバイスに関する。 The present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device.

 現代では様々な分野において、樹脂を含む樹脂組成物から製造された樹脂材料を活用することが行われている。
 例えば、ポリイミド等の環化樹脂は、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。
2. Description of the Related Art Nowadays, resin materials produced from resin compositions containing resins are being used in various fields.
For example, cyclized resins such as polyimide are used in various applications because of their excellent heat resistance and insulating properties. The applications are not particularly limited, but for example, in the case of semiconductor devices for mounting, they can be used as insulating films, sealing materials, or protective films. They are also used as base films or coverlays for flexible substrates.

 例えば上述した用途において、ポリイミド等の環化樹脂は、環化樹脂、又は、ポリイミド前駆体等の環化樹脂の前駆体を含む樹脂組成物の形態で用いられる。
 このような樹脂組成物を、例えば塗布等により基材に適用して感光膜を形成し、その後、必要に応じて露光、現像、加熱等を行うことにより、硬化物を基材上に形成することができる。
 ポリイミド前駆体等の上記環化樹脂の前駆体は、例えば加熱により環化され、硬化物中でポリイミド等の環化樹脂となる。
 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。ポリイミド等の環化樹脂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。
 また、このような樹脂材料について、基材との密着性に優れることが求められており、様々な方法により基材との密着性を向上させることが検討されている。
For example, in the applications mentioned above, the cyclized resin, such as a polyimide, is used in the form of a resin composition that includes the cyclized resin or a precursor of the cyclized resin, such as a polyimide precursor.
Such a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate.
The precursor of the cyclized resin, such as a polyimide precursor, is cyclized, for example, by heating, and becomes a cyclized resin, such as a polyimide, in the cured product.
Since the resin composition can be applied by a known coating method, etc., it can be said to have excellent adaptability in manufacturing, for example, high degree of freedom in designing the shape, size, application position, etc. of the resin composition when applied. In addition to the high performance of cyclized resins such as polyimide, from the viewpoint of such excellent adaptability in manufacturing, industrial application development of the above-mentioned resin composition is expected to continue.
Furthermore, such resin materials are required to have excellent adhesion to substrates, and various methods for improving adhesion to substrates have been investigated.

 例えば、特許文献1には、ポリイミド前駆体、ポリベンゾオキサゾール前駆体及びポリアミドイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂、及び、アルコキシシリル基を有する光塩基発生剤を含む、硬化性樹脂組成物が記載されている。
 特許文献2には、以下の成分:(A)ポリイミド前駆体;(B)光重合開始剤;(C)特定の構造であるシランカップリング剤;及び(D)γ-ブチロラクトン、ジメチルスルホキシド、テトラヒドロフルフリルアルコール、アセト酢酸エチル、こはく酸ジメチル、マロン酸ジメチル、及びε-カプロラクトンからなる群から選択される少なくとも1種を含有する、有機溶媒;を含む、ネガ型感光性樹脂組成物が記載されている。
For example, Patent Document 1 describes a curable resin composition containing at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor, and a photobase generator having an alkoxysilyl group.
Patent Document 2 describes a negative type photosensitive resin composition containing the following components: (A) a polyimide precursor; (B) a photopolymerization initiator; (C) a silane coupling agent having a specific structure; and (D) an organic solvent containing at least one selected from the group consisting of γ-butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ε-caprolactone.

国際公開第2022/050278号International Publication No. 2022/050278 特開2020-173431号公報JP 2020-173431 A

 環化樹脂又はその前駆体を含む樹脂組成物について、基材との密着性に優れた硬化物が得られることが求められている。 There is a demand for resin compositions containing cyclized resins or their precursors to produce cured products that have excellent adhesion to substrates.

 本発明は、基材との密着性に優れた硬化物が得られる樹脂組成物、上記樹脂組成物を硬化してなる硬化物、上記硬化物を含む積層体、上記硬化物の製造方法、上記積層体の製造方法、上記硬化物の製造方法を含む半導体デバイスの製造方法、及び、上記硬化物を含む半導体デバイスを提供することを目的とする。 The present invention aims to provide a resin composition that can give a cured product that has excellent adhesion to a substrate, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product.

 本発明の代表的な実施態様の例を以下に示す。
<1> 環化樹脂及びその前駆体からなる群より選ばれた少なくとも1種の樹脂、並びに、
 式(A1-1)で表される化合物Aを含む
 樹脂組成物。

 式(A1-1)中、Rは酸素原子、窒素原子及び硫黄原子から選ばれる少なくとも1つ以上の原子を有する有機基であり、Rが複数ある場合は同一であってもよいし、異なっていてもよく、Rは水素原子又は上記Rに該当しない任意の有機基であり、Rが複数ある場合は同一であってもよいし、異なっていてもよく、R及びRのうち少なくとも2つが結合して環構造を形成してもよく、nは1~3の整数を表し、mは1以上の整数を表し、Rはm価の有機基を表す。
<2> 化合物Aが、下記式(A1-2)で表される化合物である、<1>に記載の樹脂組成物。

 式(A1-2)中、Rは酸素原子、窒素原子及び硫黄原子から選ばれる少なくとも1つ以上の原子を有する有機基であり、Rが複数ある場合は同一であってもよいし、異なっていてもよく、Rは水素原子又は上記Rに該当しない任意の有機基であり、Rが複数ある場合は同一であってもよいし、異なっていてもよく、R及びRのうち少なくとも2つが結合して環構造を形成してもよく、nは1~3の整数を表し、Lは2価の連結基を表し、Rは水素原子又は1価の有機基を表す。
<3> 上記式(A1-1)におけるRのうち少なくとも1つが、アミノ基またはエステル結合を含む、<1>に記載の樹脂組成物。
<4> 上記式(A1-1)におけるRが、下記式(R3-1)で表される基である、<1>に記載の樹脂組成物。

 式(R3-1)中、L31はそれぞれ独立に、2価の連結基を表し、R31はそれぞれ独立に、水素原子が置換基で置換されてもよい芳香族炭化水素基、又は、*-C(=O)R32-#で表される基を表し、*は式(R3-1)中の窒素原子との結合部位を表し、#は式(R3-1)中のL32との結合部位を表し、R32は有機基を表し、mは1以上の整数を表し、mが1である場合L32は水素原子又は置換基を表し、mが2以上である場合L32は単結合又はm価の連結基を表し、*は式(A1-1)中のケイ素原子との結合部位を表す。
<5> 環化樹脂及びその前駆体からなる群より選ばれた少なくとも1種の樹脂、並びに、
 式(A2-1)で表される化合物Aを含む
 樹脂組成物。

 式(A2-1)中、R21はHSP値が17.0~27.0MPa1/2である有機基であり、R21が複数ある場合は同一であってもよいし、異なっていてもよく、R22は水素原子又は上記R21に該当しない任意の有機基であり、R22が複数ある場合は同一であってもよいし、異なっていてもよく、R21及びR22のうち少なくとも2つが結合して環構造を形成してもよく、nは1~3の整数を表し、mは1以上の整数を表し、R23はm価の有機基を表す。
<6> 上記樹脂がポリイミド又はポリイミド前駆体である、<1>~<5>のいずれか1つに記載の樹脂組成物。
<7> 上記樹脂がポリイミドである、<1>~<6>のいずれか1つに記載の樹脂組成物。
<8> 光重合開始剤を更に含む、<1>~<7>のいずれか1つに記載の樹脂組成物。
<9> 増感剤を更に含む、<8>に記載の樹脂組成物。
<10> ウレア結合を有する化合物を更に含む、<1>~<9>のいずれか1つに記載の樹脂組成物。
<11> ウレア結合及びウレタン結合の少なくとも一方を有する重合性化合物を更に含む、<1>~<10>のいずれか1つに記載の樹脂組成物。
<12> アミド結合又はヒドロキシ基の少なくとも一つを有する溶剤を更に含む、<1>~<11>のいずれか1つに記載の樹脂組成物。
<13> 再配線層用層間絶縁膜の形成に用いられる、<1>~<12>のいずれか1つに記載の樹脂組成物。
<14> <1>~<13>のいずれか1つに記載の樹脂組成物を硬化してなる硬化物。
<15> <14>に記載の硬化物からなる層を2層以上含み、上記硬化物からなる層同士のいずれかの間に金属層を含む積層体。
<16> <1>~<13>のいずれか1つに記載の樹脂組成物を基材上に適用して膜を形成する膜形成工程を含む、硬化物の製造方法。
<17> 上記膜を選択的に露光する露光工程及び上記膜を現像液を用いて現像してパターンを形成する現像工程を含む、<16>に記載の硬化物の製造方法。
<18> 上記膜を50~450℃で加熱する加熱工程を含む、<16>又は<17>に記載の硬化物の製造方法。
<19> <16>~<18>のいずれか1つに記載の硬化物の製造方法を含む、積層体の製造方法。
<20> <16>~<18>のいずれか1つに記載の硬化物の製造方法を含む、半導体デバイスの製造方法。
<21> <14>に記載の硬化物を含む、半導体デバイス。
Representative embodiments of the present invention are illustrated below.
<1> At least one resin selected from the group consisting of cyclized resins and precursors thereof, and
A resin composition comprising a compound A represented by formula (A1-1):

In formula (A1-1), R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different, R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different, at least two of R 1 and R 2 may be bonded to form a ring structure, n represents an integer of 1 to 3, m represents an integer of 1 or more, and R 3 represents an m-valent organic group.
<2> The resin composition according to <1>, wherein compound A is a compound represented by the following formula (A1-2):

In formula (A1-2), R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different, R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different, at least two of R 1 and R 2 may be bonded to form a ring structure, n represents an integer of 1 to 3, L represents a divalent linking group, and R 4 represents a hydrogen atom or a monovalent organic group.
<3> The resin composition according to <1>, wherein at least one of R 1 in the formula (A1-1) contains an amino group or an ester bond.
<4> The resin composition according to <1>, wherein R 3 in the above formula (A1-1) is a group represented by the following formula (R3-1):

In formula (R3-1), L 31 each independently represents a divalent linking group, R 31 each independently represents an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or a group represented by *-C(═O)R 32 -#, * represents a bonding site to the nitrogen atom in formula (R3-1), # represents a bonding site to L 32 in formula (R3-1), R 32 represents an organic group, m represents an integer of 1 or more, when m is 1, L 32 represents a hydrogen atom or a substituent, and when m is 2 or more, L 32 represents a single bond or an m-valent linking group, and * represents a bonding site to the silicon atom in formula (A1-1).
<5> At least one resin selected from the group consisting of cyclized resins and precursors thereof, and
A resin composition comprising a compound A represented by formula (A2-1):

In formula (A2-1), R 21 is an organic group having an HSP value of 17.0 to 27.0 MPa 1/2 , and when there is a plurality of R 21 , they may be the same or different, R 22 is a hydrogen atom or any organic group not corresponding to the above R 21 , and when there is a plurality of R 22 , they may be the same or different, at least two of R 21 and R 22 may be bonded to form a ring structure, n represents an integer of 1 to 3, m represents an integer of 1 or more, and R 23 represents an m-valent organic group.
<6> The resin composition according to any one of <1> to <5>, wherein the resin is a polyimide or a polyimide precursor.
<7> The resin composition according to any one of <1> to <6>, wherein the resin is a polyimide.
<8> The resin composition according to any one of <1> to <7>, further comprising a photopolymerization initiator.
<9> The resin composition according to <8>, further comprising a sensitizer.
<10> The resin composition according to any one of <1> to <9>, further comprising a compound having a urea bond.
<11> The resin composition according to any one of <1> to <10>, further comprising a polymerizable compound having at least one of a urea bond and a urethane bond.
<12> The resin composition according to any one of <1> to <11>, further comprising a solvent having at least one of an amide bond or a hydroxyl group.
<13> The resin composition according to any one of <1> to <12>, which is used for forming an interlayer insulating film for a redistribution layer.
<14> A cured product obtained by curing the resin composition according to any one of <1> to <13>.
<15> A laminate comprising two or more layers made of the cured product according to <14>, and a metal layer between any two adjacent layers made of the cured product.
<16> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of <1> to <13> onto a substrate to form a film.
<17> The method for producing a cured product according to <16>, comprising: an exposure step of selectively exposing the film to light; and a development step of developing the film with a developer to form a pattern.
<18> A method for producing a cured product according to <16> or <17>, comprising a heating step of heating the film at 50 to 450° C.
<19> A method for producing a laminate, comprising the method for producing a cured product according to any one of <16> to <18>.
<20> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <16> to <18>.
<21> A semiconductor device comprising the cured product according to <14>.

 本発明によれば、基材との密着性に優れた硬化物が得られる樹脂組成物、上記樹脂組成物を硬化してなる硬化物、上記硬化物を含む積層体、上記硬化物の製造方法、上記積層体の製造方法、上記硬化物の製造方法を含む半導体デバイスの製造方法、及び、上記硬化物を含む半導体デバイスが提供される。 The present invention provides a resin composition that can produce a cured product that has excellent adhesion to a substrate, a cured product obtained by curing the resin composition, a laminate that includes the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device that includes the method for producing the cured product, and a semiconductor device that includes the cured product.

 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)法を用いて測定した値であり、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、及び、TSKgel Super HZ2000(以上、東ソー(株)製)を直列に連結して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。ただし、溶解性が低い場合など、溶離液としてTHFが適していない場合にはNMP(N-メチル-2-ピロリドン)を用いることもできる。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。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、樹脂組成物層がある場合には、基材から樹脂組成物層へ向かう方向を「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。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。
The main embodiments of the present invention will be described below, however, the present invention is not limited to the embodiments explicitly described.
In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values before and after "to" as the lower limit and upper limit, respectively.
In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, so long as the process can achieve its intended effect.
In the description of groups (atomic groups) in this specification, when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, an "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
In this specification, unless otherwise specified, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", and "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl".
In this specification, in the structural formulae, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent, and in this specification, the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) method, and are defined as polystyrene equivalent values, unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series as columns. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as an eluent. However, when THF is not suitable as an eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. In addition, unless otherwise specified, detection in GPC measurement is performed using a UV (ultraviolet) light detector with a wavelength of 254 nm.
In this specification, when the positional relationship of each layer constituting the laminate is described as "upper" or "lower", it is sufficient that there is another layer above or below the reference layer among the multiple layers being noted. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer. Unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper" direction in this specification may be different from the vertical upward direction.
In this specification, unless otherwise specified, the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
In this specification, unless otherwise specified, the temperature is 23° C., the pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
As used herein, combinations of preferred aspects are more preferred aspects.

(樹脂組成物)
 本発明の第一の態様に係る樹脂組成物(以下、単に「第一の樹脂組成物」ともいう。)は、環化樹脂及びその前駆体からなる群より選ばれた少なくとも1種の樹脂、並びに、式(A1-1)で表される化合物Aを含む。
 本発明の第二の態様に係る樹脂組成物(以下、単に「第二の樹脂組成物」ともいう。)は、環化樹脂及びその前駆体からなる群より選ばれた少なくとも1種の樹脂、並びに、
 式(A2-1)で表される化合物Aを含む。
 以下、第一の樹脂組成物と第二の樹脂組成物とを合わせて単に「樹脂組成物」ともいう。
 以下、第一の樹脂組成物に含まれる、式(A1-1)で表される化合物Aを「第一の化合物A」ともいう。
 以下、第二の樹脂組成物に含まれる、式(A2-1)で表される化合物Aを「第二の化合物A」ともいう。
 以下、単に「化合物A」と記載した場合には、第一の化合物A、及び、第二の化合物Aの全てを指すものとする。
(Resin composition)
The resin composition according to the first aspect of the present invention (hereinafter, also simply referred to as the "first resin composition") contains at least one resin selected from the group consisting of cyclized resins and precursors thereof, and a compound A represented by formula (A1-1).
The resin composition according to the second aspect of the present invention (hereinafter, also simply referred to as the "second resin composition") comprises at least one resin selected from the group consisting of cyclized resins and precursors thereof,
It contains a compound A represented by formula (A2-1).
Hereinafter, the first resin composition and the second resin composition will be collectively referred to simply as the "resin composition".
Hereinafter, the compound A contained in the first resin composition and represented by formula (A1-1) will also be referred to as the "first compound A".
Hereinafter, the compound A contained in the second resin composition and represented by formula (A2-1) is also referred to as the "second compound A".
Hereinafter, when simply described as "compound A", it refers to both the first compound A and the second compound A.

 本発明の樹脂組成物は、露光及び現像に供される感光膜の形成に用いられることが好ましく、露光及び有機溶剤を含む現像液を用いた現像に供される膜の形成に用いられることが好ましい。
 本発明の樹脂組成物は、例えば、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等の形成に用いることができ、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、本発明の樹脂組成物は、ポジ型現像に供される感光膜の形成に用いられてもよいし、ネガ型現像に供される感光膜の形成に用いられてもよい。
 本発明において、ネガ型現像とは、露光及び現像において、現像により非露光部が除去される現像をいい、ポジ型現像とは、現像により露光部が除去される現像をいう。
 上記露光の方法、上記現像液、及び、上記現像の方法としては、例えば、後述する硬化物の製造方法の説明における露光工程において説明された露光方法、現像工程において説明された現像液及び現像方法が使用される。
The resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent.
The resin composition of the present invention can be used, for example, to form an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer.
The resin composition of the present invention may be used to form a photosensitive film to be subjected to positive development, or may be used to form a photosensitive film to be subjected to negative development.
In the present invention, negative development refers to a development in which the non-exposed areas are removed by development during exposure and development, and positive development refers to a development in which the exposed areas are removed by development.
As the exposure method, the developer, and the development method, for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the production method of the cured product described later can be used.

 本発明の樹脂組成物によれば、基材との密着性に優れた硬化物が得られる。
 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 resin composition of the present invention, a cured product having excellent adhesion to a substrate can be obtained.
The mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.

 従来より、基材との密着性等を目的として、樹脂組成物にシランカップリング剤が使用されてきた。これらのシランカップリング剤はトリメトキシシリル基など単純な無置換トリアルコキシシリル構造を有するものであった。
 本発明の第一の態様においては、トリアルコキシシリル構造のうち、少なくとも1つのアルコキシ基が、酸素原子、窒素原子及び硫黄原子から選ばれる少なくとも1つ以上の原子を有する有機基に置換されている。これにより、従来品を使用した場合に比べ、硬化膜の耐熱試験後の基材との密着性が向上することが見出された。上記効果が得られるメカニズムは定かではないが、以下の様に推察される。
 疎水的なアルコキシシリル基に極性の高いヘテロ原子が導入されたことにより、シランカップリング剤と金属基材とうの基材の相互作用性が向上し、膜の硬化時においてシランカップリング剤が基材近傍に偏在していると考えられる。その結果、従来品に比べ効率的に基材表面でゾルゲル反応が進行するため、硬化膜の基材との密着性が向上すると考えられる。
 また、本発明の第二の態様においては、トリアルコキシシリル構造のうち、少なくとも1つのアルコキシ基が、HSP値が17.0~27.0MPa1/2である有機基により置換されている。これにより、従来品を使用した場合に比べ、硬化膜の耐熱試験後の基材との密着性が向上することが見出された。上記効果が得られるメカニズムは定かではないが、以下の様に推察される。
 疎水的なアルコキシシリル基に極性の高い有機基であるHSP値が17.0~27.0MPa1/2である有機基が導入されたことにより、上述の通り膜の硬化時においてシランカップリング剤が基材近傍に偏在していると考えられる。その結果、従来品に比べ効率的に基材表面でゾルゲル反応が進行するため、硬化膜の基材との密着性が向上すると考えられる。
Silane coupling agents have been used in resin compositions for the purpose of improving adhesion to substrates, etc. These silane coupling agents have a simple unsubstituted trialkoxysilyl structure such as a trimethoxysilyl group.
In the first aspect of the present invention, at least one alkoxy group in the trialkoxysilyl structure is substituted with an organic group having at least one atom selected from oxygen atom, nitrogen atom and sulfur atom.It has been found that this improves the adhesion of the cured film to the substrate after heat resistance test compared with the case of using the conventional product.The mechanism by which the above effect is obtained is not clear, but is presumed to be as follows.
The introduction of a highly polar heteroatom into the hydrophobic alkoxysilyl group improves the interaction between the silane coupling agent and the metal substrate, and it is believed that the silane coupling agent is unevenly distributed near the substrate when the film is cured. As a result, the sol-gel reaction proceeds more efficiently on the substrate surface than with conventional products, which is believed to improve the adhesion of the cured film to the substrate.
In the second embodiment of the present invention, at least one alkoxy group in the trialkoxysilyl structure is substituted with an organic group having an HSP value of 17.0 to 27.0 MPa 1/2 . This has been found to improve the adhesion of the cured film to the substrate after heat resistance testing compared to the case where a conventional product is used. The mechanism by which the above effect is obtained is unclear, but is presumed to be as follows.
It is believed that the introduction of an organic group with a highly polar HSP value of 17.0 to 27.0 MPa 1/2 into the hydrophobic alkoxysilyl group causes the silane coupling agent to be unevenly distributed near the substrate when the film is cured, as described above. As a result, the sol-gel reaction proceeds more efficiently on the substrate surface than with conventional products, which is believed to improve the adhesion of the cured film to the substrate.

 ここで、特許文献1及び2には、第一の化合物A及び第二の化合物Aについては記載されていない。 Here, Patent Documents 1 and 2 do not describe the first compound A and the second compound A.

 以下、本発明の樹脂組成物に含まれる成分について詳細に説明する。 The components contained in the resin composition of the present invention are described in detail below.

<特定樹脂>
 本発明の樹脂組成物は、環化樹脂およびその前駆体からなる群より選ばれた少なくとも1種の樹脂(特定樹脂)を含む。
 環化樹脂は、主鎖構造中にイミド環構造又はオキサゾール環構造を含む樹脂であることが好ましい。
 本発明において、「主鎖」とは、樹脂分子中で相対的に最も長い結合鎖を表し、「側鎖」とはそれ以外の結合鎖をいう。
 環化樹脂としては、ポリイミド、ポリベンゾオキサゾール、ポリアミドイミド等が挙げられる。
 環化樹脂の前駆体とは、外部刺激により化学構造の変化を生じて環化樹脂となる樹脂をいい、熱により化学構造の変化を生じて環化樹脂となる樹脂が好ましく、熱により閉環反応を生じて環構造が形成されることにより環化樹脂となる樹脂がより好ましい。
 環化樹脂の前駆体としては、ポリイミド前駆体、ポリベンゾオキサゾール前駆体、ポリアミドイミド前駆体等が挙げられる。
 すなわち、樹脂組成物は、特定樹脂として、ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、ポリベンゾオキサゾール前駆体、ポリアミドイミド、及び、ポリアミドイミド前駆体からなる群より選ばれた少なくとも1種の樹脂を含むことが好ましい。
 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、ポリイミドを含むことがより好ましい。
 特定樹脂は重合性基を有することが好ましく、ラジカル重合性基を含むことがより好ましい。
 特定樹脂がラジカル重合性基を有する場合、本発明の樹脂組成物は、ラジカル重合開始剤を含むことが好ましく、ラジカル重合開始剤を含み、かつ、ラジカル架橋剤を含むことがより好ましい。さらに必要に応じて、増感剤を含むことができる。このような樹脂組成物からは、例えば、ネガ型感光膜が形成される。
 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、樹脂組成物は、光酸発生剤を含むことが好ましい。このような樹脂組成物からは、例えば、化学増幅型であるポジ型感光膜又はネガ型感光膜が形成される。
<Specific resin>
The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.
The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.
In the present invention, the term "main chain" refers to the relatively longest bonding chain in a resin molecule, and the term "side chain" refers to any other bonding chain.
Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamideimide.
The precursor of a cyclized resin refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a cyclized resin. A resin that undergoes a change in chemical structure due to heat to become a cyclized resin is preferred, and a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a cyclized resin is more preferred.
Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor.
That is, the resin composition preferably contains, as the specific resin, at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor.
The resin composition preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide.
The specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator, more preferably contains a radical polymerization initiator and a radical crosslinking agent. If necessary, it can further contain a sensitizer. For example, a negative photosensitive film is formed from such a resin composition.
The specific resin may also have a polarity conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive or negative photosensitive film is formed.

〔ポリイミド前駆体〕
 本発明で用いるポリイミド前駆体は、その種類等は特に限定されないが、下記式(2)で表される繰返し単位を含むことが好ましい。

Figure JPOXMLDOC01-appb-C000009

 式(2)中、A及びAは、それぞれ独立に、酸素原子又は-NR-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価の有機基を表し、Rは水素原子又は1価の有機基を表す。 [Polyimide precursor]
The polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000009

In formula (2), A1 and A2 each independently represent an oxygen atom or -NRz- , R111 represents a divalent organic group, R115 represents a tetravalent organic group, R113 and R114 each independently represent a hydrogen atom or a monovalent organic group, and Rz represents 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-NR-を表し、酸素原子が好ましい。
 Rは水素原子又は1価の有機基を表し、水素原子が好ましい。
 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3~20の環状の脂肪族基、炭素数3~20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。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく、上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。式(2)におけるR111の例としては、-Ar-および-Ar-L-Ar-で表される基が挙げられ、-Ar-L-Ar-で表される基が好ましい。但し、Arは、それぞれ独立に、芳香族基であり、Lは、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-若しくは-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。
In formula (2), A 1 and A 2 each independently represent an oxygen atom or —NR z —, and preferably an oxygen atom.
Rz represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.
R 111 in 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. A linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Examples of R 111 in formula (2) include groups represented by -Ar- and -Ar-L-Ar-, and a group represented by -Ar-L-Ar- is preferred. Here, Ar is each independently an aromatic group, and L is a single bond, 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. The preferred ranges of these 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、R111は、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数3~20の環状の脂肪族基、炭素数3~20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の芳香族基を含むジアミンであることがより好ましい。上記直鎖又は分岐の脂肪族基は鎖中の炭化水素基がヘテロ原子を含む基で置換されていてもよく上記環状の脂肪族基および芳香族基は環員の炭化水素基がヘテロ原子を含む基で置換されていてもよい。芳香族基を含む基の例としては、下記が挙げられる。
R 111 is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
Specifically, R 111 is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom. Examples of groups containing an aromatic group include the following.

Figure JPOXMLDOC01-appb-C000010

 式中、Aは単結合又は2価の連結基を表し、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、又は、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-、若しくは、-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-C000010

In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO 2 -, -NHCO-, or a group selected from combinations thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO 2 -, and further preferably -CH 2 -, -O-, -S-, -SO 2 -, -C(CF 3 ) 2 -, or -C(CH 3 ) 2 -.
In the formula, * represents a bonding site with other structures.

 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-ジアミノブタン又は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’-又は3,3’-ジアミノジフェニルメタン、4,4’-又は3,3’-ジアミノジフェニルスルホン、4,4’-又は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、ビス(p-アミノフェニル)オクタメチルペンタシロキサン、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 diamines 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'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 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 phenyl, 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'-diaminoparaterphenyl , 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'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-di Ethyl-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-dihydro 4,4'-dimethyl-3,3'-diaminodiphenyl sulfone, 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, bis(p-aminophenyl)octamethylpentasiloxane , 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 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-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4 and at least one diamine selected from 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl.

 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。 Also preferred are the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017/038598.

 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。 Also preferably used are diamines having two or more alkylene glycol units in the main chain, as described in paragraphs 0032 to 0034 of WO 2017/038598.

 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。 From the viewpoint of flexibility of the resulting organic film, R 111 is preferably represented by -Ar-L-Ar-. Here, each Ar is independently an aromatic group, 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 preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 -. 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)

 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り、*はそれぞれ独立に、式(2)中の窒素原子との結合部位を表す。
 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。

 式(61)中、R58及びR59は、それぞれ独立に、フッ素原子、メチル基、又はトリフルオロメチル基であり、*はそれぞれ独立に、式(2)中の窒素原子との結合部位を表す。
 式(51)又は式(61)の構造を与えるジアミンとしては、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種又は2種以上を組み合わせて用いてもよい。
From the viewpoint of i-line transmittance, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoints of i-line transmittance and ease of availability, R 111 is more preferably a divalent organic group represented by formula (61).
Equation (51)

In formula (51), R 50 to R 57 each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group, at least one of R 50 to R 57 represents a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2).
Examples of the monovalent organic group for R 50 to R 57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

In formula (61), R 58 and R 59 each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in formula (2).
Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

 また、R111は下記式(71)で表される基であることも好ましい。上記態様において、R111は下記式(72)で表される基であることがより好ましい。

 式(71)中、A~Aはそれぞれ独立に、単結合又は2価の連結基であり、*は式(2)中の窒素原子との結合部位を表し、式(71)中に記載された4つのベンゼン環は、それぞれ水素原子が置換基により置換されていてもよい。
 本明細書において、環構造の辺と交差する結合は、その環構造における水素原子のいずれかを置換することを意味している。
 式(72)中、*は式(2)中の窒素原子との結合部位を表す。
Furthermore, R 111 is also preferably a group represented by the following formula (71): In the above embodiment, R 111 is more preferably a group represented by the following formula (72).

In formula (71), A 1 to A 3 each independently represent a single bond or a divalent linking group, * represents a bonding site with the nitrogen atom in formula (2), and each of the four benzene rings described in formula (71) may have a hydrogen atom substituted by a substituent.
As used herein, a bond that crosses an edge of a ring structure is meant to replace any of the hydrogen atoms in that ring structure.
In formula (72), * represents a bonding site with the nitrogen atom in formula (2).

 式(71)中、A~A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-、-S(=O)-、-NHC(=O)-、又は、これらの2つ以上の組み合わせからなる基であることが好ましく、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)-、又は、これらの2つ以上の組み合わせからなる基であることより好ましく、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又は-O-であることが更に好ましい。
 特に、A及びAは-O-であることが好ましい。
 特に、A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であることが好ましい。
 これらの中でも、A及びAが-O-であり、かつ、Aが-C(CH-である態様も、本発明の好ましい態様の一つである。
 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の炭素数は、特に限定されないが、1~6であることが好ましく、1~4であることがより好ましい。
 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具体例としては、-CH-、-C(CH-、-C(CF-等が挙げられ、中でも-C(CH-が好ましい。
 式(71)中に記載された4つのベンゼン環における置換基としては、フッ素原子、水素原子がフッ素原子により置換されていてもよい炭素数1~10の炭化水素基等が挙げられる。
 また式(71)中に記載された4つのベンゼン環がいずれも無置換である態様も、本発明の好ましい態様の一つである。
In formula (71), A 1 to A 3 are preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(═O)-, -S-, -S(═O) 2 -, -NHC(═O)-, or a group consisting of a combination of two or more of these, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(═O)-, or a group consisting of a combination of two or more of these, and further preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-.
In particular, A 1 and A 3 are preferably —O—.
In particular, A2 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom.
Among these, an embodiment in which A 1 and A 3 are —O— and A 2 is —C(CH 3 ) 2 — is also one of the preferred embodiments of the present invention.
The number of carbon atoms in the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 4.
Specific examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom include -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 - and the like, with -C(CH 3 ) 2 - being preferred.
Examples of the substituents on the four benzene rings shown in formula (71) include a fluorine atom and a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom.
An embodiment in which all of the four benzene rings in formula (71) are unsubstituted is also one of the preferred embodiments of the present invention.

 また、R111は下記式(81)で表される基であることも好ましい。上記態様において、R111は下記式(82)で表される基であることがより好ましい。

 式(81)中、A及びAはそれぞれ独立に、単結合又は2価の連結基であり、*は式(2)中の窒素原子との結合部位を表し、式(81)中に記載された3つのベンゼン環は、それぞれ水素原子が置換基により置換されていてもよい。
 式(82)中、*は式(2)中の窒素原子との結合部位を表す。
Furthermore, R 111 is also preferably a group represented by the following formula (81): In the above embodiment, R 111 is more preferably a group represented by the following formula (82).

In formula (81), A1 and A2 each independently represent a single bond or a divalent linking group, * represents a bonding site with the nitrogen atom in formula (2), and each of the three benzene rings depicted in formula (81) may have a hydrogen atom substituted with a substituent.
In formula (82), * represents a bonding site with the nitrogen atom in formula (2).

 式(81)中、A及びAはそれぞれ独立に、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-、-S(=O)-、-NHC(=O)-、又は、これらの2つ以上の組み合わせからなる基であることが好ましく、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)-、又は、これらの2つ以上の組み合わせからなる基であることより好ましく、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又は-O-であることが更に好ましく、-C(CH-であることが特に好ましい。 In formula (81), A 1 and A 2 are each preferably independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(═O)-, -S-, -S(═O) 2 -, -NHC(═O)-, or a group consisting of a combination of two or more of these, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(═O)-, or a group consisting of a combination of two or more of these, further preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-, and particularly preferably -C(CH 3 ) 2 -.

 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。

 式(5)中、R112は単結合又は2価の連結基であり、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、または、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-からなる群より選択される2価の基であることが更に好ましい。
In formula (2), R 115 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 (6), each * independently represents a bonding site to another structure.

In formula (5), R 112 is a single bond or a divalent linking group and is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -, -NHCO-, and a combination thereof, more preferably a single bond, or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO 2 -, and still more preferably a divalent group selected from the group consisting of -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -O-, -CO-, -S-, and -SO 2 -.

 また、R115は下記式(7)で表される基であることも好ましい。上記態様において、R115は下記式(7-2)で表される基であることがより好ましい。

 式(7)中、A~Aはそれぞれ独立に、単結合又は2価の連結基であり、*は式(2)中のカルボニル基との結合部位を表し、式(7)中に記載された4つのベンゼン環は、それぞれ水素原子が置換基により置換されていてもよい。
 式(7-2)中、*は式(2)中のカルボニル基との結合部位を表す。
Furthermore, R 115 is also preferably a group represented by the following formula (7): In the above embodiment, R 115 is more preferably a group represented by the following formula (7-2).

In formula (7), A 1 to A 3 each independently represent a single bond or a divalent linking group, * represents a bonding site with the carbonyl group in formula (2), and each of the four benzene rings described in formula (7) may have a hydrogen atom substituted by a substituent.
In formula (7-2), * represents a bonding site with the carbonyl group in formula (2).

 式(7)中、A~A、及び、ベンゼン環における置換基の好ましい態様は、上述の式(7-1)におけるA~A、及び、ベンゼン環における置換基の好ましい態様と同様である。 In formula (7), preferred embodiments of A 1 to A 3 and the substituent on the benzene ring are the same as the preferred embodiments of A 1 to A 3 and the substituent on the benzene ring in formula (7-1) described above.

 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。ポリイミド前駆体は、R115に該当する構造として、テトラカルボン酸二無水物残基を、1種のみ含んでもよいし、2種以上含んでもよい。
 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-C000017

 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 anhydride groups from tetracarboxylic dianhydride. The polyimide precursor may contain only one type of tetracarboxylic dianhydride residue or two or more types of tetracarboxylic dianhydride residues as the structure corresponding to R 115 .
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
Figure JPOXMLDOC01-appb-C000017

In formula (O), R 115 represents a tetravalent organic group. The preferred range of R 115 is the same as that of R 115 in formula (2), and the preferred range is also the same.

 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 dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl methane tetracarboxylic dianhydride, 2 ,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2 ,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride These include tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and their alkyl and alkoxy derivatives 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。 Furthermore, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.

 式(2)において、R111とR115の少なくとも一方がOH基を有することも可能である。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。 In the formula (2), at least one of R 111 and R 115 may have an OH group. More specifically, R 111 may be a residue of a bisaminophenol derivative.

 式(2)における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。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、又はポリアルキレンオキシ基を含むことが好ましい。また、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。R113及びR114の少なくとも一方が2以上の重合性基を含むことも好ましい。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。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、アミノ基が挙げられる。ポリイミド前駆体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、アリル基、イソアリル基、2-メチルアリル基、ビニル基と直接結合した芳香環を有する基(例えば、ビニルフェニル基など)、(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(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 in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. In addition, it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both contain a polymerizable group. It is also preferable that at least one of R 113 and R 114 contains two or more polymerizable groups. The polymerizable group is a group capable of crosslinking by the action of heat, radicals, etc., and is preferably a radical polymerizable group. Specific examples of the polymerizable group 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 an amino group. As the radical polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018

 式(III)において、R200は、水素原子、メチル基、エチル基又はメチロール基を表し、水素原子又はメチル基が好ましい。
 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-、シクロアルキレン基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、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基等のアルキレン基、1,2-ブタンジイル基、1,3-ブタンジイル基、-CHCH(OH)CH-、ポリアルキレンオキシ基が挙げられ、エチレン基、プロピレン基等のアルキレン基、-CHCH(OH)CH-、シクロヘキシル基、ポリアルキレンオキシ基がより好ましく、エチレン基、プロピレン基等のアルキレン基、又は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であることがより一層好ましく、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であることがより更に好ましく、2であることが特に好ましい。
 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返し数の好ましい態様は上述の通りである。
In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
In formula (III), * represents a bonding 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 —, a cycloalkylene group or a polyalkyleneoxy group.
Suitable examples of R 201 include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CH 2 CH(OH)CH 2 -, and polyalkyleneoxy groups, of which alkylene groups such as ethylene group and propylene group, -CH 2 CH(OH)CH 2 -, cyclohexyl group, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy groups are even more preferred.
In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating.
The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent, when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.
The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.
From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating.The preferred embodiment of the number of repetitions of the ethyleneoxy group in these groups is as described above.

 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 when R 114 is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

 式(2)において、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、アセタール基又はケ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。
In formula (2), at least one of R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred.
Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

 ポリイミド前駆体は、構造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 fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and 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を用いる態様が挙げられる。 In order to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine.

 式(2)で表される繰返し単位は、式(2-A)で表される繰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の少なくとも1種が、式(2-A)で表される繰返し単位を有する前駆体であることが好ましい。ポリイミド前駆体が式(2-A)で表される繰返し単位を含むことにより、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-C000019

 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、両方が重合性基を含む基であることが好ましい。 The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
Formula (2-A)
Figure JPOXMLDOC01-appb-C000019

In formula (2-A), A 1 and A 2 represent an oxygen atom, R 111 and R 112 each independently represent a divalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.

 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。R112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 the preferred range is also the same. R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.

 ポリイミド前駆体は、式(2)で表される繰返し単位を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)で表される繰返し単位の構造異性体を含んでいてもよい。ポリイミド前駆体は、上記式(2)の繰返し単位のほかに、他の種類の繰返し単位をも含んでいてもよい。 The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2). The polyimide precursor may contain other types of repeating units in addition to the repeating unit of 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、式(2)で表される繰返し単位の含有量が、全繰返し単位の50モル%以上である態様が挙げられる。上記合計含有量は、70モル%以上であることがより好ましく、90モル%以上であることが更に好ましく、90モル%超であることが特に好ましい。上記合計含有量の上限は、特に限定されず、末端を除くポリイミド前駆体における全ての繰返し単位が、式(2)で表される繰返し単位であってもよい。 One embodiment of the polyimide precursor of the present invention is one in which the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular upper limit to the total content, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

 ポリイミド前駆体の重量平均分子量(Mw)は、5,000~100,000が好ましく、10,000~50,000がより好ましく、15,000~40,000が更に好ましい。ポリイミド前駆体の数平均分子量(Mn)は、2,000~40,000が好ましく、3,000~30,000がより好ましく、4,000~20,000が更に好ましい。
 上記ポリイミド前駆体の分子量の分散度は、1.5以上が好ましく、1.8以上がより好ましく、2.0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、7.0以下が好ましく、6.5以下がより好ましく、6.0以下が更に好ましい。
 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。
 樹脂組成物が特定樹脂として複数種のポリイミド前駆体を含む場合、少なくとも1種のポリイミド前駆体の重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。また、上記複数種のポリイミド前駆体を1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。
The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
The polyimide precursor has a molecular weight dispersity of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
In this specification, the dispersity of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.
When the resin composition contains multiple polyimide precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as one resin are each within the above ranges.

〔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。
 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。
[Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide that is soluble in a developer containing an organic solvent as a main component.
In this specification, the alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C., and from the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferable, and a polyimide that dissolves at 1.0 g or more is more preferable. The upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less.
From the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.

-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も好ましい。
 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、5質量%以上が好ましく、また、20質量%以下が好ましい。
-Fluorine atom-
From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains fluorine atoms.
The fluorine atom is preferably contained, for example, in R 132 in the repeating unit represented by formula (4) described later or in R 131 in the repeating unit represented by formula (4) described later, and more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by formula (4) described later or in R 131 in the repeating unit represented by formula (4) described later.
The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.

-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も好ましい。
 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。
 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、1質量%以上が好ましく、また、20質量%以下が好ましい。
-Silicon atom-
From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains a silicon atom.
The silicon atom is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and more preferably contained in R 131 in the repeating unit represented by formula (4) described later as an organically modified (poly)siloxane structure described later.
The silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass % or more and 20 mass % or less.

-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R131に含まれることが好ましく、R132又は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、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。
- Ethylenically unsaturated bond -
From the viewpoint of the film strength of the resulting 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 in a side chain, but preferably in the side chain.
The ethylenically unsaturated bond is preferably radically polymerizable.
The ethylenically unsaturated bond is preferably contained in R 132 or R 131 in the repeating unit represented by formula (4) described below, and more preferably contained in R 132 or R 131 as a group having an ethylenically unsaturated bond.
Among these, the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described below, and more preferably contained in R 131 as a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020

 式(IV)中、R20は、水素原子、メチル基、エチル基又はメチロール基を表し、水素原子又はメチル基が好ましい。 In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.

 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、アルキレンオキシ基の繰返し数は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。
 上記炭素数2~12のアルキレン基としては、直鎖状、分岐鎖状、環状又はこれらの組み合わせにより表されるアルキレン基のいずれであってもよい。
 上記炭素数2~12のアルキレン基としては、炭素数2~8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い。
In formula (IV), R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -C(═O)O-, -O(C═O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions in the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group consisting of a combination of two or more of these.
The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, and alkylene groups represented by a combination thereof.
The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

 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-C000021
 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(IV)中のR21が結合する酸素原子との結合部位を表す。
 式(R1)~(R3)中、Lとしての炭素数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、式(IV)のR21としての炭素数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。 Among these, R 21 is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).
Figure JPOXMLDOC01-appb-C000021
In 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 in which two or more of these are bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents a bonding site with the oxygen atom to which R21 in formula (IV) is bonded.
In formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L are the same as the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as R 21 in formula (IV).
In formula (R1), X is preferably an oxygen atom.
In formulae (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).
The structure represented by formula (R2) can be 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 formula (R3) can be obtained, for example, by reacting 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, etc.).

 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 bonding site with another structure, and is preferably a bonding site with the main chain of the 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、0.0001~0.1mol/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 ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.

-エチレン性不飽和結合を有する基以外の重合性基-
 ポリイミドは、エチレン性不飽和結合を有する基以外の重合性基を有していてもよい。
 エチレン性不飽和結合を有する基以外の重合性基としては、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を有する基以外の重合性基は、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を有する基以外の重合性基の量は、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。
--Polymerizable group other than a group having an ethylenically unsaturated bond--
The polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
Examples of the polymerizable group other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
The polymerizable group other than the group having an ethylenically unsaturated bond is preferably included in, for example, R 131 in the repeating unit represented by formula (4) described below.
The amount of polymerizable groups other than groups having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

-極性変換基-
 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。
 極性変換基は、例えば、後述する式(4)で表される繰返し単位におけるR131、R132、ポリイミドの末端などに含まれる。
- Polarity conversion group -
The polyimide may have a polarity 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 preferred embodiments are also the same.
The polarity conversion group is contained, for example, in R 131 and R 132 in the repeating unit represented by formula (4) described later, or at the terminal of the polyimide.

-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。
 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。
 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、「溶剤現像」)に供される場合、ポリイミドの酸価は、1~35mgKOH/gが好ましく、2~30mgKOH/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。
 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。pKa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。
 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からなる群より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, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
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 developer containing an organic solvent as a main component (for example, "solvent development"), the acid value of the polyimide is preferably from 1 to 35 mgKOH/g, more preferably from 2 to 30 mgKOH/g, and even more preferably from 5 to 20 mgKOH/g.
The acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
The acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability.
pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa. In this specification, pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified. For pKa, the value listed in "Revised 5th Edition Chemistry Handbook: Basics" compiled by the Chemical Society of Japan may be referred to.
When the acid group is a polyacid, such as phosphoric acid, the pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one type 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。
-Phenol hydroxy group-
From the viewpoint of ensuring an appropriate development speed with an alkaline developer, the polyimide preferably has a phenolic hydroxy group.
The polyimide may have a phenolic hydroxy group at the end of the main chain or on a side chain.
The phenolic hydroxy group is preferably contained in, for example, R 132 or R 131 in the repeating unit represented by formula (4) described below.
The amount of the phenolic hydroxy group relative 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、イミド構造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)で表される繰返し単位を含むことが好ましい。

Figure JPOXMLDOC01-appb-C000022

 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-C000023

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-C000024

式(4-2)中、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 polymeric compound having an imide structure, but it is preferable that the polyimide contains a repeating unit represented by the following formula (4).
Figure JPOXMLDOC01-appb-C000022

In formula (4), R 131 represents a divalent organic group, and R 132 represents a tetravalent organic group.
When the polyimide has a polymerizable group, the polymerizable group may be located 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).
Formula (4-1)
Figure JPOXMLDOC01-appb-C000023

In formula (4-1), R 133 is a polymerizable group, and the other groups are the same as those in formula (4).
Formula (4-2)
Figure JPOXMLDOC01-appb-C000024

In formula (4-2), at least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are as defined in formula (4).

 重合性基としては、上述のエチレン性不飽和結合を含む基、又は、上述のエチレン性不飽和結合を有する基以外の架橋性基が挙げられる。
 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。
 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。
Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond, and crosslinkable groups other than the above-mentioned group having an ethylenically unsaturated bond.
R 131 represents a divalent organic group. Examples of the divalent organic group include the same as those of R 111 in formula (2), and the preferred range is also the same.
R 131 may be a diamine residue remaining after removal of the amino group of the diamine. The diamine may be an aliphatic, cycloaliphatic or aromatic diamine. 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、更に好ましくは上記ジアミンであって、芳香環を含まないジアミン残基である。 R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.

 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, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-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、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. Examples of the tetravalent organic group include the same as those of R 115 in formula (2), and the preferred range is also the same.
For example, the four bonds of the tetravalent organic group exemplified as R 115 bond to the four —C(═O)— portions in formula (4) to form a condensed ring.

 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。 R 132 may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. A specific example is 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 that at least one of R 131 and R 132 has an OH group. More specifically, preferred examples of R 131 include 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), and more preferred examples of R 132 include the above (DAA-1) to (DAA-5).

 ポリイミドは、構造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、20質量%以下がより好ましい。 It is also preferable that the polyimide has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

 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。 In order to improve adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

 樹脂組成物の保存安定性を向上させるため、ポリイミドの主鎖末端はモノアミン、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により封止されていることが好ましい。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。 In order to improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. Of these, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end-capping agents.

-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%以上であることが更に好ましい。
 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)-
From the viewpoints of the film strength, insulating properties, etc. of the resulting organic film, the imidization rate of the polyimide (also referred to as the "ring closure rate") is preferably 70% or more, and more preferably 80% or more. It is more preferable that the content is 90% or more.
There is no particular upper limit to the imidization rate, and it is sufficient if it is 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 at about 1377 cm −1 , which is an 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. is measured to determine the peak intensity P2 near 1377 cm −1 . Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be calculated based on the following formula:
Imidization rate (%)=(peak intensity P1/peak intensity P2)×100

 ポリイミドは、繰り返し単位のすべてがR131及びR132の組み合わせが同じである上記式(4)で表される繰返し単位を含んでいてもよく、R131及びR132の組み合わせが異なる2種以上を含む上記式(4)で表される繰返し単位を含んでいてもよい。ポリイミドは、上記式(4)で表される繰返し単位のほかに、他の種類の繰返し単位を含んでいてもよい。他の種類の繰返し単位としては、例えば、上述の式(2)で表される繰返し単位等が挙げられる。 The polyimide may contain repeating units represented by the above formula (4) in which all of the repeating units have the same combination of R 131 and R 132 , or may contain repeating units represented by the above formula (4) containing two or more different combinations of R 131 and R 132. The polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Examples of other types of repeating units include the repeating units represented by the above formula (2).

 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(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。また、その他公知のポリイミドの合成方法を適用することもできる。 Polyimides can be synthesized, for example, by reacting tetracarboxylic dianhydride with diamine (partially substituted with a terminal blocking agent that is a monoamine) at low temperature, by reacting tetracarboxylic dianhydride (partially substituted with a terminal blocking agent that is an acid anhydride, monoacid chloride compound, or monoactive ester compound) with diamine at low temperature, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine) in the presence of a condensing agent, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine), or by using a method in which a polyimide precursor is obtained and then completely imidized using a known imidization reaction method, or by stopping the imidization reaction midway and introducing a partial imide structure, or by blending a completely imidized polymer with the polyimide precursor to partially introduce an imide structure. Other known methods for synthesizing polyimides can also be applied.

 ポリイミドの重量平均分子量(Mw)は、5,000~100,000が好ましく、10,000~50,000がより好ましく、15,000~40,000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(例えば、破断伸び)に優れた有機膜を得るため、重量平均分子量は、15,000以上が特に好ましい。
 ポリイミドの数平均分子量(Mn)は、2,000~40,000が好ましく、3,000~30,000がより好ましく、4,000~20,000が更に好ましい。
 上記ポリイミドの分子量の分散度は、1.5以上が好ましく、1.8以上がより好ましく、2.0以上が更に好ましい。ポリイミド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、7.0以下が好ましく、6.5以下がより好ましく、6.0以下が更に好ましい。
 樹脂組成物が特定樹脂として複数種のポリイミドを含む場合、少なくとも1種のポリイミドの重量平均分子量、数平均分子量、及び、分散度が上記範囲であることが好ましい。上記複数種のポリイミドを1つの樹脂として算出した重量平均分子量、数平均分子量、及び、分散度が、それぞれ、上記範囲内であることも好ましい。
The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties (e.g., breaking elongation), the weight average molecular weight is particularly preferably 15,000 or more.
The number average molecular weight (Mn) of the polyimide is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000.
The polyimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the polyimide molecular weight dispersity is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
When the resin composition contains multiple polyimides as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimides as one resin are each within the above ranges.

〔ポリベンゾオキサゾール前駆体〕
 ポリベンゾオキサゾール前駆体としては、国際公開第2022/145355号の段落0073~0095に記載の化合物が挙げられる。上記記載は本明細書に組み込まれる。
[Polybenzoxazole precursor]
The polybenzoxazole precursor includes the compounds described in paragraphs 0073 to 0095 of WO 2022/145355. The above descriptions are incorporated herein by reference.

〔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、国際公開第2022/145355号の段落0096~0103に記載の化合物が挙げられる。上記記載は本明細書に組み込まれる。
[Polybenzoxazole]
Examples of polybenzoxazoles include compounds described in paragraphs 0096 to 0103 of WO 2022/145355. The above descriptions are incorporated herein by reference.

〔ポリアミドイミド前駆体〕
 ポリアミドイミド前駆体としては、国際公開第2022/145355号の段落0104~0119に記載の化合物が挙げられる。上記記載は本明細書に組み込まれる。
[Polyamide-imide precursor]
Examples of polyamideimide precursors include compounds described in paragraphs 0104 to 0119 of WO 2022/145355. The above descriptions are incorporated herein by reference.

〔ポリアミドイミド〕
 ポリアミドイミドとしては、国際公開第2022/145355号の段落0120~0133に記載の化合物が挙げられる。上記記載は本明細書に組み込まれる。
[Polyamide-imide]
Examples of polyamideimides include the compounds described in paragraphs 0120 to 0133 of WO 2022/145355. The above descriptions are incorporated herein by reference.

〔ポリイミド前駆体等の製造方法〕
 ポリイミド前駆体等は、例えば、国際公開第2022/145355号の段落0134~0136に記載の方法により製造される。上記記載は本明細書に組み込まれる。
[Method for producing polyimide precursor, etc.]
The polyimide precursor or the like is produced, for example, by the method described in paragraphs 0134 to 0136 of WO 2022/145355. The above description is incorporated herein by reference.

〔含有量〕
 本発明の樹脂組成物における特定樹脂の含有量は、樹脂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、本発明の樹脂組成物における樹脂の含有量は、樹脂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。
 本発明の樹脂組成物は、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 resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. The content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition.
The resin composition of the present invention may contain only one specific resin, or may contain two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.

 本発明の樹脂組成物は、少なくとも2種の樹脂を含むことも好ましい。
 具体的には、本発明の樹脂組成物は、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。
It is also preferable that the resin composition of the present invention contains at least two types of resins.
Specifically, the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resins described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins.
When the resin composition of the present invention contains two or more specific resins, it preferably contains, for example, two or more polyimide precursors having different dianhydride-derived structures (R 115 in the above formula (2)).

<他の樹脂>
 本発明の樹脂組成物は、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、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、(メタ)アクリル樹脂、(メタ)アクリルアミド樹脂、ウレタン樹脂、ブチラール樹脂、スチリル樹脂、ポリエーテル樹脂、ポリエステル樹脂等が挙げられる。
 例えば、(メタ)アクリル樹脂を更に加えることにより、塗布性に優れた樹脂組成物が得られ、また、耐溶剤性に優れたパターン(硬化物)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(例えば、樹脂1gにおける重合性基の含有モル量が1×10-3モル/g以上である)(メタ)アクリル樹脂を樹脂組成物に添加することにより、樹脂組成物の塗布性、パターン(硬化物)の耐溶剤性等を向上させることができる。
<Other resins>
The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, simply referred to as "another resin").
Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
For example, by further adding a (meth)acrylic resin, a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
For example, instead of or in addition to the polymerizable compound described later, by adding a (meth)acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, the molar content of polymerizable groups per 1 g of resin is 1×10 −3 mol/g or more) to the resin composition, the coatability of the resin composition and the solvent resistance of the pattern (cured product) can be improved.

 本発明の樹脂組成物が他の樹脂を含む場合、他の樹脂の含有量は、樹脂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。
 本発明の樹脂組成物が他の樹脂を含む場合、他の樹脂の含有量は、樹脂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。
 本発明の樹脂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、樹脂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。
 本発明の樹脂組成物は、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 resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition.
When the resin composition of the present invention contains other resins, the content of the other resins is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, even more preferably 60 mass% or less, and even more preferably 50 mass% or less, based on the total solid content of the resin composition.
As a preferred embodiment of the resin 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, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

<化合物A>
 本発明の第一の樹脂組成物は、第一の化合物Aを含む。
 第一の化合物Aは、式(A1-1)で表される化合物である。

 式(A1-1)中、Rは酸素原子、窒素原子及び硫黄原子から選ばれる少なくとも1つ以上の原子を有する有機基であり、Rが複数ある場合は同一であってもよいし、異なっていてもよく、Rは水素原子又は上記Rに該当しない任意の有機基であり、Rが複数ある場合は同一であってもよいし、異なっていてもよく、R及びRのうち少なくとも2つが結合して環構造を形成してもよく、nは1~3の整数を表し、mは1以上の整数を表し、Rはm価の有機基を表す。
<Compound A>
The first resin composition of the present invention contains a first compound A.
The first compound A is a compound represented by formula (A1-1).

In formula (A1-1), R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different, R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different, at least two of R 1 and R 2 may be bonded to form a ring structure, n represents an integer of 1 to 3, m represents an integer of 1 or more, and R 3 represents an m-valent organic group.

 式(A1-1)中、Rは酸素原子及び窒素原子から選ばれる少なくとも1つ以上の原子を有する有機基であることが好ましい。ここで、Rが酸素原子及び窒素原子を有する態様も、本発明の好ましい態様の一つである。 In formula (A1-1), R 1 is preferably an organic group having at least one atom selected from an oxygen atom and a nitrogen atom. Here, an embodiment in which R 1 has an oxygen atom and a nitrogen atom is also one of the preferred embodiments of the present invention.

 式(A1-1)中、Rはアミノ基又はエステル結合を含むことが好ましい。
 式(A1-1)中、Rは水素原子が置換基で置換されてもよい1以上の炭化水素基と、カルボキシ基、エステル結合(-C(=O)O-)、ウレア結合(-NR-C(=O)NR-)及び置換アミノ基よりなる群から選ばれた少なくとも1つの基とを含むことが好ましい。
 上記Rは水素原子又は水素原子が置換基で置換されてもよい炭化水素基を表す。上記置換基としてはヒドロキシ基、アルコキシ基、ハロゲン原子等が挙げられ、ヒドロキシ基が好ましい。
 上記炭化水素基としては、水素原子が置換基で置換されてもよい飽和脂肪族炭化水素基又は水素原子が置換基で置換されてもよい芳香族炭化水素基が好ましい。
 上記飽和脂肪族炭化水素基としては、炭素数2~10の炭化水素基であることが好ましく、炭素数2~4の炭化水素基であることがより好ましい。飽和脂肪族炭化水素基の水素原子が置換される場合の置換基としては、ヒドロキシ基、アルコキシ基、ハロゲン原子、重合性基等が挙げられ、ヒドロキシ基が好ましい。重合性基としては、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミド基、ビニルフェニルエーテル基、グリシジルエーテル基、トリアルコキシシリル基等が挙げられる。
 上記芳香族炭化水素基としては、炭素数6~20の芳香族炭化水素基が好ましく、炭素数6の芳香族炭化水素基がより好ましい。芳香族炭化水素基の水素原子が置換される場合の置換基としては、アルキル基、ヒドロキシ基、アルコキシ基、ハロゲン原子、重合性基等が挙げられ、ヒドロキシ基が好ましい。重合性基としては、ビニル基、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミド基、ビニルフェニルエーテル基、グリシジルエーテル基、トリアルコキシシリル基等が挙げられる。
 上記エステル結合の向きは特に限定されないが、式(A1-1)のケイ素原子の側がエステル結合に含まれる炭素原子である向きが好ましい。
 上記置換アミノ基における置換基としては、水素原子が置換基で置換されてもよいアルキル基又は水素原子が置換基で置換されてもよいアリール基が挙げられる。上記アルキル基における水素原子が置換される場合の置換基としては、ヒドロキシ基、アルコキシ基、ハロゲン原子等が挙げられ、ヒドロキシ基が好ましい。上記アリール基における水素原子が置換される場合の置換基としては、ヒドロキシ基、アルコキシ基、ハロゲン原子等が挙げられる。
In formula (A1-1), R 1 preferably contains an amino group or an ester bond.
In formula (A1-1), R 1 preferably contains one or more hydrocarbon groups in which a hydrogen atom may be substituted with a substituent, and at least one group selected from the group consisting of a carboxy group, an ester bond (-C(=O)O-), a urea bond (-NR N -C(=O)NR N -), and a substituted amino group.
The above R N represents a hydrogen atom or a hydrocarbon group in which the hydrogen atom may be substituted with a substituent. The above substituent includes a hydroxy group, an alkoxy group, a halogen atom, etc., and is preferably a hydroxy group.
The above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
The saturated aliphatic hydrocarbon group is preferably a hydrocarbon group having 2 to 10 carbon atoms, and more preferably a hydrocarbon group having 2 to 4 carbon atoms. When a hydrogen atom of the saturated aliphatic hydrocarbon group is substituted, examples of the substituent include a hydroxy group, an alkoxy group, a halogen atom, a polymerizable group, and the like, and a hydroxy group is preferred. Examples of the polymerizable group include a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, and the like.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 carbon atoms. When a hydrogen atom of the aromatic hydrocarbon group is substituted, examples of the substituent include an alkyl group, a hydroxy group, an alkoxy group, a halogen atom, a polymerizable group, etc., and a hydroxy group is preferred. Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, etc.
The orientation of the ester bond is not particularly limited, but it is preferable that the carbon atom included in the ester bond faces the silicon atom in formula (A1-1).
The substituent in the substituted amino group may be an alkyl group in which the hydrogen atom may be substituted with a substituent, or an aryl group in which the hydrogen atom may be substituted with a substituent. The substituent in the alkyl group in which the hydrogen atom is substituted may be a hydroxyl group, an alkoxyl group, a halogen atom, etc., and preferably a hydroxyl group. The substituent in the aryl group in which the hydrogen atom is substituted may be a hydroxyl group, an alkoxyl group, a halogen atom, etc.

 Rは下記式(R-1)、式(R-2)又は式(R-3)で表される基であることが好ましい。

 式(R-1)中、LR1は炭化水素基、又は、炭化水素基と-O-の組み合わせにより表される基を表し、RR1及びRR2はそれぞれ独立に、水素原子が置換基で置換されてもよい炭化水素基を表し、*は式(A1-1)における酸素原子との結合部位を表す。
 式(R-2)中、LR1は炭化水素基、又は、炭化水素基と-O-の組み合わせにより表される基を表し、RR3は水素原子又は水素原子が置換基で置換されてもよい炭化水素基を表し、*は式(A1-1)における酸素原子との結合部位を表す。
 式(R-3)中、LR1は炭化水素基、又は、炭化水素基と-O-の組み合わせにより表される基を表し、RR4及びRR5は水素原子又は水素原子が置換基で置換されてもよい炭化水素基を表し、RR6は水素原子が置換基で置換されてもよい炭化水素基を表し、*は式(A1-1)における酸素原子との結合部位を表す。
R 1 is preferably a group represented by the following formula (R-1), formula (R-2) or formula (R-3).

In formula (R-1), L 5 R1 represents a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-, R 5 R1 and R 5 R2 each independently represent a hydrocarbon group in which a hydrogen atom may be substituted with a substituent, and * represents a bonding site with the oxygen atom in formula (A1-1).
In formula (R-2), L R1 represents a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-, R R3 represents a hydrogen atom or a hydrocarbon group in which the hydrogen atom may be substituted with a substituent, and * represents the bonding site with the oxygen atom in formula (A1-1).
In formula (R-3), L 1 R1 represents a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-, R 4 R4 and R 5 represent hydrogen atoms or hydrocarbon groups in which the hydrogen atoms may be substituted with substituents, R 6 represents a hydrocarbon group in which the hydrogen atoms may be substituted with substituents, and * represents the bonding site with the oxygen atom in formula (A1-1).

 式(R-1)中、LR1はアルキレン基、又は、アルキレンオキシアルキレン基が好ましく、アルキレン基がより好ましい。LR1における炭化水素基(好ましくは、アルキレン基)の炭素数は、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又は3であることが更に好ましい。
 式(R-1)中、RR1及びRR2はそれぞれ独立に、水素原子が置換基で置換されてもよいアルキル基、又は、水素原子が置換基で置換されてもよい芳香族炭化水素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2~10のアルキル基であることが好ましく、炭素数2~4のアルキル基であることがより好ましい。アルキル基の水素原子が置換される場合の置換基としては、ヒドロキシ基、アルコキシ基、ハロゲン原子等が挙げられ、ヒドロキシ基が好ましい。重合性基としては、ビニル基、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミド基、ビニルフェニルエーテル基、グリシジルエーテル基、トリアルコキシシリル基等が挙げられる。
 上記芳香族炭化水素基としては、炭素数6~20の芳香族炭化水素基が好ましく、フェニル基がより好ましい。芳香族炭化水素基の水素原子が置換される場合の置換基としては、アルキル基、ヒドロキシ基、アルコキシ基、ハロゲン原子、重合性基等が挙げられ、ヒドロキシ基が好ましい。重合性基としては、ビニル基、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミド基、ビニルフェニルエーテル基、グリシジルエーテル基、トリアルコキシシリル基等が挙げられる。
 ここで、式(R-1)において、RR1がヒドロキシアルキル基であり、RR2が芳香族炭化水素基である態様も、本発明の好ましい態様の一つである。例えば、RR1がヒドロキシエチル基であり、RR2がフェニル基であることが好ましい。
In formula (R-1), L 1 R1 is preferably an alkylene group or an alkyleneoxyalkylene group, more preferably an alkylene group. The number of carbon atoms in the hydrocarbon group (preferably an alkylene group) in L 1 R1 is preferably 2 to 10, more preferably 2 to 4, and even more preferably 2 or 3.
In formula (R-1), it is preferable that R 1 R1 and R 2 R2 each independently represent an alkyl group in which a hydrogen atom may be substituted with a substituent, or an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
The alkyl group is preferably an alkyl group having 2 to 10 carbon atoms, and more preferably an alkyl group having 2 to 4 carbon atoms. When a hydrogen atom of the alkyl group is substituted, examples of the substituent include a hydroxy group, an alkoxy group, a halogen atom, etc., and a hydroxy group is preferred. Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, etc.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a phenyl group. When a hydrogen atom of the aromatic hydrocarbon group is substituted, examples of the substituent include an alkyl group, a hydroxy group, an alkoxy group, a halogen atom, a polymerizable group, etc., and a hydroxy group is preferred. Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, etc.
Here, in formula (R-1), an embodiment in which R 1 R1 is a hydroxyalkyl group and R 2 R2 is an aromatic hydrocarbon group is also one of the preferred embodiments of the present invention. For example, it is preferred that R 1 R1 is a hydroxyethyl group and R 2 R2 is a phenyl group.

 式(R-2)中、LR1の好ましい態様は上述の式(R-1)におけるLR1の好ましい態様と同様である。
 式(R-2)中、RR3が水素原子が置換基で置換されてもよい炭化水素基である場合の好ましい態様は上述の式(R-1)におけるRR1の好ましい態様と同様である。
 ここで、式(R-2)において、LR1がアルキレン基であり、RR3が水素原子又は無置換のアルキル基である態様も、本発明の好ましい態様の一つである。例えば、LR1がトリメチレン基であり、RR3が水素原子、メチル基又はエチル基であることが好ましい。
In formula (R-2), preferred embodiments of L 3 R1 are the same as the preferred embodiments of L 3 R1 in formula (R-1) described above.
In formula (R-2), when R 1 R3 is a hydrocarbon group in which a hydrogen atom may be substituted with a substituent, the preferred embodiments are the same as the preferred embodiments of R 1 R1 in formula (R-1) described above.
Here, in formula (R-2), an embodiment in which L 1 R1 is an alkylene group and R 1 R3 is a hydrogen atom or an unsubstituted alkyl group is also one of the preferred embodiments of the present invention. For example, it is preferred that L 1 R1 is a trimethylene group and R 1 R3 is a hydrogen atom, a methyl group or an ethyl group.

 式(R-3)中、LR1の好ましい態様は上述の式(R-1)におけるLR1の好ましい態様と同様である。
 式(R-3)中、RR4及びRR5は水素原子又は水素原子が置換基で置換されてもよいアルキル基が好ましい。
 上記アルキル基の炭素数は、1~10が好ましく、2~4がより好ましい。アルキル基の水素原子が置換される場合の置換基としては、ヒドロキシ基、アルコキシ基、ハロゲン原子等が挙げられ、ヒドロキシ基が好ましい。重合性基としては、ビニル基、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミド基、ビニルフェニルエーテル基、グリシジルエーテル基、トリアルコキシシリル基等が挙げられる。
 式(R-3)中、RR6は水素原子が置換基で置換されてもよいアルキル基が好ましい。
 上記アルキル基の炭素数は、1~10が好ましく、2~4がより好ましい。アルキル基の水素原子が置換される場合の置換基としては、ヒドロキシ基、アルコキシ基、ハロゲン原子等が挙げられ、ヒドロキシ基が好ましい。重合性基としては、ビニル基、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミド基、ビニルフェニルエーテル基、グリシジルエーテル基、トリアルコキシシリル基等が挙げられる。
 ここで、式(R-3)において、LR1がアルキレン基又はアルキレンオキシアルキレン基であり、RR4が水素原子又はヒドロキシアルキル基であり、Rが水素原子であり、Rが水素原子が重合性基で置換されたアルキル基である態様も、本発明の好ましい態様の一つである。例えば、LR1がエチレン基又はエチレンオキシエチレン基であり、RR4が水素原子又はヒドロキシエチル基であり、Rが水素原子であり、Rが(メタ)アクリロイルオキシエチル基である態様も、本発明の好ましい態様の一つである。
In formula (R-3), preferred embodiments of L 3 R1 are the same as the preferred embodiments of L 3 R1 in formula (R-1) described above.
In formula (R-3), R 1 R4 and R 1 R5 are preferably a hydrogen atom or an alkyl group whose hydrogen atom may be substituted with a substituent.
The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 2 to 4. When a hydrogen atom in the alkyl group is substituted, examples of the substituent include a hydroxy group, an alkoxy group, and a halogen atom, and a hydroxy group is preferred. Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, and a trialkoxysilyl group.
In formula (R-3), R 1 and R 6 are preferably an alkyl group in which the hydrogen atom may be substituted with a substituent.
The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 2 to 4. When a hydrogen atom in the alkyl group is substituted, examples of the substituent include a hydroxy group, an alkoxy group, and a halogen atom, and a hydroxy group is preferred. Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, and a trialkoxysilyl group.
In the formula (R-3), an embodiment in which L 1 R1 is an alkylene group or an alkyleneoxyalkylene group, R 1 R4 is a hydrogen atom or a hydroxyalkyl group, R 5 is a hydrogen atom, and R 6 is an alkyl group in which a hydrogen atom is substituted with a polymerizable group is also one of the preferred embodiments of the present invention. For example, an embodiment in which L 1 R1 is an ethylene group or an ethyleneoxyethylene group, R 1 R4 is a hydrogen atom or a hydroxyethyl group, R 5 is a hydrogen atom, and R 6 is a (meth)acryloyloxyethyl group is also one of the preferred embodiments of the present invention.

 式(A1-1)中のRの具体例について以下に記載するが、本発明はこれらに限定されるものではない。下記式中、*は式(A1-1)における酸素原子との結合部位を表す。また、下記具体例について、後述するHSP値(*を水素原子に置換した場合の後述するtotal HSPの値)を、HSPとして記載した。
Specific examples of R 1 in formula (A1-1) are described below, but the present invention is not limited thereto. In the following formula, * represents a bonding site with an oxygen atom in formula (A1-1). In addition, for the following specific examples, the HSP value described below (the total HSP value described below when * is replaced with a hydrogen atom) is described as HSP.

 式(A1-1)中、Rはアルキル基であることが好ましく、炭素数1~4のアルキル基であることが好ましく、メチル基、エチル基又はイソプロピル基がより好ましく、メチル基又はエチル基が更に好ましい。
 ここで、後述するHSP値(*を水素原子に置換した場合の後述するtotal HSPの値)は、メチル基:16.9、エチル基:14.8、へキシル基:15.0である。
In formula (A1-1), R 2 is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, and still more preferably a methyl group or an ethyl group.
Here, the HSP values described below (total HSP values described below when * is replaced with a hydrogen atom) are 16.9 for the methyl group, 14.8 for the ethyl group, and 15.0 for the hexyl group.

 式(A1-1)中、R及びRのうち少なくとも2つが結合して形成される環構造としては、環員として窒素原子を含む環構造が好ましい。
 具体的には、下記式(R-4)又は式(R-5)で表される構造を含む環構造であることが好ましい。

 式(R-4)中、LR2及びLR3はそれぞれ独立に、水素原子が置換基で置換されてもよい炭化水素基を表し、RR7は水素原子が置換基で置換されてもよい炭化水素基を表し、*はそれぞれ、式(A1-1)中の酸素原子との結合部位を表す。
 式(R-5)中、LR4及びLR5はそれぞれ独立に、水素原子が置換基で置換されてもよい炭化水素基を表し、RR8は水素原子又は水素原子が置換基で置換されてもよい炭化水素基を表し、RR9は水素原子が置換基で置換されてもよい炭化水素基を表し、*はそれぞれ、式(A1-1)中の酸素原子との結合部位を表す。
In formula (A1-1), the ring structure formed by combining at least two of R 1 and R 2 is preferably a ring structure containing a nitrogen atom as a ring member.
Specifically, it is preferably a ring structure containing a structure represented by the following formula (R-4) or formula (R-5).

In formula (R-4), L1R2 and L1R3 each independently represent a hydrocarbon group in which a hydrogen atom may be substituted with a substituent, R2R7 represents a hydrocarbon group in which a hydrogen atom may be substituted with a substituent, and * each represents a bonding site with the oxygen atom in formula (A1-1).
In formula (R-5), L1R4 and L1R5 each independently represent a hydrocarbon group in which a hydrogen atom may be substituted with a substituent, R1R8 represents a hydrogen atom or a hydrocarbon group in which a hydrogen atom may be substituted with a substituent, R1R9 represents a hydrocarbon group in which a hydrogen atom may be substituted with a substituent, and * each represents a bonding site to the oxygen atom in formula (A1-1).

 式(R-4)中、LR2及びLR3はそれぞれ独立に、アルキレン基であることが好ましい。上記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、エチレン基が更に好ましい。
 式(R-4)中、RR7の好ましい態様は、上述の式(R-1)におけるRR1の好ましい態様と同様である。
 式(R-4)中、*はそれぞれ、式(A1-1)中の酸素原子と連結基を介さずに単結合で結合することが好ましい。
In formula (R-4), L 1 R2 and L 1 R3 are each preferably independently an alkylene group. The alkylene group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and further preferably an ethylene group.
In formula (R-4), preferred embodiments of R 1 R7 are the same as the preferred embodiments of R 1 R1 in formula (R-1) above.
In formula (R-4), it is preferable that each * is bonded to the oxygen atom in formula (A1-1) via a single bond without a linking group.

 式(R-5)中、LR4及びLR5の好ましい態様は、それぞれ、上述の式(R-4)におけるLR2及びLR3の好ましい態様と同様である。
 式(R-5)中、RR8の好ましい態様は、上述の式(R-3)におけるRR5の好ましい態様と同様である。
 式(R-5)中、RR9の好ましい態様は、上述の式(R-3)におけるRR6の好ましい態様と同様である。
 式(R-5)中、*はそれぞれ、式(A1-1)中の酸素原子と連結基を介さずに単結合で結合することが好ましい。
In formula (R-5), preferred embodiments of L 1 R4 and L 1 R5 are the same as the preferred embodiments of L 1 R2 and L 1 R3 in formula (R-4) above, respectively.
In formula (R-5), preferred embodiments of R 1 R8 are the same as preferred embodiments of R 1 R5 in formula (R-3) above.
In formula (R-5), preferred embodiments of R 1 R9 are the same as preferred embodiments of R 1 R6 in formula (R-3) above.
In formula (R-5), it is preferable that each * is bonded to the oxygen atom in formula (A1-1) via a single bond without a linking group.

 式(A1-1)中、R及びRのうち少なくとも2つが結合して環構造を形成する場合の、形成される環構造に含まれる構造の例を以下に示すが、本発明はこれらに限定されるものではない。*はそれぞれ、式(A1-1)中の酸素原子と連結基を介さずに単結合で結合する。また、下記具体例について、後述するHSP値(*を水素原子に置換した場合の後述するtotal HSPの値)を、HSPとして記載した。
In the formula (A1-1), when at least two of R 1 and R 2 are bonded to form a ring structure, examples of the structure contained in the ring structure formed are shown below, but the present invention is not limited to these. * is each bonded to the oxygen atom in the formula (A1-1) by a single bond without a linking group. In addition, for the following specific examples, the HSP value described below (the total HSP value described below when * is replaced with a hydrogen atom) is described as HSP.

 式(A1-1)中、nは1又は2であることが好ましい。また、nが1である態様も、本発明の好ましい態様の一つである。 In formula (A1-1), n is preferably 1 or 2. In addition, an embodiment in which n is 1 is also one of the preferred embodiments of the present invention.

 式(A1-1)中、mは1~3の整数であることが好ましく、1又は2であることがより好ましい。また、mが1である態様も、本発明の好ましい態様の一つである。 In formula (A1-1), m is preferably an integer of 1 to 3, and more preferably 1 or 2. In addition, an embodiment in which m is 1 is also one of the preferred embodiments of the present invention.

 式(A1-1)中、Rはm価の有機基を表す。
 式(A1-1)中、Rは水素原子が置換基で置換されてもよい1以上の炭化水素基と、アミド結合(-C(=O)NR-)、イミノ基(-NR-)よりなる群から選ばれた少なくとも1つの基とを含むことが好ましい。
 上記Rは水素原子又は水素原子が置換基で置換されてもよい炭化水素基を表し、水素原子が好ましい。上記置換基としてはヒドロキシ基、アルコキシ基、ハロゲン原子等が挙げられる。
 上記炭化水素基としては、水素原子が置換基で置換されてもよい飽和脂肪族炭化水素基又は水素原子が置換基で置換されてもよい芳香族炭化水素基が好ましい。
 上記飽和脂肪族炭化水素基としては、炭素数2~10の炭化水素基であることが好ましく、炭素数2~4の炭化水素基であることがより好ましい。飽和脂肪族炭化水素基の水素原子が置換される場合の置換基としては、ヒドロキシ基、アルコキシ基、ハロゲン原子、重合性基等が挙げられる。重合性基としては、ビニル基、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミド基、ビニルフェニルエーテル基、グリシジルエーテル基、トリアルコキシシリル基等が挙げられる。
 上記芳香族炭化水素基としては、炭素数6~20の芳香族炭化水素基が好ましく、炭素数6の芳香族炭化水素基がより好ましい。芳香族炭化水素基の水素原子が置換される場合の置換基としては、カルボキシ基、アルキル基、ヒドロキシ基、アルコキシ基、ハロゲン原子、重合性基等が挙げられる。重合性基としては、ビニル基、(メタ)アクリロイルオキシ基、(メタ)アクリロイルアミド基、ビニルフェニルエーテル基、グリシジルエーテル基、トリアルコキシシリル基等が挙げられる。
In formula (A1-1), R3 represents an m-valent organic group.
In formula (A1-1), R 3 preferably contains one or more hydrocarbon groups in which a hydrogen atom may be substituted with a substituent, and at least one group selected from the group consisting of an amide bond (-C(=O)NR N -) and an imino group (-NR N -).
R N represents a hydrogen atom or a hydrocarbon group in which the hydrogen atom may be substituted with a substituent, preferably a hydrogen atom. Examples of the substituent include a hydroxyl group, an alkoxy group, and a halogen atom.
The above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
The saturated aliphatic hydrocarbon group is preferably a hydrocarbon group having 2 to 10 carbon atoms, and more preferably a hydrocarbon group having 2 to 4 carbon atoms. When a hydrogen atom of the saturated aliphatic hydrocarbon group is substituted, examples of the substituent include a hydroxy group, an alkoxy group, a halogen atom, and a polymerizable group. Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, and a trialkoxysilyl group.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 carbon atoms. When a hydrogen atom of the aromatic hydrocarbon group is substituted, examples of the substituent include a carboxy group, an alkyl group, a hydroxy group, an alkoxy group, a halogen atom, and a polymerizable group. Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, and a trialkoxysilyl group.

 式(A1-1)中、Rは下記式(R3-1)で表される基であることが好ましい。

 式(R3-1)中、L31はそれぞれ独立に、2価の連結基を表し、R31はそれぞれ独立に、2価の連結基を表し、mは1以上の整数を表し、mが1である場合L32は水素原子又は置換基を表し、mが2以上である場合L32はm価の連結基を表し、*は式(A1-1)中のケイ素原子との結合部位を表す。
In formula (A1-1), R 3 is preferably a group represented by the following formula (R3-1).

In formula (R3-1), L 31 each independently represents a divalent linking group, R 31 each independently represents a divalent linking group, m represents an integer of 1 or more, when m is 1, L 32 represents a hydrogen atom or a substituent, when m is 2 or more, L 32 represents an m-valent linking group, and * represents a bonding site to the silicon atom in formula (A1-1).

 式(R3-1)中、L31は水素原子が置換されていてもよいアルキレン基であることが好ましい。上記アルキレン基の炭素数は、2~10であることが好ましく、2~4であることが更に好ましい。また、上記アルキレン基が無置換のアルキレン基である態様も、本発明の好ましい態様の一つである。
 R31は炭化水素基、又は、*-C(=O)R32-#で表される基であることが好ましい。
 R31が表す炭化水素基としては、水素原子が置換基で置換されてもよい芳香族炭化水素基、又は、水素原子が置換基で置換されてもよい脂肪族不飽和炭化水素基がより好ましく、水素原子が置換基で置換されてもよい芳香族炭化水素基がより好ましい。
 上記水素原子が置換基で置換されてもよい芳香族炭化水素基としては、水素原子が置換基で置換されてもよい炭素数6~20の芳香族炭化水素基が好ましく、水素原子が置換基で置換されてもよいフェニレン基がより好ましい。上記水素原子が置換基で置換されてもよい芳香族炭化水素基における置換基としては、カルボキシ基、ヒドロキシ基、アルキル基、アルコキシ基、ハロゲン原子等が挙げられ、カルボキシ基が好ましい。
 上記水素原子が置換基で置換されてもよい脂肪族不飽和炭化水素基としては、エチレン基等が挙げられる。
 R31が表す*-C(=O)R32-#で表される基において、*は式(R3-1)中の窒素原子との結合部位を表し、#は式(R3-1)中のL32との結合部位を表す。上記R32は有機基を表し、水素原子が置換基で置換されてもよい芳香族炭化水素基が好ましい。この水素原子が置換基で置換されてもよい芳香族炭化水素基の好ましい態様は、上記R31が炭化水素基である場合の水素原子が置換基で置換されてもよい芳香族炭化水素基の好ましい態様と同様である。
In formula (R3-1), L31 is preferably an alkylene group which may be substituted with a hydrogen atom. The number of carbon atoms in the alkylene group is preferably 2 to 10, and more preferably 2 to 4. In addition, an embodiment in which the alkylene group is an unsubstituted alkylene group is also one of the preferred embodiments of the present invention.
R 31 is preferably a hydrocarbon group or a group represented by *-C(=O)R 32 -#.
The hydrocarbon group represented by R31 is preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or an aliphatic unsaturated hydrocarbon group in which a hydrogen atom may be substituted with a substituent, and more preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
The aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms in which a hydrogen atom may be substituted with a substituent, and more preferably a phenylene group in which a hydrogen atom may be substituted with a substituent. Examples of the substituent in the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent include a carboxy group, a hydroxy group, an alkyl group, an alkoxy group, a halogen atom, etc., and a carboxy group is preferred.
Examples of the aliphatic unsaturated hydrocarbon group in which a hydrogen atom may be substituted with a substituent include an ethylene group.
In the group represented by *-C(=O) R32- # represented by R31 , * represents the bonding site to the nitrogen atom in formula (R3-1), and # represents the bonding site to L32 in formula (R3-1). R32 represents an organic group, and is preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent. Preferred aspects of this aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent are the same as the preferred aspects of the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent when R31 is a hydrocarbon group.

 mは式(A1-1)におけるmと同一の数である。 m is the same number as m in formula (A1-1).

 mが1である場合L32は水素原子又は置換基を表し、水素原子又はカルボキシ基が好ましい。その他、本発明の効果が得られる範囲内において、公知の置換基を用いてもよい。
 mが2以上である場合L32は単結合又はm価の連結基を表し、水素原子が置換基で置換されてもよい炭化水素基、-O-、-C(=O)-、-S-、-S(=O)-、-NR-、若しくは、これらが2以上結合した基が好ましい。特に、mが2である場合、L32は-CH-、-O-、-C(=O)-、-C(CF-、又は、-C(CH-であることがより好ましく、-C(=O)-であることが更に好ましい。
When m is 1, L 32 represents a hydrogen atom or a substituent, preferably a hydrogen atom or a carboxy group. In addition, known substituents may be used within the range in which the effects of the present invention can be obtained.
When m is 2 or more, L 32 represents a single bond or an m-valent linking group, and is preferably a hydrocarbon group in which a hydrogen atom may be substituted with a substituent, -O-, -C(=O)-, -S-, -S(=O) 2 -, -NR N -, or a group in which two or more of these are bonded. In particular, when m is 2, L 32 is more preferably -CH 2 -, -O-, -C(=O)-, -C(CF 3 ) 2 -, or -C(CH 3 ) 2 -, and even more preferably -C(=O)-.

 式(A1-1)中のRの具体例について以下に記載するが、本発明はこれらに限定されるものではない。下記式中、*は式(A1-1)中のケイ素原子との結合部位を表す。
Specific examples of R3 in formula (A1-1) are shown below, but the present invention is not limited to these. In the following formula, * represents the bonding site to the silicon atom in formula (A1-1).

 第一の化合物Aは、下記式(A1-2)で表される化合物であることが好ましい。

 式(A1-2)中、Rは酸素原子、窒素原子及び硫黄原子から選ばれる少なくとも1つ以上の原子を有する有機基であり、Rが複数ある場合は同一であってもよいし、異なっていてもよく、Rは水素原子又は上記Rに該当しない任意の有機基であり、Rが複数ある場合は同一であってもよいし、異なっていてもよく、R及びRのうち少なくとも2つが結合して環構造を形成してもよく、nは1~3の整数を表し、Lは2価の連結基を表し、Rは水素原子又は1価の有機基を表す。
The first compound A is preferably a compound represented by the following formula (A1-2).

In formula (A1-2), R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different, R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different, at least two of R 1 and R 2 may be bonded to form a ring structure, n represents an integer of 1 to 3, L represents a divalent linking group, and R 4 represents a hydrogen atom or a monovalent organic group.

 式(A1-2)中、R、R及びnの好ましい態様は、上述の式(A1-1)におけるR、R及びnの好ましい態様と同様である。
 式(A1-2)中、Lは水素原子が置換されていてもよいアルキレン基であることが好ましい。上記アルキレン基の炭素数は、2~10であることが好ましく、2~4であることが更に好ましい。また、上記アルキレン基が無置換のアルキレン基である態様も、本発明の好ましい態様の一つである。
 式(A1-2)中、Rは炭化水素基、又は、*-C(=O)R33で表される基であることが好ましい。
 式(A1-2)中、Rが表す炭化水素基としては、水素原子が置換基で置換されてもよい芳香族炭化水素基、又は、水素原子が置換基で置換されてもよい脂肪族不飽和炭化水素基がより好ましく、水素原子が置換基で置換されてもよい芳香族炭化水素基がより好ましい。
 上記水素原子が置換基で置換されてもよい芳香族炭化水素基としては、水素原子が置換基で置換されてもよい炭素数6~20の芳香族炭化水素基が好ましく、水素原子が置換基で置換されてもよいフェニレン基がより好ましい。上記水素原子が置換基で置換されてもよい芳香族炭化水素基における置換基としては、カルボキシ基、ヒドロキシ基、アルキル基、アルコキシ基、ハロゲン原子等が挙げられ、カルボキシ基が好ましい。
 上記水素原子が置換基で置換されてもよい脂肪族不飽和炭化水素基としては、エチレン基等が挙げられる。
 R31が表す*-C(=O)R33で表される基において、*は式(A1-2)中の窒素原子との結合部位を表す。上記R33は有機基を表し、水素原子が置換基で置換されてもよい芳香族炭化水素基が好ましい。この水素原子が置換基で置換されてもよい芳香族炭化水素基の好ましい態様は、上記Rが炭化水素基である場合の水素原子が置換基で置換されてもよい芳香族炭化水素基の好ましい態様と同様である。
In formula (A1-2), preferred embodiments of R 1 , R 2 and n are the same as the preferred embodiments of R 1 , R 2 and n in formula (A1-1) described above.
In formula (A1-2), L is preferably an alkylene group which may be substituted with a hydrogen atom. The number of carbon atoms in the alkylene group is preferably 2 to 10, and more preferably 2 to 4. In addition, an embodiment in which the alkylene group is an unsubstituted alkylene group is also one of the preferred embodiments of the present invention.
In formula (A1-2), R 4 is preferably a hydrocarbon group or a group represented by *-C(=O)R 33 .
In formula (A1-2), the hydrocarbon group represented by R 4 is preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or an aliphatic unsaturated hydrocarbon group in which a hydrogen atom may be substituted with a substituent, and more preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
The aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms in which a hydrogen atom may be substituted with a substituent, and more preferably a phenylene group in which a hydrogen atom may be substituted with a substituent. Examples of the substituent in the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent include a carboxy group, a hydroxy group, an alkyl group, an alkoxy group, a halogen atom, etc., and a carboxy group is preferred.
Examples of the aliphatic unsaturated hydrocarbon group in which a hydrogen atom may be substituted with a substituent include an ethylene group.
In the group represented by *-C(=O) R33 represented by R31 , * represents the bonding site with the nitrogen atom in formula (A1-2). R33 represents an organic group, and is preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent. Preferred aspects of this aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent are the same as the preferred aspects of the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent when R4 is a hydrocarbon group.

 本発明の第二の樹脂組成物は、第二の化合物Aを含む。
 第二の化合物Aは、式(A2-1)で表される化合物である。

 式(A2-1)中、R21はHSP値が17.0~27.0MPa1/2である有機基であり、R21が複数ある場合は同一であってもよいし、異なっていてもよく、R22は水素原子又は上記R21に該当しない任意の有機基であり、R22が複数ある場合は同一であってもよいし、異なっていてもよく、R21及びR22のうち少なくとも2つが結合して環構造を形成してもよく、nは1~3の整数を表し、mは1以上の整数を表し、R23はm価の有機基を表す。
The second resin composition of the present invention contains a second compound A.
The second compound A is a compound represented by formula (A2-1).

In formula (A2-1), R 21 is an organic group having an HSP value of 17.0 to 27.0 MPa 1/2 , and when there is a plurality of R 21 , they may be the same or different, R 22 is a hydrogen atom or any organic group not corresponding to the above R 21 , and when there is a plurality of R 22 , they may be the same or different, at least two of R 21 and R 22 may be bonded to form a ring structure, n represents an integer of 1 to 3, m represents an integer of 1 or more, and R 23 represents an m-valent organic group.

 式(A2-1)中、R21はHSP値が17.0~25.0MPa1/2である有機基でであることが好ましく、HSP値が17.5~24.5MPa1/2である有機基であることが更に好ましい。
 本明細書において、R21及び後述するR22のSP値は、R21又はR22の酸素との結合を水素に置き換えた構造に関して計算ソフトHSPiP(バージョン4.1.07)で3成分(dD、dP、dH)を算出し、下記式により導かれるtotalHSPをHSP値とした。
totalHSP(MPa1/2) = (dD+dP+dH1/2
In formula (A2-1), R 21 is preferably an organic group having an HSP value of 17.0 to 25.0 MPa 1/2 , and more preferably an organic group having an HSP value of 17.5 to 24.5 MPa 1/2 .
In this specification, the SP values of R21 and R22 described later were calculated by calculating three components (dD, dP, dH) using the calculation software HSPiP (version 4.1.07) for a structure in which the bond with oxygen of R21 or R22 was replaced with hydrogen, and the total HSP derived by the following formula was used as the HSP value.
totalHSP(MPa 1/2 ) = (dD 2 +dP 2 +dH 2 ) 1/2

 式(A2-1)中、R21の構造の好ましい態様は、上述の式(A1-1)におけるRの構造の好ましい態様と同様である。 In formula (A2-1), the preferred embodiments of the structure of R 21 are the same as the preferred embodiments of the structure of R 1 in formula (A1-1) described above.

 式(A2-1)中、R22は水素原子又は上記R21に該当しない任意の有機基であり、上記R21に該当しない任意の有機基であることが好ましい。
 上記R21に該当しない任意の有機基とは、HSP値が17.0MPa1/2未満であるか、又は、HSP値が27.0MPa1/2を超える有機基であり、HSP値が17.0MPa1/2未満であることが好ましい。
In formula (A2-1), R 22 is a hydrogen atom or any organic group other than the above R 21 , and is preferably any organic group other than the above R 21 .
The arbitrary organic group not corresponding to R 21 is an organic group having an HSP value of less than 17.0 MPa 1/2 or an HSP value of more than 27.0 MPa 1/2 , and preferably an HSP value of less than 17.0 MPa 1/2 .

 式(A2-1)中、R22の構造の好ましい態様は、上述の式(A1-1)におけるR23の構造の好ましい態様と同様である。 In formula (A2-1), the preferred embodiments of the structure of R 22 are the same as the preferred embodiments of the structure of R 23 in formula (A1-1) described above.

 式(A2-1)中、n、m及びR23の構造の好ましい態様は、上述の式(A1-1)におけるn、m及びRの構造の好ましい態様と同様である。 In formula (A2-1), the preferred embodiments of the structures of n, m and R 23 are the same as the preferred embodiments of the structures of n, m and R 3 in formula (A1-1) described above.

 第二の化合物Aは、下記式(A2-2)で表される化合物であることが好ましい。

 式(A2-2)中、R21はHSP値が17.0~27.0MPa1/2である有機基であり、R21は酸素原子、窒素原子及び硫黄原子から選ばれる少なくとも1つ以上の原子を有する有機基であり、R21が複数ある場合は同一であってもよいし、異なっていてもよく、R22は水素原子又は上記R21に該当しない任意の有機基であり、R22が複数ある場合は同一であってもよいし、異なっていてもよく、R21及びR22のうち少なくとも2つが結合して環構造を形成してもよく、nは1~3の整数を表し、Lは2価の連結基を表し、R24は水素原子又は1価の有機基を表す。
The second compound A is preferably a compound represented by the following formula (A2-2).

In formula (A2-2), R 21 is an organic group having an HSP value of 17.0 to 27.0 MPa 1/2 , R 21 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, when there is a plurality of R 21 , they may be the same or different, R 22 is a hydrogen atom or any organic group not corresponding to the above R 21 , when there is a plurality of R 22 , they may be the same or different, at least two of R 21 and R 22 may be bonded to form a ring structure, n represents an integer of 1 to 3, L represents a divalent linking group, and R 24 represents a hydrogen atom or a monovalent organic group.

 式(A2-2)中、R21及びR22の好ましい態様は、式(1-2)中のR21及びR22の好ましい態様と同様である。
 式(A2-2)中、n、L及びR24の好ましい態様は、式(1-2)中のn、L及びR24の好ましい態様と同様である。
In formula (A2-2), preferred embodiments of R 21 and R 22 are the same as the preferred embodiments of R 21 and R 22 in formula (1-2).
In formula (A2-2), the preferred embodiments of n, L and R 24 are the same as the preferred embodiments of n, L and R 24 in formula (1-2).

〔分子量〕
 化合物Aの分子量は、300~1500であることが好ましく、320~1000であることがより好ましく、350~800であることが更に好ましい。
[Molecular weight]
The molecular weight of compound A is preferably 300-1,500, more preferably 320-1,000, and even more preferably 350-800.

〔合成方法〕
 化合物Aは、例えば、無水条件かつ塩酸など強酸の存在下で、トリアルコキシシリル化合物に対して、対応するアルコール化合物を作用させてアルコキシ交換反応を実施することで合成される。また、その他公知の合成方法を用いて合成してもよく、合成方法は特に限定されるものではない。
[Synthesis Method]
Compound A is synthesized, for example, by reacting a corresponding alcohol compound with a trialkoxysilyl compound under anhydrous conditions and in the presence of a strong acid such as hydrochloric acid to carry out an alkoxy exchange reaction. Alternatively, compound A may be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.

〔具体例〕
 化合物Aの具体例としては、特に限定されないが、後述する実施例において使用された化合物が挙げられる。
[Specific examples]
Specific examples of compound A include, but are not limited to, the compounds used in the examples described below.

〔含有量〕
 本発明の樹脂組成物の全固形分に対する、化合物Aの含有量は、0.02~10質量%であることが好ましい。下限は0.05質量%以上がより好ましく、0.10質量%以上が更に好ましく、0.20質量%以上が特に好ましい。上限は、8質量%以下であることがより好ましく、4質量%以下であることが更に好ましく、2質量%以下であることが特に好ましい。また、0.5質量%以下である態様も、本発明の好ましい態様の一つである。
 化合物Aは1種を単独で用いてもよいが、2種以上を併用してもよい。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。
[Content]
The content of compound A relative to the total solid content of the resin composition of the present invention is preferably 0.02 to 10 mass%. The lower limit is more preferably 0.05 mass% or more, even more preferably 0.10 mass% or more, and particularly preferably 0.20 mass% or more. The upper limit is more preferably 8 mass% or less, even more preferably 4 mass% or less, and particularly preferably 2 mass% or less. In addition, an embodiment in which the content is 0.5 mass% or less is also one of the preferred embodiments of the present invention.
Compound A may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.

<化合物X1>
 本発明の樹脂組成物は、化合物X1を含んでもよい。
 化合物X1は1,3-ジカルボニル構造及びβ-ヒドロキシカルボニル構造からなる群より選ばれた少なくとも一方の構造を有し、分子量が1,000以下である化合物である。
 ここで、1,3-ジカルボニル構造とは、下記式(DC-1)で表される構造をいい、β-ヒドロキシカルボニル構造とは、下記式(HC-1)で表される構造をいう。
<Compound X1>
The resin composition of the present invention may contain compound X1.
Compound X1 is a compound having at least one structure selected from the group consisting of a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure, and having a molecular weight of 1,000 or less.
Here, the 1,3-dicarbonyl structure refers to a structure represented by the following formula (DC-1), and the β-hydroxycarbonyl structure refers to a structure represented by the following formula (HC-1).


 式(DC-1)又は式(HC-1)中、*及び#はそれぞれ、他の構造との結合部位を表す。ここで、*は炭素原子、酸素原子、窒素原子又は硫黄原子との結合部位であることが好ましい。また、#は水素原子又は炭素原子との結合部位であることが好ましい。
 ここで、上記(DC-1)で表される構造は、下記式(DC-2)のようにエノール型であってもよい。
 また、上記(HC-1)で表される構造は、下記式(HC-2)のようにエノール型であってもよい。

 式(DC-2)又は式(HC-2)中、*及び#はそれぞれ、他の構造との結合部位を表す。*は炭素原子、酸素原子、窒素原子又は硫黄原子との結合部位であることが好ましい。また、#は水素原子又は炭素原子との結合部位であることが好ましい。

In formula (DC-1) or formula (HC-1), * and # each represent a bonding site with another structure. Here, * is preferably a bonding site with a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. Also, # is preferably a bonding site with a hydrogen atom or a carbon atom.
Here, the structure represented by the above formula (DC-1) may be an enol type as represented by the following formula (DC-2).
The structure represented by the above formula (HC-1) may be an enol type as represented by the following formula (HC-2).

In formula (DC-2) or formula (HC-2), * and # each represent a bonding site with another structure. * is preferably a bonding site with a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. Also, # is preferably a bonding site with a hydrogen atom or a carbon atom.

 化合物X1は、構造中に金属原子を含まないことが好ましい。ここでいう金属原子には、シリカ等の半金属原子は含まないものとする。
 また、化合物X1は、樹脂組成物中で金属原子に配位していないことが好ましい。
It is preferable that compound X1 does not contain a metal atom in the structure. The metal atom in this case does not include a metalloid atom such as silica.
In addition, it is preferable that the compound X1 is not coordinated to a metal atom in the resin composition.

〔分子量〕
 化合物X1の分子量は、1,000以下であり、100~500であることが好ましく、100~400であることがより好ましく、100~350であることが更に好ましく、100~300であることが特に好ましく、100~250であることが一層好ましい。
[Molecular weight]
The molecular weight of compound X1 is 1,000 or less, preferably 100 to 500, more preferably 100 to 400, even more preferably 100 to 350, particularly preferably 100 to 300, and even more preferably 100 to 250.

〔具体例〕
 化合物X1の具体例としては、特に限定されないが、下記構造の化合物が挙げられる。
[Specific examples]
Specific examples of compound X1 include, but are not limited to, compounds having the following structures:

〔含有量〕
 本発明の樹脂組成物の全固形分に対する、化合物X1の含有量は、0.01~30質量%であることが好ましい。下限は0.02質量%以上がより好ましく、0.05質量%以上が更に好ましく、0.10質量%以上が特に好ましい。上限は、20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%以下であることが特に好ましい。また、1質量%以下である態様も、本発明の好ましい態様の一つである。
 化合物X1は1種を単独で用いてもよいが、2種以上を併用してもよい。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。
[Content]
The content of compound X1 relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 30 mass%. The lower limit is more preferably 0.02 mass% or more, even more preferably 0.05 mass% or more, and particularly preferably 0.10 mass% or more. The upper limit is more preferably 20 mass% or less, even more preferably 10 mass% or less, and particularly preferably 5 mass% or less. In addition, an embodiment in which the content is 1 mass% or less is also one of the preferred embodiments of the present invention.
Compound X1 may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.

<化合物X2>
 本発明の樹脂組成物は、化合物X2を含むことが好ましい。
 化合物X2は下記式(B-1)で表される化合物である。

 式(B-1)中、RB1は第三級アルキル基を表し、RB2はそれぞれ独立に、水素原子又は有機基を表す。
<Compound X2>
The resin composition of the present invention preferably contains compound X2.
Compound X2 is a compound represented by the following formula (B-1).

In formula (B-1), R B1 represents a tertiary alkyl group, and R B2 each independently represents a hydrogen atom or an organic group.

 式(B-1)中、RB1は第三級アルキル基を表し、下記式(B1-1)で表される基であることが好ましく、t-ブチル基であることがより好ましい。

 式(B1-1)中、RB3はそれぞれ独立に、アルキル基を表し、*は式(B-1)中のベンゼン環との結合部位を表す。
 式(B1-1)中、RB3はそれぞれ独立に、炭素数1~10のアルキル基が好ましく、炭素数1~4のアルキル基がより好ましく、メチル基又はエチル基が更に好ましく、メチル基が特に好ましい。また、上記アルキル基は直鎖アルキル基であることが好ましい。
In formula (B-1), R B1 represents a tertiary alkyl group and is preferably a group represented by the following formula (B1-1), and more preferably a t-butyl group.

In formula (B1-1), R B3 each independently represents an alkyl group, and * represents a bonding site to the benzene ring in formula (B-1).
In formula (B1-1), R B3 are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. In addition, the alkyl group is preferably a linear alkyl group.

 式(B-1)中、RB2が有機基である場合、RB2は、炭化水素基、又は、炭化水素基と環構造の組み合わせにより表される基が好ましい。炭化水素基としては、脂肪族飽和炭化水素基、又は、脂肪族炭化水素基と芳香族炭化水素基との組み合わせにより表される基であることが好ましい。環構造としては、芳香族環構造、脂肪族環構造のいずれであってもよいが、脂肪族環構造が好ましく、イソシアヌル環構造がより好ましい。 In formula (B-1), when R B2 is an organic group, R B2 is preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and a ring structure. The hydrocarbon group is preferably an aliphatic saturated hydrocarbon group or a group represented by a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The ring structure may be either an aromatic ring structure or an aliphatic ring structure, but is preferably an aliphatic ring structure, and more preferably an isocyanuric ring structure.

 化合物X2の分子量は、100~2000であることが好ましく、150~1000であることがより好ましく、200~800であることが更に好ましい。 The molecular weight of compound X2 is preferably 100 to 2000, more preferably 150 to 1000, and even more preferably 200 to 800.

 式(B-1)で表される化合物の具体例としては、特に限定されないが、2,6-ジ-tert-ブチル-4-メチルフェノール、ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、チオジエチレンビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート、N,N’-ヘキサン-1,6-ジイルビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオンアミド]、3,3’,3”,5,5’,5”-ヘキサ-tert-ブチル-a,a’,a”-(メシチレン-2,4,6-トリイル)トリ-p-クレゾール、エチレンビス(オキシエチレン)ビス[3-(5-tert-ブチル-4-ヒドロキシ-m-トリル)プロピオネート]、ヘキサメチレンビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート、1,3,5-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン、2,6-ジ-tert-ブチル-4-(4,6-ビス(オクチルチオ)-1,3,5-トリアジン-2-イルアミノ)フェノール、4,4’,4”-(1-メチルプロパニル-3-イリデン)トリス(6-tert-ブチル-m-クレゾール)、6,6’-ジ-tert-ブチル-4,4’-ブチリデン-m-クレゾール、3,9-ビス[2-[3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ]-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5,5]ウンデカン、t-ブチルハイドロキノン、ジ-t-ブチル-p-クレゾール、4,4-チオビス(3-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)等が挙げられる。 Specific examples of the compound represented by formula (B-1) include, but are not limited to, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N, N'-Hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 4,4',4"-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl- Examples include 4,4'-butylidene-m-cresol, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, t-butylhydroquinone, di-t-butyl-p-cresol, 4,4-thiobis(3-methyl-6-t-butylphenol), and 2,2'-methylenebis(4-methyl-6-t-butylphenol).

 本発明の樹脂組成物の全固形分に対する、化合物X2の含有量は、0.1~5質量%であることが好ましい。下限は0.2質量%以上がより好ましく、0.3質量%以上が更に好ましい。上限は、3質量%以下であることがより好ましく、1質量%以下であることが更に好ましい。
 化合物X2は1種を単独で用いてもよいが、2種以上を併用してもよい。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 content of compound X2 relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 5 mass %. The lower limit is more preferably 0.2 mass % or more, and even more preferably 0.3 mass % or more. The upper limit is more preferably 3 mass % or less, and even more preferably 1 mass % or less.
Compound X2 may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.

<化合物X3>
 本発明の樹脂組成物は、現像性の向上等の観点から、下記式(X-3)で表される化合物を含むことが好ましい。

 式(X-3)中、RX1は、水素原子又はアルキル基を表し、nは1~10の整数である。
 式(X-3)中、RX1は水素原子又は炭素数1~15のアルキル基が好ましく、水素原子又は炭素数1~12のアルキル基がより好ましく、水素原子又は炭素数1~4のアルキル基が更に好ましく、水素原子、メチル基又はエチル基であることが特に好ましい。
<Compound X3>
From the viewpoint of improving developability, etc., the resin composition of the present invention preferably contains a compound represented by the following formula (X-3).

In formula (X-3), R 1 X1 represents a hydrogen atom or an alkyl group, and n is an integer of 1 to 10.
In formula (X-3), R X1 is preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, still more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

 化合物X3の具体例としては、4-ヒドロキシ酪酸、4-ヒドロキシ酪酸メチル、4-ヒドロキシ酪酸エチル、4-ヒドロキシ酪酸プロピル、4-ヒドロキシ酪酸イソプロピル、4-ヒドロキシ酪酸ブチル、4-ヒドロキシ酪酸ペンチル、4-ヒドロキシ酪酸ヘキシル、4-ヒドロキシ酪酸ヘプチル、4-ヒドロキシ酪酸オクチル、4-ヒドロキシ酪酸ノニル、4-ヒドロキシ酪酸デシル等が挙げられる。 Specific examples of compound X3 include 4-hydroxybutyric acid, methyl 4-hydroxybutyrate, ethyl 4-hydroxybutyrate, propyl 4-hydroxybutyrate, isopropyl 4-hydroxybutyrate, butyl 4-hydroxybutyrate, pentyl 4-hydroxybutyrate, hexyl 4-hydroxybutyrate, heptyl 4-hydroxybutyrate, octyl 4-hydroxybutyrate, nonyl 4-hydroxybutyrate, and decyl 4-hydroxybutyrate.

 化合物X3の含有量は、特定樹脂100質量部に対して、0.01~10質量部であることが好ましく、0.05~5質量部であることがより好ましい。 The content of compound X3 is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the specific resin.

<第四族元素を含む化合物>
 本発明の樹脂組成物は、耐薬品性の観点から、第四族元素を含む化合物を含んでいてもよい。
 第四族元素を含む化合物は、チタン、ジルコニウム又はハフニウムを含む化合物であることが好ましく、チタンを含む化合物であることがより好ましい。
 また、第四族元素を含む化合物は、有機金属錯体であることが好ましく、有機チタン錯体であることがより好ましい。
<Compounds containing Group 4 elements>
From the viewpoint of chemical resistance, the resin composition of the present invention may contain a compound containing a Group 4 element.
The compound containing a Group 4 element is preferably a compound containing titanium, zirconium or hafnium, and more preferably a compound containing titanium.
The compound containing a Group 4 element is preferably an organometallic complex, and more preferably an organotitanium complex.

 チタンを含む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、アルコキシ基を2個以上有するチタンキレートが、ネガ型感光性樹脂組成物の保存安定性及び良好なパターンが得られることからより好ましく、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。
Specific examples of titanium-containing compounds are shown below in I) to VII):
I) Titanium chelate compounds: Among these, titanium chelates having two or more alkoxy groups are more preferred because they provide good storage stability for the negative photosensitive resin composition and a good pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.

 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。 II) Tetraalkoxytitanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc.

 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(η-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(η-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。 III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

 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。 IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.

 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。 V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.

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。 VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, etc.

 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。 VII) Titanate coupling agents: For example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

 上記I)~VII)の中でも、チタンを含む化合物が、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(η-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 the above I) to VII), the titanium-containing compound is preferably at least one compound selected from the group consisting of the above I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

 樹脂組成物が第四族元素を含む化合物を含有する場合、含有量は、特定樹脂100質量部に対し、0.05質量部~10質量部であることが好ましく、0.1質量部~2質量部であることがより好ましい。上記含有量が0.05質量部以上である場合には耐熱性及び耐薬品性が向上し、10質量部以下である場合には保存安定性が向上する。 When the resin composition contains a compound containing a Group 4 element, the content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance are improved, and when it is 10 parts by mass or less, the storage stability is improved.

<重合性化合物>
 本発明の樹脂組成物は、重合性化合物を含むことが好ましい。
 特に、本発明の樹脂組成物は、ウレア結合及びウレタン結合の少なくとも一方を有する重合性化合物を更に含むことが好ましい。本発明の樹脂組成物は、ウレア結合及びウレタン結合の少なくとも一方を有する重合性化合物として、後述のウレア結合及びウレタン結合の少なくとも一方を有するラジカル架橋剤を更に含むことが好ましい。
 重合性化合物としては、ラジカル架橋剤、又は、他の架橋剤が挙げられる。
<Polymerizable Compound>
The resin composition of the present invention preferably contains a polymerizable compound.
In particular, the resin composition of the present invention preferably further contains a polymerizable compound having at least one of a urea bond and a urethane bond. The resin composition of the present invention preferably further contains a radical crosslinking agent having at least one of a urea bond and a urethane bond, which will be described later, as the polymerizable compound having at least one of a urea bond and a urethane bond.
The polymerizable compound may include a radical crosslinking agent or other crosslinking agents.

〔ラジカル架橋剤〕
 本発明の樹脂組成物は、ラジカル架橋剤を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、マレイミド基、(メタ)アクリルアミド基などが挙げられる。
 これらの中でも、(メタ)アクリロイル基、(メタ)アクリルアミド基、ビニルフェニル基が好ましく、反応性の観点からは、(メタ)アクリロイル基がより好ましい。
[Radical Crosslinking Agent]
The resin composition of the present invention preferably contains a radical crosslinking agent.
The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

 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ることが好ましいが、2個以上有する化合物であることがより好ましい。ラジカル架橋剤は、エチレン性不飽和結合を3個以上有していてもよい。
 上記エチレン性不飽和結合を2個以上有する化合物としては、エチレン性不飽和結合を2~15個有する化合物が好ましく、エチレン性不飽和結合を2~10個有する化合物がより好ましく、2~6個有する化合物が更に好ましい。
 得られるパターン(硬化物)の膜強度の観点からは、本発明の樹脂組成物は、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 crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.
As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is even more preferable.
From the viewpoint of the film strength of the obtained pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the above-mentioned compound having three or more ethylenically unsaturated bonds.

 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 crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

 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 radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxy groups, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids are also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. As another example, it is also possible to use a compound group in which the above unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

 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。常圧下で100℃以上の沸点を持つ化合物としては、国際公開第2021/112189号公報の段落0203に記載の化合物等が挙げられる。この内容は本明細書に組み込まれる。 The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021/112189, the contents of which are incorporated herein by reference.

 上述以外の好ましいラジカル架橋剤としては、国際公開第2021/112189号公報の段落0204~0208に記載のラジカル重合性化合物等が挙げられる。この内容は本明細書に組み込まれる。 Preferable radical crosslinking agents other than those mentioned above include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021/112189, the contents of which are incorporated herein by reference.

 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(新中村化学工業社製))、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。 The radical crosslinking agent is preferably dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), or a structure in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomer types of these may also be used.

 ラジカル架橋剤の市販品としては、例えば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SR-209、231、239(以上、サートマー社製)、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(以上、日本化薬(株)製)、ウレタンオリゴマーであるUAS-10、UAB-140(以上、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(以上、新中村化学工業社製)、DPHA-40H(日本化薬(株)製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(以上、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 radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates with four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers. Examples include UAS-10 and UAB-140 (all manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corp.).

 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。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。 As radical crosslinking agents, urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also suitable. As radical crosslinking agents, compounds having an amino structure or sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, can also be used.

 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 crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride. Particularly preferred is a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.

 酸基を有するラジカル架橋剤の酸価は、0.1~300mgKOH/gが好ましく、1~100mgKOH/gがより好ましい。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、現像性に優れる。また、重合性が良好である。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 crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, more preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, the agent has excellent handling properties during manufacturing and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

 ラジカル架橋剤としては、ウレア結合、及び、ウレタン結合からなる群より選ばれた少なくとも一方を有するラジカル架橋剤(以下、「架橋剤U」ともいう。)も好ましい。
 本発明において、ウレア結合とは、*-NR-C(=O)-NR-*で表される結合であり、Rはそれぞれ独立に、水素原子又は1価の有機基を表し、*はそれぞれ、炭素原子との結合部位を表す。
 本発明において、ウレタン結合とは*-O-C(=O)-NR-*で表される結合であり、Rは水素原子又は1価の有機基を表し、*はそれぞれ、炭素原子との結合部位を表す。
 樹脂組成物が架橋剤Uを含むことにより、耐薬品性、解像性等が向上する場合が有る。
 上記効果が得られるメカニズムは不明だが、例えば、加熱等による硬化時に架橋剤Uの一部が熱分解することにより、アミンなどが発生し、上記アミン等がポリイミド前駆体等のポリイミドの前駆体の環化を促進すると考えられる。
 架橋剤Uはウレア結合又はウレタン結合を1つのみ有してもよいし、1以上のウレア結合と1以上のウレタン結合とを有してもよいし、ウレタン結合を有さず2以上のウレア結合を有してもよいし、ウレア結合を有さず2以上のウレタン結合を有してもよい。
 架橋剤Uにおけるウレア結合及びウレタン結合の合計数は、1以上であり、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。
 架橋剤Uがウレタン結合を有しない場合、架橋剤Uにおけるウレア結合の数は1以上であり、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。
 架橋剤Uがウレア結合を有しない場合、架橋剤Uにおけるウレタン結合の数は1以上であり、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。
As the radical crosslinking agent, a radical crosslinking agent having at least one bond selected from the group consisting of a urea bond and a urethane bond (hereinafter, also referred to as "crosslinking agent U") is also preferred.
In the present invention, the urea bond is a bond represented by *-NR N -C(=O)-NR N -*, where each R N independently represents a hydrogen atom or a monovalent organic group, and each * represents a bonding site with a carbon atom.
In the present invention, a urethane bond is a bond represented by *--O--C(.dbd.O)-- NR.sub.N --*, where R.sub.N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom.
When the resin composition contains the crosslinking agent U, the chemical resistance, resolution, and the like may be improved.
The mechanism by which the above-mentioned effect is obtained is unclear; however, it is considered that, for example, during curing by heating or the like, a part of the crosslinking agent U is thermally decomposed to generate amines or the like, and the amines or the like promote cyclization of polyimide precursors such as polyimide precursors.
The crosslinking agent U may have only one urea bond or one urethane bond, may have one or more urea bonds and one or more urethane bonds, may have no urethane bonds but two or more urea bonds, or may have no urea bonds but two or more urethane bonds.
The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
When the crosslinking agent U has no urethane bond, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
When crosslinking agent U has no urea bond, the number of urethane bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

 架橋剤Uにおけるラジカル重合性基は、特に限定されないが、ビニル基、アリル基、(メタ)アクリロイル基、(メタ)アクリロキシ基、(メタ)アクリルアミド基、ビニルフェニル基、マレイミド基等が挙げられ、(メタ)アクリロキシ基、(メタ)アクリルアミド基、ビニルフェニル基、又は、マレイミド基が好ましく、(メタ)アクリロキシ基がより好ましい。
 架橋剤Uがラジカル重合性基を2以上有する場合、それぞれのラジカル重合性基の構造は同一であってもよいし、異なっていてもよい。
 架橋剤Uにおけるラジカル重合性基の数は、1つのみであってもよいし、2以上であってもよく、1~10が好ましく、1~6が更に好ましく、1~4が特に好ましい。
 架橋剤Uにおけるラジカル重合性基価(ラジカル重合性基1モル当たりの化合物の質量)は、150~400g/molであることが好ましい。
 上記ラジカル重合性基価の下限は、硬化物の耐薬品性の観点より、200g/mol以上であることがより好ましく、210g/mol以上であることが更に好ましく、220g/mol以上であることが一層好ましく、230g/mol以上であることがより一層好ましく、240g/mol以上であることがより更に好ましく、250g/mol以上であることが特に好ましい。
 上記ラジカル重合性基価の上限は、現像性の観点より、350g/mol以下であることがより好ましく、330g/mol以下であることが更に好ましく、300g/mol以下であることが特に好ましい。
 中でも、架橋剤Uの重合性基価は、210~400g/molであることが好ましく、220~400g/molであることがより好ましい。
The radical polymerizable group in the crosslinking agent U is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. Of these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred.
When the crosslinking agent U has two or more radically polymerizable groups, the structures of the respective radically polymerizable groups may be the same or different.
The number of radical polymerizable groups in the crosslinking agent U may be only one or may be two or more, and is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
The radically polymerizable group value (mass of compound per mole of radically polymerizable group) in the crosslinking agent U is preferably 150 to 400 g/mol.
From the viewpoint of chemical resistance of the cured product, the lower limit of the radically polymerizable group value is more preferably 200 g/mol or more, even more preferably 210 g/mol or more, still more preferably 220 g/mol or more, even more preferably 230 g/mol or more, still more preferably 240 g/mol or more, and particularly preferably 250 g/mol or more.
From the viewpoint of developability, the upper limit of the radically polymerizable group value is more preferably 350 g/mol or less, further preferably 330 g/mol or less, and particularly preferably 300 g/mol or less.
In particular, the polymerizable group value of the crosslinking agent U is preferably from 210 to 400 g/mol, and more preferably from 220 to 400 g/mol.

 架橋剤Uは、例えば下記式(U-1)で表される構造であることが好ましい。

Figure JPOXMLDOC01-appb-C000041

 式(U-1)中、RU1は水素原子又は1価の有機基であり、Aは-O-又は-NR-であり、Rは水素原子又は1価の有機基であり、ZU1はm価の有機基であり、ZU2はn+1価の有機基であり、Xはラジカル重合性基であり、nは1以上の整数であり、mは1以上の整数である。 The crosslinking agent U preferably has a structure represented by the following formula (U-1).
Figure JPOXMLDOC01-appb-C000041

In formula (U-1), R U1 is a hydrogen atom or a monovalent organic group, A is -O- or -NR N -, R N is a hydrogen atom or a monovalent organic group, Z U1 is an m-valent organic group, Z U2 is an (n+1)-valent organic group, X is a radical polymerizable group, n is an integer of 1 or more, and m is an integer of 1 or more.

 RU1は水素原子、アルキル基又は芳香族炭化水素基が好ましく、水素原子がより好ましい。
 Rは水素原子、アルキル基又は芳香族炭化水素基が好ましく、水素原子がより好ましい。
 ZU1は炭化水素基、-O-、-C(=O)-、-S-、-S(=O)-、-NR-、若しくは、これらが2以上結合した基が好ましく、炭化水素基、又は、炭化水素基と、-O-、-C(=O)-、-S-、-S(=O)-、及び、-NR-からなる群より選ばれた少なくとも1種の基とが結合した基がより好ましい。
 上記炭化水素基としては、炭素数20以下の炭化水素基が好ましく、18以下の炭化水素基がより好ましく、16以下の炭化水素基が更に好ましい。上記炭化水素基としては、飽和脂肪族炭化水素基、芳香族炭化水素基、又は、これらの結合により表される基などが挙げられる。Rは水素原子又は1価の有機基を表し、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、水素原子又はメチル基であることが更に好ましい。
 ZU2は炭化水素基、-O-、-C(=O)-、-S-、-S(=O)-、-NR-、若しくは、これらが2以上結合した基が好ましく、炭化水素基、又は、炭化水素基と、-O-、-C(=O)-、-S-、-S(=O)-、及び、-NR-からなる群より選ばれた少なくとも1種の基とが結合した基がより好ましい。
 上記炭化水素基としては、ZU1において挙げられたものと同様のものが挙げられ、好ましい態様も同様である。
 Xは特に限定されないが、ビニル基、アリル基、(メタ)アクリロイル基、(メタ)アクリロキシ基、(メタ)アクリルアミド基、ビニルフェニル基、マレイミド基等が挙げられ、(メタ)アクリロキシ基、(メタ)アクリルアミド基、ビニルフェニル基、又は、マレイミド基が好ましく、(メタ)アクリロキシ基がより好ましい。
 nは1~10の整数であることが好ましく、1~4の整数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。
 mは1~10の整数であることが好ましく、1~4の整数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。
R U1 is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
R 3 N is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
Z U1 is preferably a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) 2 -, -NR N -, or a group in which two or more of these are bonded, and more preferably a hydrocarbon group, or a group in which a hydrocarbon group is bonded to at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) 2 -, and -NR N -.
The above-mentioned hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. The above-mentioned hydrocarbon group includes a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof. R N represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.
Z U2 is preferably a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) 2 -, -NR N -, or a group in which two or more of these are bonded together, and more preferably a hydrocarbon group, or a group in which a hydrocarbon group is bonded to at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) 2 -, and -NR N -.
The hydrocarbon group includes the same as those exemplified for ZU1 , and preferred embodiments are also the same.
X is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. Of these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferable, and a (meth)acryloxy group is more preferable.
n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.
m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

 架橋剤Uは、ヒドロキシ基、アルキレンオキシ基、アミド基及びシアノ基の少なくとも1つを有することも好ましい。
 得られる硬化膜の耐薬品性の観点から、ヒドロキシ基は、アルコール性ヒドロキシ基であってもフェノール性ヒドロキシ基であってもよいが、アルコール性ヒドロキシ基であることが好ましい。
 得られる硬化膜の耐薬品性の観点から、アルキレンオキシ基としては、炭素数2~20のアルキレンオキシ基が好ましく、炭素数2~10のアルキレンオキシ基がより好ましく、炭素数2~4のアルキレンオキシ基が更に好ましく、エチレンオキシ基又はプロピレンオキシ基が更により好ましく、エチレン基が特に好ましい。
 アルキレンオキシ基は、ポリアルキレンオキシ基として架橋剤Uに含まれてもよい。この場合のアルキレンオキシ基の繰返し数は、2~10であることが好ましく、2~6であることがより好ましい。
 アミド基は、-C(=O)-NR-により表される結合をいう。Rは上述の通りである。架橋剤Uがアミド基を有する場合、架橋剤Uは、例えば、R-C(=O)-NR-*で表される基、又は、*-C(=O)-NR-Rで表される基として含むことができる。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であることが好ましく、水素原子、アルキル基又は芳香族炭化水素基であることがより好ましい。
 架橋剤Uは、ヒドロキシ基、アルキレンオキシ基(ただし、ポリアルキレンオキシ基を構成する場合は、ポリアルキレンオキシ基)、アミド基及びシアノ基からなる群より選ばれた構造を、分子内に2以上有してもよいが、分子内に1つのみ有する態様も好ましい。
 上記ヒドロキシ基、アルキレンオキシ基、アミド基及びシアノ基は架橋剤Uのいずれの位置に存在してもよいが、耐薬品性の観点からは、架橋剤Uは、上記ヒドロキシ基、アルキレンオキシ基、アミド基及びシアノ基からなる群より選ばれた少なくとも1つと、架橋剤Uに含まれる少なくとも1つのラジカル重合性基とが、ウレア結合又はウレタン結合を含む連結基(以下、「連結基L2-1」ともいう。)により連結されていることも好ましい。
 特に、架橋剤Uがラジカル重合性基を1つのみ含む場合、架橋剤Uに含まれるラジカル重合性基と、ヒドロキシ基、アルキレンオキシ基、アミド基及びシアノ基からなる群より選ばれた少なくとも1つとが、ウレア結合又はウレタン結合を含む連結基(以下、「連結基L2-2」ともいう。)により連結されていることが好ましい。
 架橋剤Uがアルキレンオキシ基(ただし、ポリアルキレンオキシ基を構成する場合は、ポリアルキレンオキシ基)を含み、かつ、上記連結基L2-1又は上記連結基L2-2を有する場合、アルキレンオキシ基(ただし、ポリアルキレンオキシ基を構成する場合は、ポリアルキレンオキシ基)の連結基L2-1又は連結基L2-2とは反対の側に結合する構造は、特に限定されないが、炭化水素基、ラジカル重合性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、炭素数20以下の炭化水素基が好ましく、18以下の炭化水素基がより好ましく、16以下の炭化水素基が更に好ましい。上記炭化水素基としては、飽和脂肪族炭化水素基、芳香族炭化水素基、又は、これらの結合により表される基などが挙げられる。また、ラジカル重合性基の好ましい態様は上述の架橋剤Uにおけるラジカル重合性基の好ましい態様と同様である。
 架橋剤Uがアミド基を含み、かつ、上記連結基L2-1又は上記連結基L2-2を有する場合、アミド基の連結基L2-1又は連結基L2-2とは反対の側に結合する構造は、特に限定されないが、炭化水素基、ラジカル重合性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、炭素数20以下の炭化水素基が好ましく、18以下の炭化水素基がより好ましく、16以下の炭化水素基が更に好ましい。また、上記炭化水素基としては、飽和脂肪族炭化水素基、芳香族炭化水素基、又は、これらの結合により表される基などが挙げられる。ラジカル重合性基の好ましい態様は上述の架橋剤Uにおけるラジカル重合性基の好ましい態様と同様である。また、上記態様において、アミド基の炭素原子側が連結基L2-1又は連結基L2-2と結合してもよいし、アミド基の窒素原子側が連結基L2-1又は連結基L2-2と結合してもよい。
 これらの中でも、基材との密着性、耐薬品性、及び、Cuボイド抑制の観点からは、架橋剤Uはヒドロキシ基を有することが好ましい。
It is also preferred that the cross-linking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group.
From the viewpoint of the chemical resistance of the resulting cured film, the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group.
From the viewpoint of the chemical resistance of the obtained cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, still more preferably an ethyleneoxy group or a propyleneoxy group, and particularly preferably an ethylene group.
The alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U. In this case, the number of repetitions of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6.
The amide group refers to a bond represented by -C(=O)-NR N -, where R N is as described above. When crosslinking agent U has an amide group, crosslinking agent U can contain it, for example, as a group represented by R-C(=O)-NR N -*, or a group represented by *-C(=O)-NR N -R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.
The crosslinking agent U may have, in the molecule, two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (when a polyalkyleneoxy group is formed, the group is a polyalkyleneoxy group), an amide group, and a cyano group. An embodiment having only one such structure in the molecule is also preferred.
The hydroxy group, alkyleneoxy group, amide group and cyano group may be present at any position of the crosslinking agent U. From the viewpoint of chemical resistance, however, it is also preferable that the crosslinking agent U is such that at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, amide group and cyano group and at least one radical polymerizable group contained in the crosslinking agent U are linked via a linking group containing a urea bond or a urethane bond (hereinafter, also referred to as "linking group L2-1").
In particular, when the crosslinking agent U contains only one radically polymerizable group, it is preferable that the radically polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").
When the crosslinking agent U contains an alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2, the structure bonded to the side of the alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. As the hydrocarbon group, a hydrocarbon group having 20 or less carbon atoms is preferable, a hydrocarbon group having 18 or less carbon atoms is more preferable, and a hydrocarbon group having 16 or less carbon atoms is even more preferable. As the hydrocarbon group, a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond thereof can be mentioned. In addition, a preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking agent U described above.
When the crosslinking agent U contains an amide group and has the linking group L2-1 or the linking group L2-2, the structure bonded to the side of the amide group opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. In addition, examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by bonds thereof. A preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking agent U described above. In addition, in the above embodiment, the carbon atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2.
Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that the crosslinking agent U has a hydroxy group.

 架橋剤Uは、特定樹脂との相溶性等の観点より、芳香族基を含むことが好ましい。
 上記芳香族基は、架橋剤Uに含まれるウレア結合又はウレタン結合と直接結合することが好ましい。架橋剤Uがウレア結合又はウレタン結合を2以上含む場合、ウレア結合又はウレタン結合のうち1つと、芳香族基とが直接結合することが好ましい。
 芳香族基は、芳香族炭化水素基であっても、芳香族ヘテロ環基であってもよく、これらが縮合環を形成した構造でもよいが、芳香族炭化水素基であることが好ましい。
 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、ベンゼン環構造から2以上の水素原子を除いた基が更に好ましい。
 上記芳香族ヘテロ環基としては、5員環又は6員環の芳香族ヘテロ環基が好ましい。このような芳香族ヘテロ環基における芳香族ヘテロ環としては、ピロール、イミダゾール、トリアゾール、テトラゾール、ピラゾール、フラン、チオフェン、オキサゾール、イソオキサゾール、チアゾール、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン等が挙げられる。これらの環は、例えば、インドール、ベンゾイミダゾールのように更に他の環と縮合していてもよい。
 上記芳香族ヘテロ環基に含まれるヘテロ原子としては、窒素原子、酸素原子又は硫黄原子が好ましい。
 上記芳香族基は、例えば、2以上のラジカル重合性基を連結し、ウレア結合又はウレタン結合を含む連結基、又は、上述のヒドロキシ基、アルキレンオキシ基、アミド基及びシアノ基からなる群より選ばれた少なくとも1つと、架橋剤Uに含まれる少なくとも1つのラジカル重合性基とを連結する連結基に含まれることが好ましい。
From the viewpoint of compatibility with the specific resin, the crosslinking agent U preferably contains an aromatic group.
The aromatic group is preferably directly bonded to a urea bond or a urethane bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.
The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure.
The aromatic heterocyclic group is preferably a 5-membered or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocyclic ring in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be further condensed with other rings, such as indole and benzimidazole.
The heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
The aromatic group is preferably contained in a linking group that links two or more radically polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radically polymerizable group contained in the crosslinking agent U.

 架橋剤Uにおけるウレア結合又はウレタン結合とラジカル重合性基との間の原子数(連結鎖長)は、特に限定されないが、30以下であることが好ましく、2~20であることがより好ましく、2~10であることが更に好ましい。
 架橋剤Uがウレア結合又はウレタン結合を合計で2以上含む場合、ラジカル重合性基を2以上含む場合、又は、ウレア結合若しくはウレタン結合を2以上含み、かつ、ラジカル重合性基を2以上含む場合、ウレア結合又はウレタン結合とラジカル重合性基の間の原子数(連結鎖長)のうち、最小のものが上記範囲内であればよい。
 本明細書において、「ウレア結合又はウレタン結合と重合性基との間の原子数(連結鎖長)」とは、連結対象の2つの原子または原子群の間を結ぶ経路上の原子鎖のうち、これらの連結対象を最短(最小原子数)で結ぶものをいう。例えば、下記式で表される構造において、ウレア結合とラジカル重合性基(メタクリロイルオキシ基)との間の原子数(連結鎖長)は2である。

Figure JPOXMLDOC01-appb-C000042
The number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10.
When the crosslinking agent U contains two or more urea bonds or urethane bonds in total, when it contains two or more radically polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radically polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond or urethane bond and the radically polymerizable group may be within the above range.
In this specification, the "number of atoms (linking chain length) between a urea bond or a urethane bond and a polymerizable group" refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked that links these objects with the shortest length (minimum number of atoms). For example, in the structure represented by the following formula, the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.
Figure JPOXMLDOC01-appb-C000042

〔対称軸〕
 架橋剤Uは対称軸を有しない構造の化合物であることも好ましい。
 架橋剤Uが対称軸を有しないとは、化合物全体を回転させることにより元の分子と同一の分子を生じる軸を有さず、左右非対称の化合物である事をいう。また、架橋剤Uの構造式を紙面上に表記した場合において、架橋剤Uが対称軸を有しないとは、架橋剤Uの構造式を、対称軸を有する形に表記することができないことをいう。
 架橋剤Uが対称軸を有しないことにより、組成物膜中では架橋剤U同士の凝集が抑制されると考えられる。
[Axis of symmetry]
It is also preferred that the crosslinking agent U is a compound having a structure that does not have an axis of symmetry.
The fact that the crosslinking agent U does not have an axis of symmetry means that the compound is a bilaterally asymmetric compound that does not have an axis that would produce an identical molecule to the original molecule by rotating the entire compound. In addition, when the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry.
It is believed that since the crosslinking agent U does not have an axis of symmetry, aggregation of the crosslinking agents U within the composition film is suppressed.

〔分子量〕
 架橋剤Uの分子量は、100~2,000であることが好ましく、150~1500であることがより好ましく、200~900であることが更に好ましい。
[Molecular weight]
The molecular weight of the crosslinking agent U is preferably 100-2,000, more preferably 150-1500, and even more preferably 200-900.

 架橋剤Uの製造方法は特に限定されないが、例えば、ラジカル重合性化合物とイソシアネート基とを有する化合物と、ヒドロキシ基又はアミノ基の少なくとも一方を有する化合物とを反応することにより得ることができる。 The method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a compound having a radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxy group or an amino group.

 架橋剤Uの具体例を以下に示すが、架橋剤Uはこれに限定されるものではない。


Specific examples of the crosslinking agent U are shown below, but the crosslinking agent U is not limited thereto.


 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、PEG(ポリエチレングリコール)200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、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレート、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(エチレンオキシド)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(プロピレンオキシド)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EO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。
 なお、例えばPEG200ジアクリレートとは、ポリエチレングリコールジアクリレートであって、ポリエチレングリコール鎖の式量が200程度のものをいう。
 本発明の樹脂組成物は、パターン(硬化物)の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。
 その他、2官能以上のラジカル架橋剤としては、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が挙げられる。
From the viewpoints of pattern resolution and film stretchability, it is preferable to use a difunctional methacrylate or acrylate for the resin composition.
Specific examples of the compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexyl 1,5-dimethylphenyl ... Xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, other bifunctional acrylates having a urethane bond, and bifunctional methacrylates having a urethane bond can be used. Two or more of these can be mixed and used as necessary.
For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain.
In the resin composition of the present invention, from the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional radical crosslinking agent, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether are preferably used. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100° C. or more under normal pressure is also preferred in order to suppress volatilization before exposure.
Other examples of the difunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

 ラジカル架橋剤を含有する場合、ラジカル架橋剤の含有量は、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 crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0 mass% and not more than 60 mass% based on the total solid content of the resin composition. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50 mass% or less, and even more preferably 30 mass% or less.

 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 crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount is within the above range.

〔他の架橋剤〕
 本発明の樹脂組成物は、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。
 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、上述の光酸発生剤、又は、光塩基発生剤の感光により、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、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、国際公開第2022/145355号の段落0179~0207に記載の化合物が挙げられる。上記記載は本明細書に組み込まれる。
[Other crosslinking agents]
The resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
The other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photoacid generator or photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
Other cross-linking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022/145355, the disclosures of which are incorporated herein by reference.

〔重合開始剤〕
 本発明の樹脂組成物は、重合開始剤を含むことが好ましい。
 重合開始剤は熱重合開始剤であっても光重合開始剤であってもよいが、特に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作用し、活性ラジカルを生成する活性剤であってもよい。
[Polymerization initiator]
The resin composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

 光ラジカル重合開始剤は、波長約240~800nm(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 preferably contains at least one compound having a molar absorption coefficient of at least about 50 L·mol −1 ·cm −1 in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.

 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などのα-アミノケトン化合物、ヒドロキシアセトフェノンなどのα-ヒドロキシケトン化合物、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。また、特開2014-130173号公報の段落0065~0111、特許第6301489号公報に記載された化合物、MATERIAL STAGE 37~60p,vol.19,No.3,2019に記載されたパーオキサイド系光重合開始剤、国際公開第2018/221177号に記載の光重合開始剤、国際公開第2018/110179号に記載の光重合開始剤、特開2019-043864号公報に記載の光重合開始剤、特開2019-044030号公報に記載の光重合開始剤、特開2019-167313号公報に記載の過酸化物系開始剤が挙げられ、これらの内容は本明細書に組み込まれる。 Any known compound can be used as the photoradical polymerization initiator. For example, halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenones, α-hydroxyketone compounds such as hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. For details of these, please refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of WO 2015/199219, the contents of which are incorporated herein by reference. Further examples include the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A and JP 6301489 A, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in WO 2018/221177 A, the photopolymerization initiators described in WO 2018/110179 A, the photopolymerization initiators described in JP 2019-043864 A, the photopolymerization initiators described in JP 2019-044030 A, and the peroxide-based initiators described in JP 2019-167313 A, the contents of which are incorporated herein by reference.

 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-DETX-S(日本化薬(株)製)も好適に用いられる。 Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. As a commercially available product, Kayacure-DETX-S (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、この内容は本明細書に組み込まれる。 In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

 α-ヒドロキシケトン系開始剤としては、Omnirad 184、Omnirad 1173、Omnirad 2959、Omnirad 127(以上、IGM Resins B.V.社製)、IRGACURE 184(IRGACUREは登録商標)、DAROCUR 1173、IRGACURE 500、IRGACURE-2959、IRGACURE 127(以上、BASF社製)を用いることができる。 α-Hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

 α-アミノケトン系開始剤としては、Omnirad 907、Omnirad 369、Omnirad 369E、Omnirad 379EG(以上、IGM Resins B.V.社製)、IRGACURE 907、IRGACURE 369、及び、IRGACURE 379(以上、BASF社製)を用いることができる。 As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

 アミノアセトフェノン系開始剤、アシルホスフィンオキシド系開始剤、メタロセン化合物としては、例えば、国際公開第2021/112189号の段落0161~0163に記載の化合物も好適に使用することができる。この内容は本明細書に組み込まれる。 As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of WO 2021/112189 can also be suitably used. The contents of this specification are incorporated herein.

 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。 As a photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it becomes possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function 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、J.C.S.Perkin II(1979年、pp.1653-1660)に記載の化合物、J.C.S.Perkin II(1979年、pp.156-162)に記載の化合物、Journal of Photopolymer Science and Technology(1995年、pp.202-232)に記載の化合物、特開2000-066385号公報に記載の化合物、特表2004-534797号公報に記載の化合物、特開2017-019766号公報に記載の化合物、特許第6065596号公報に記載の化合物、国際公開第2015/152153号に記載の化合物、国際公開第2017/051680号に記載の化合物、特開2017-198865号公報に記載の化合物、国際公開第2017/164127号の段落番号0025~0038に記載の化合物、国際公開第2013/167515号に記載の化合物などが挙げられ、この内容は本明細書に組み込まれる。 Specific examples of oxime compounds include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, the compounds described in JP-A-2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, Examples of the compounds include those described in WO 6065596, WO 2015/152153, WO 2017/051680, JP 2017-198865, WO 2017/164127, paragraphs 0025 to 0038, and WO 2013/167515, the contents of which are incorporated herein by reference.

 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。樹脂組成物においては、特に光ラジカル重合開始剤としてオキシム化合物を用いることが好ましい。光ラジカル重合開始剤としてのオキシム化合物は、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 structure, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

 オキシム化合物の市販品としては、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)、TR-PBG-304、TR-PBG-305(常州強力電子新材料有限公司製)、アデカアークルズNCI-730、NCI-831及びアデカアークルズNCI-930((株)ADEKA製)、DFI-091(ダイトーケミックス(株)製)、SpeedCure PDO(SARTOMER ARKEMA製)が挙げられる。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。
Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemistry Co., Ltd.), and SpeedCure PDO (SARTOMER Also usable are oxime compounds having the following structure:

 光ラジカル重合開始剤としては、例えば、国際公開第2021/112189号の段落0169~0171に記載のフルオレン環を有するオキシム化合物、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、フッ素原子を有するオキシム化合物を用いることもできる。
 また、国際公開第2021/020359号に記載の段落0208~0210に記載のニトロ基を有するオキシム化合物、ベンゾフラン骨格を有するオキシム化合物、カルバゾール骨格にヒドロキシ基を有する置換基が結合したオキシム化合物を用いることもできる。これらの内容は本明細書に組み込まれる。
As the photoradical polymerization initiator, for example, an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of WO 2021/112189, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, or an oxime compound having a fluorine atom can be used.
In addition, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group-containing substituent bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of WO 2021/020359 can also be used. The contents of these compounds are incorporated herein by reference.

 光重合開始剤としては、芳香族環に電子求引性基が導入された芳香族環基ArOX1を有するオキシム化合物(以下、オキシム化合物OXともいう)を用いることもできる。上記芳香族環基ArOX1が有する電子求引性基としては、アシル基、ニトロ基、トリフルオロメチル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、シアノ基が挙げられ、アシル基およびニトロ基が好ましく、耐光性に優れた膜を形成しやすいという理由からアシル基であることがより好ましく、ベンゾイル基であることが更に好ましい。ベンゾイル基は、置換基を有していてもよい。置換基としては、ハロゲン原子、シアノ基、ニトロ基、ヒドロキシ基、アルキル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルケニル基、アルキルスルファニル基、アリールスルファニル基、アシル基またはアミノ基であることが好ましく、アルキル基、アルコキシ基、アリール基、アリールオキシ基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基またはアミノ基であることがより好ましく、アルコキシ基、アルキルスルファニル基またはアミノ基であることが更に好ましい。 As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar OX1 in which an electron-withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used. The electron-withdrawing group of the aromatic ring group Ar OX1 includes an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An acyl group and a nitro group are preferred, and an acyl group is more preferred because it is easy to form a film with excellent light resistance, and a benzoyl group is even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group, and further preferably an alkoxy group, an alkylsulfanyl group, or an amino group.

 オキシム化合物OXは、式(OX1)で表される化合物および式(OX2)で表される化合物から選ばれる少なくとも1種であることが好ましく、式(OX2)で表される化合物であることがより好ましい。

 式中、RX1は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アシルオキシ基、アミノ基、ホスフィノイル基、カルバモイル基またはスルファモイル基を表し、
 RX2は、アルキル基、アルケニル基、アルコキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシルオキシ基またはアミノ基を表し、
 RX3~RX14は、それぞれ独立して水素原子または置換基を表す。
 ただし、RX10~RX14のうち少なくとも一つは、電子求引性基である。
The oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), and more preferably the compound represented by the formula (OX2).

In the formula, R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group;
R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group;
R X3 to R X14 each independently represent a hydrogen atom or a substituent.
However, at least one of R X10 to R X14 is an electron-withdrawing group.

 上記式において、RX12が電子求引性基であり、RX10、RX11、RX13、RX14は水素原子であることが好ましい。 In the above formula, it is preferable that R X12 is an electron-withdrawing group, and R X10 , R X11 , R X13 and R X14 are each a hydrogen atom.

 オキシム化合物OXの具体例としては、特許第4600600号公報の段落番号0083~0105に記載の化合物が挙げられ、この内容は本明細書に組み込まれる。 Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.

 特に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、この内容は本明細書に組み込まれる。 Particularly preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP 2007-269779 A and oxime compounds having thioaryl groups as disclosed in JP 2009-191061 A, the contents of which are incorporated herein by reference.

 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からなる群より選択される化合物が好ましい。 From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

 また、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、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、ベンゾフェノン化合物からなる群より選ばれる少なくとも1種の化合物がより好ましく、メタロセン化合物又はオキシム化合物が更に好ましい。 The photoradical polymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound is more preferred, and a metallocene compound or an oxime compound is even more preferred.

 光ラジカル重合開始剤としては、国際公開第2021/020359号に記載の段落0175~0179に記載の化合物、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、この内容は本明細書に組み込まれる。 As the photoradical polymerization initiator, the compounds described in paragraphs [0175] to [0179] of WO 2021/020359 and the compounds described in paragraphs [0048] to [0055] of WO 2015/125469 can also be used, the contents of which are incorporated herein by reference.

 光ラジカル重合開始剤としては、2官能あるいは3官能以上の光ラジカル重合開始剤を用いてもよい。そのような光ラジカル重合開始剤を用いることにより、光ラジカル重合開始剤の1分子から2つ以上のラジカルが発生するため、良好な感度が得られる。また、非対称構造の化合物を用いた場合においては、結晶性が低下して溶剤などへの溶解性が向上して、経時で析出しにくくなり、樹脂組成物の経時安定性を向上させることができる。2官能あるいは3官能以上の光ラジカル重合開始剤の具体例としては、特表2010-527339号公報、特表2011-524436号公報、国際公開第2015/004565号、特表2016-532675号公報の段落番号0407~0412、国際公開第2017/033680号の段落番号0039~0055に記載されているオキシム化合物の2量体、特表2013-522445号公報に記載されている化合物(E)および化合物(G)、国際公開第2016/034963号に記載されているCmpd1~7、特表2017-523465号公報の段落番号0007に記載されているオキシムエステル類光開始剤、特開2017-167399号公報の段落番号0020~0033に記載されている光開始剤、特開2017-151342号公報の段落番号0017~0026に記載されている光重合開始剤(A)、特許第6469669号公報に記載されているオキシムエステル光開始剤などが挙げられ、この内容は本明細書に組み込まれる。 As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time, and improving the stability of the resin composition over time. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015/004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017/033680, paragraphs 0039 to 0055; compound (E) and compound (G) described in WO-T-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Publication No. 4963, the oxime ester photoinitiators described in paragraph 0007 of JP-T-2017-523465, the photoinitiators described in paragraphs 0020 to 0033 of JP-A-2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, and the oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

 樹脂組成物が光重合開始剤を含む場合、その含有量は、樹脂組成物の全固形分に対し0.1~30質量%が好ましく、0.1~20質量%がより好ましく、0.5~15質量%が更に好ましく、1.0~10質量%が更により好ましい。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。
 なお、光重合開始剤は熱重合開始剤としても機能する場合があるため、オーブンやホットプレート等の加熱によって光重合開始剤による架橋を更に進行させられる場合がある。
When the resin composition contains a photopolymerization initiator, the content is preferably 0.1 to 30 mass% based on the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range.
In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking caused by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

〔増感剤〕
 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。
 使用可能な増感剤として、ベンゾフェノン系、ミヒラーズケトン系、クマリン系、ピラゾールアゾ系、アニリノアゾ系、トリフェニルメタン系、アントラキノン系、アントラセン系、アントラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ペンゾピラン系、インジゴ系等の化合物を使用することができる。
 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(7-(ジエチルアミノ)クマリン-3-カルボン酸エチル)、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)ベンゾチアゾール、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。
 また、他の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 resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and are decomposed to generate a radical, an acid, or a base.
Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based compounds, and the like.
Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, and p-dimethylaminobenzylidene indanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 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 phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoethylaminobenzoate Examples of such an alkyl ether compound include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide.
Other sensitizing dyes may also be used.
For details about the sensitizing dye, the description in paragraphs [0161] to [0163] of JP2016-027357A can be referred to, the contents of which are incorporated herein by reference.

 樹脂組成物が増感剤を含む場合、増感剤の含有量は、樹脂組成物の全固形分に対し、0.01~20質量%が好ましく、0.1~15質量%がより好ましく、0.5~10質量%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 resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %. The sensitizer may be used alone or in combination of two or more types.

〔連鎖移動剤〕
 本発明の樹脂組成物は、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-S-S-、-SO-S-、-N-O-、SH、PH、SiH、及びGeHを有する化合物群、RAFT(Reversible Addition Fragmentation chain Transfer)重合に用いられるチオカルボニルチオ基を有するジチオベンゾアート、トリチオカルボナート、ジチオカルバマート、キサンタート化合物等が用いられる。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 resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of the chain transfer agent include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These donate hydrogen to a low activity radical to generate a radical, or are oxidized and then deprotonated to generate a radical. 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、この内容は本明細書に組み込まれる。 In addition, the chain transfer agent may be the compound described in paragraphs 0152 to 0153 of WO 2015/199219, the contents of which are incorporated herein by reference.

 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、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、0.1~10質量部がより好ましく、0.5~5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 resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total solid content of the resin composition. The chain transfer agent may be one type or two or more types. When there are two or more types of chain transfer agents, the total is preferably within the above range.

 また、本発明の樹脂組成物が、重合開始剤として、2種以上の重合開始剤を含むことも本発明の好ましい態様の一つである。
 具体的には、本発明の樹脂組成物は、光重合開始剤及び後述の熱重合開始剤を含むか、又は、上述の光ラジカル重合開始剤及び上述の光酸発生剤を含むことが好ましい。
In one preferred embodiment of the present invention, the resin composition of the present invention contains two or more types of polymerization initiators.
Specifically, the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

 光重合開始剤及び後述の熱重合開始剤を含むことにより、露光によるパターン形成が可能となり、かつ、後述の加熱工程による硬化時にラジカル重合も進行しやすくなり、耐薬品性等の性能が向上する場合が有る。
 光重合開始剤及び後述の熱重合開始剤を含む場合の含有比率としては、光重合開始剤及び熱重合開始剤の合計含有量に対し、熱重合開始剤の含有量が20~70質量%であることが好ましく、30~60質量%であることがより好ましい。
By including a photopolymerization initiator and a thermal polymerization initiator described below, it becomes possible to form a pattern by exposure to light, and radical polymerization also becomes more likely to proceed during curing by a heating step described below, and performance such as chemical resistance may be improved.
In the case where a photopolymerization initiator and a thermal polymerization initiator described later are contained, the content of the thermal polymerization initiator is preferably 20 to 70 mass%, and more preferably 30 to 60 mass%, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

 光ラジカル重合開始剤及び光酸発生剤を含むことにより解像性等の性能が向上する場合が有る。
 光重合開始剤及び光酸発生剤を含む場合の含有比率としては、光重合開始剤及び光酸発生剤の合計含有量に対し、光酸発生剤の含有量が20~70質量%であることが好ましく、30~60質量%であることがより好ましい。
By including a photoradical polymerization initiator and a photoacid generator, performance such as resolution may be improved.
When a photopolymerization initiator and a photoacid generator are contained, the content of the photoacid generator is preferably 20 to 70 mass%, and more preferably 30 to 60 mass%, relative to the total content of the photopolymerization initiator and the photoacid generator.

〔熱重合開始剤〕
 熱重合開始剤としては、例えば、熱ラジカル重合開始剤が挙げられる。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]
Examples of the thermal polymerization initiator include a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be promoted, 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、この内容は本明細書に組み込まれる。 Specific examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A, the contents of which are incorporated herein by reference.

 熱重合開始剤を含む場合、その含有量は、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い。樹脂組成物は熱重合開始剤を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。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 a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. The resin composition may contain only one type of thermal polymerization initiator, or may contain two or more types. When two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

<塩基発生剤>
 本発明の樹脂組成物は、塩基発生剤を含んでもよい。ここで、塩基発生剤とは、物理的または化学的な作用によって塩基を発生することができる化合物である。好ましい塩基発生剤としては、熱塩基発生剤および光塩基発生剤が挙げられる。
 特に、樹脂組成物がポリイミドの前駆体を含む場合、樹脂組成物は塩基発生剤を含むことが好ましい。樹脂組成物が熱塩基発生剤を含有することによって、例えば加熱により前駆体の環化反応を促進でき、硬化物の機械特性や耐薬品性が良好なものとなり、例えば半導体パッケージ中に含まれる再配線層用層間絶縁膜としての性能が良好となる。
 塩基発生剤としては、イオン型塩基発生剤でもよく、非イオン型塩基発生剤でもよい。塩基発生剤から発生する塩基としては、例えば、2級アミン、3級アミンが挙げられる。
 塩基発生剤は特に限定されず、公知の塩基発生剤を用いることができる。公知の塩基発生剤としては、例えば、カルバモイルオキシム化合物、カルバモイルヒドロキシルアミン化合物、カルバミン酸化合物、ホルムアミド化合物、アセトアミド化合物、カルバメート化合物、ベンジルカルバメート化合物、ニトロベンジルカルバメート化合物、スルホンアミド化合物、イミダゾール誘導体化合物、アミンイミド化合物、ピリジン誘導体化合物、α-アミノアセトフェノン誘導体化合物、4級アンモニウム塩誘導体化合物、イミニウム塩、ピリジニウム塩、α-ラクトン環誘導体化合物、アミンイミド化合物、フタルイミド誘導体化合物、アシルオキシイミノ化合物等が挙げられる。
 非イオン型塩基発生剤の具体例としては、国際公開第2022/145355号の段落0249~0275に記載の化合物が挙げられる。上記記載は本明細書に組み込まれる。
<Base Generator>
The resin composition of the present invention may contain a base generator. Here, the base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators.
In particular, when the resin composition contains a polyimide precursor, the resin composition preferably contains a base generator. By containing the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, and the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package can be improved.
The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
The base generator is not particularly limited, and a known base generator can be used. Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds.
Specific examples of the non-ionic base generator include the compounds described in paragraphs 0249 to 0275 of WO 2022/145355. The above descriptions are incorporated herein by reference.

 塩基発生剤としては、下記の化合物が挙げられるが、これらに限定されない。 Base generators include, but are not limited to, the following compounds:

 非イオン型塩基発生剤の分子量は、800以下が好ましく、600以下がより好ましく、500以下が更に好ましい。下限は、100以上が好ましく、200以上がより好ましく、300以上が更に好ましい。 The molecular weight of the nonionic 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.

 イオン型塩基発生剤の具体的な好ましい化合物としては、例えば、国際公開第2018/038002号の段落番号0148~0163に記載の化合物が挙げられる。 Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018/038002.

 アンモニウム塩の具体例としては、下記の化合物が挙げられるが、これらに限定されない。
Specific examples of ammonium salts include, but are not limited to, the following compounds:

 イミニウム塩の具体例としては、下記の化合物が挙げられるが、これらに限定されない。
Specific examples of iminium salts include, but are not limited to, the following compounds:

 また、塩基発生剤としては、保存安定性およびキュア時に脱保護で塩基を発生させる観点からアミノ基がt-ブトキシカルボニル基によって保護されたアミンであることが好ましい。 In addition, the base generator is preferably an amine in which the amino group is protected by a t-butoxycarbonyl group, from the viewpoints of storage stability and generating a base by deprotection during curing.

 t-ブトキシカルボニル基によって保護されたアミン化合物としては、例えば、エタノールアミン、3-アミノ-1-プロパノール、1-アミノ-2-プロパノール、2-アミノ-1-プロパノール、4-アミノ-1-ブタノール、2-アミノ-1-ブタノール、1-アミノ-2-ブタノール、3-アミノ-2,2-ジメチル-1-プロパノール、4-アミノ-2-メチル-1-ブタノール、バリノール、3-アミノ-1,2-プロパンジオール、2-アミノ-1,3-プロパンジオール、チラミン、ノルエフェドリン、2-アミノ-1-フェニル-1,3-プロパンジオール、2-アミノシクロヘキサノール、4-アミノシクロヘキサノール、4-アミノシクロヘキサンエタノール、4-(2-アミノエチル)シクロヘキサノール、N-メチルエタノールアミン、3-(メチルアミノ)-1-プロパノール、3-(イソプロピルアミノ)プロパノール、N-シクロヘキシルエタノールアミン、α-[2-(メチルアミノ)エチル]ベンジルアルコール、ジエタノールアミン、ジイソプロパノールアミン、3-ピロリジノール、2-ピロリジンメタノール、4-ヒドロキシピペリジン、3-ヒドロキシピペリジン、4-ヒドロキシ-4-フェニルピペリジン、4-(3-ヒドロキシフェニル)ピペリジン、4-ピペリジンメタノール、3-ピペリジンメタノール、2-ピペリジンメタノール、4-ピペリジンエタノール、2-ピペリジンエタノール、2-(4-ピペリジル)-2-プロパノール、1,4-ブタノールビス(3-アミノプロピル)エーテル、1,2-ビス(2-アミノエトキシ)エタン、2,2’-オキシビス(エチルアミン)、1,14-ジアミノ-3,6,9,12-テトラオキサテトラデカン、1-アザ-15-クラウン5-エーテル、ジエチレングリコールビス(3-アミノプロピル)エーテル、1,11-ジアミノ-3,6,9-トリオキサウンデカン、又は、アミノ酸及びその誘導体のアミノ基をt-ブトキシカルボニル基によって保護した化合物が挙げられるが、これらに限定されるものではない。 Amine compounds protected by a t-butoxycarbonyl group include, for example, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, Diol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethano diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis(3-aminopropyl)ethane ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl)ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or a derivative thereof is protected with a t-butoxycarbonyl group, but are not limited to these.

 樹脂組成物が塩基発生剤を含む場合、塩基発生剤の含有量は、樹脂組成物中の樹脂100質量部に対し、0.1~50質量部が好ましい。下限は、0.3質量部以上がより好ましく、0.5質量部以上が更に好ましい。上限は、30質量部以下がより好ましく、20質量部以下が更に好ましく、10質量部以下が一層好ましく、5質量部以下がより一層好ましく、4質量部以下が特に好ましい。
 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。
When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
The base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

<溶剤>
 本発明の樹脂組成物は、溶剤を含むことが好ましい。
 本発明の樹脂組成物は、溶剤として、アミド結合又はヒドロキシ基の少なくとも一つを有する溶剤を含むことが好ましい。このような溶剤は、化合物Aの溶解性に優れ、これらの化合物の凝集を抑制することができる。
 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、環状炭化水素類、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 resin composition of the present invention preferably contains a solvent.
The resin composition of the present invention preferably contains a solvent having at least one of an amide bond or a hydroxyl group as a solvent. Such a solvent has excellent solubility for compound A and can suppress aggregation of these compounds.
The solvent may be any known solvent. 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、γ-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。 Esters, for example, 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, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2- Suitable examples of alkyloxypropionic acid alkyl esters include alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

 エーテル類として、例えば、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールブチルメチルエーテル、トリエチレングリコールジメチルエーテル、テトラ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ジメチルエーテル、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、ジプロピレングリコールジメチルエーテル等が好適なものとして挙げられる。 Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene 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 dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

 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。 Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

 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。 Preferable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

 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 an example of a sulfoxide, dimethyl sulfoxide is preferred.

 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-シクロヘキシル-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。 Preferred examples of amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

 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。 Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

 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, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methylamyl 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。 From the standpoint of improving the properties of the coating surface, it is also preferable to mix two or more types of solvents.

 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、γ-バレロラクトン、3-メトキシ-N,N-ジメチルプロピオンアミド、トルエン、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、レボグルコセノン、ジヒドロレボグルコセノンから選択される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、ジメチルスルホキシドとγ-バレロラクトンとの併用、3-メトキシ-N,N-ジメチルプロピオンアミドとγ-ブチロラクトンとの併用、3-メトキシ-N,N-ジメチルプロピオンアミドとγ-ブチロラクトンとジメチルスルホキシドとの併用、又は、N-メチル-2-ピロリドンと乳酸エチルとの併用が特に好ましい。これらの併用された溶剤に、更にトルエンを溶剤の全質量に対して1~10質量%程度添加する態様も、本発明の好ましい態様の1つである。
 特に、樹脂組成物の保存安定性等の観点からは、溶剤としてγ-バレロラクトンを含む態様も、本発明の好ましい態様の1つである。このような態様において、溶剤の全質量に対するγ-バレロラクトンの含有量は、50質量%以上であることが好ましく、60質量%以上であることがより好ましく、70質量%以上であることが更に好ましい。また、上記含有量の上限は、特に限定されず100質量%であってもよい。上記含有量は、樹脂組成物に含まれる特定樹脂などの成分の溶解度等を考慮して決定すればよい。
 また、ジメチルスルホキシドとγ-バレロラクトンとを併用する場合、溶剤の全質量に対して、60~90質量%のγ-バレロラクトンと10~40質量%のジメチルスルホキシドとを含むことが好ましく、70~90質量%のγ-バレロラクトンと10~30質量%のジメチルスルホキシドとを含むことがより好ましく、75~85質量%のγ-バレロラクトンと15~25質量%のジメチルスルホキシドとを含むことが更に好ましい。
In the present invention, one solvent selected from 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-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents, is preferred. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. An embodiment in which toluene is further added to these combined solvents in an amount of about 1 to 10% by mass based on the total mass of the solvent is also one of the preferred embodiments of the present invention.
In particular, from the viewpoint of storage stability of the resin composition, an embodiment containing γ-valerolactone as a solvent is one of the preferred embodiments of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the content is not particularly limited and may be 100% by mass. The content may be determined taking into consideration the solubility of components such as a specific resin contained in the resin composition, and the like.
Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide, relative to the total mass of the solvent.

 溶剤の含有量は、塗布性の観点から、本発明の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、20~70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。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。 From the viewpoint of coatability, the content of the solvent is preferably an amount that results in a total solids concentration of the resin composition of the present invention of 5 to 80 mass%, more preferably an amount that results in a total solids concentration of 5 to 75 mass%, even more preferably an amount that results in a total solids concentration of 10 to 70 mass%, and even more preferably an amount that results in a total solids concentration of 20 to 70 mass%. The content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method. When two or more types of solvents are contained, the total amount is preferably within the above range.

<金属接着性改良剤>
 本発明の樹脂組成物は、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観点から、金属接着性改良剤を含むことが好ましい。金属接着性改良剤としては、アルコキシシリル基を有するシランカップリング剤、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、アミノ化合物等が挙げられる。
 ただし、上述の化合物Aに該当する化合物は、ここでいう金属接着性改良剤、及び、シランカップリング剤には該当しないものとする。
<Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, and an amino compound.
However, the compound corresponding to the above-mentioned compound A does not correspond to the metal adhesion improver and the silane coupling agent referred to here.

〔シランカップリング剤〕
 シランカップリング剤としては、例えば、国際公開第2021/112189号の段落0316に記載の化合物、特開2018-173573の段落0067~0078に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。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。シランカップリング剤は、下記化合物を用いることも好ましい。以下の式中、Meはメチル基を、Etはエチル基を表す。また、下記Rはブロックイソシアネート基におけるブロック化剤由来の構造が挙げられる。ブロック化剤としては、脱離温度に応じて選択すればよいが、アルコール化合物、フェノール化合物、ピラゾール化合物、トリアゾール化合物、ラクタム化合物、活性メチレン化合物等が挙げられる。例えば、脱離温度を160~180℃としたい観点からは、カプロラクタムなどが好ましい。このような化合物の市販品としては、X-12-1293(信越化学工業株式会社製)などが挙げられる。
[Silane coupling agent]
Examples of the silane coupling agent include the compounds described in paragraph 0316 of International Publication No. 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein. 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. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group. In addition, the following R includes a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent may be selected according to the desorption temperature, and examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of setting the desorption temperature at 160 to 180 ° C., caprolactam and the like are preferred. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

 他のシランカップリング剤としては、例えば、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、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、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、N-フェニル-3-アミノプロピルトリメトキシシラン、トリス-(トリメトキシシリルプロピル)イソシアヌレート、3-ウレイドプロピルトリアルコキシシラン、3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン、3-トリメトキシシリルプロピルコハク酸無水物が挙げられる。これらは1種単独または2種以上を組み合わせて使用することができる。
 また、シランカップリング剤として、アルコキシシリル基を複数個有するオリゴマータイプの化合物を用いることもできる。
 このようなオリゴマータイプの化合物としては、下記式(S-1)で表される繰返し単位を含む化合物などが挙げられる。

 式(S-1)中、RS1は1価の有機基を表し、RS2は水素原子、ヒドロキシ基又はアルコキシ基を表し、nは0~2の整数を表す。
 RS1は重合性基を含む構造であることが好ましい。重合性基としては、エチレン性不飽和結合を有する基、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、アミノ基等が挙げられる。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、イソアリル基、2-メチルアリル基、ビニル基と直接結合した芳香環を有する基(例えば、ビニルフェニル基など)、(メタ)アクリルアミド基、(メタ)アクリロイルオキシ基などが挙げられ、ビニルフェニル基、(メタ)アクリルアミド基又は(メタ)アクリロイルオキシ基が好ましく、ビニルフェニル基又は(メタ)アクリロイルオキシ基がより好ましく、(メタ)アクリロイルオキシ基が更に好ましい。
 RS2はアルコキシ基であることが好ましく、メトキシ基又はエトキシ基であることがより好ましい。
 nは0~2の整数を表し、1であることが好ましい。
 ここで、オリゴマータイプの化合物に含まれる複数の式(S-1)で表される繰返し単位の構造は、それぞれ同一であってもよい。
 ここで、オリゴマータイプの化合物に含まれる複数の式(S-1)で表される繰返し単位のうち、少なくとも1つにおいてnが1又は2であることが好ましく、少なくとも2つにおいてnが1又は2であることがより好ましく、少なくとも2つにおいてnが1であることが更に好ましい。
 このようなオリゴマータイプの化合物としては市販品を用いることができ、市販品としては例えば、KR-513(信越化学工業株式会社製)が挙げられる。
Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples of the silane include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.
Furthermore, an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
Examples of such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1).

In formula (S-1), R 1 S1 represents a monovalent organic group, R 1 S2 represents a hydrogen atom, a hydroxyl group or an alkoxy group, and n represents an integer of 0 to 2.
R S1 is preferably a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group. Of these, a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, a vinylphenyl group or a (meth)acryloyloxy group is more preferred, and a (meth)acryloyloxy group is even more preferred.
R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
n represents an integer of 0 to 2, and is preferably 1.
Here, the structures of the repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same.
Here, among the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, it is preferable that n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and further preferably that n is 1 in at least two.
As such oligomer type compounds, commercially available products can be used, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

〔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。
[Aluminum-based adhesion promoter]
Examples of aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

 その他の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もでき、これらの内容は本明細書に組み込まれる。 Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.

 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、0.01~30質量部が好ましく、0.1~10質量部がより好ましく、0.5~5質量部が更に好ましい。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 adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By making the content equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer will be good, and by making the content equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern will be good. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.

<マイグレーション抑制剤>
 本発明の樹脂組成物は、マイグレーション抑制剤を更に含むことが好ましい。マイグレーション抑制剤を含むことにより、例えば、樹脂組成物を金属層(又は金属配線)に適用して膜を形成した際に、金属層(又は金属配線)由来の金属イオンが膜内へ移動することを効果的に抑制することができる。
 ここでいうマイグレーション抑制剤には、上述の化合物X1又は化合物X2に該当する化合物は該当しないものとする。
<Migration Inhibitor>
The resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively suppressed.
The migration inhibitor referred to here does not include compounds corresponding to the above-mentioned compound X1 or compound X2.

 マイグレーション抑制剤としては、特に制限はないが、複素環(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、ピリミジン環、ピラジン環、ピペリジン環、ピペラジン環、モルホリン環、2H-ピラン環及び6H-ピラン環、トリアジン環)を有する化合物、チオ尿素類及びスルファニル基を有する化合物、ヒンダードフェノール系化合物、サリチル酸誘導体系化合物、ヒドラジド誘導体系化合物が挙げられる。特に、1,2,4-トリアゾール、ベンゾトリアゾール、3-アミノ-1,2,4-トリアゾール、3,5-ジアミノ-1,2,4-トリアゾール等のトリアゾール系化合物、1H-テトラゾール、5-フェニルテトラゾール、5-アミノ―1H-テトラゾール等のテトラゾール系化合物が好ましく使用できる。 There are no particular limitations on the migration inhibitor, but examples include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.

 マイグレーション抑制剤としては、ハロゲンイオンなどの陰イオンを捕捉するイオントラップ剤を使用することもできる。 Ion trapping agents that capture anions such as halogen ions can also be used as migration inhibitors.

 その他のマイグレーション抑制剤としては、特開2013-015701号公報の段落0094に記載の防錆剤、特開2009-283711号公報の段落0073~0076に記載の化合物、特開2011-059656号公報の段落0052に記載の化合物、特開2012-194520号公報の段落0114、0116及び0118に記載の化合物、国際公開第2015/199219号の段落0166に記載の化合物などを使用することができ、この内容は本明細書に組み込まれる。 Other migration inhibitors that can be used include the rust inhibitors described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compounds described in paragraph 0052 of JP 2011-059656 A, the compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520 A, and the compounds described in paragraph 0166 of WO 2015/199219 A, the contents of which are incorporated herein by reference.

 マイグレーション抑制剤の具体例としては、下記化合物を挙げることができる。 Specific examples of migration inhibitors include the following compounds:

 本発明の樹脂組成物がマイグレーション抑制剤を有する場合、マイグレーション抑制剤の含有量は、樹脂組成物の全固形分に対して、0.01~5.0質量%であることが好ましく、0.05~2.0質量%であることがより好ましく、0.1~1.0質量%であることが更に好ましい。 When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %, based on the total solid content of the resin composition.

 マイグレーション抑制剤は1種のみでもよいし、2種以上であってもよい。マイグレーション抑制剤が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 migration inhibitor may be one type or two or more types. When two or more types of migration inhibitors are used, it is preferable that the total is within the above range.

<重合禁止剤>
 本発明の樹脂組成物は、重合禁止剤を含むことが好ましい。重合禁止剤としてはフェノール系化合物、キノン系化合物、アミノ系化合物、N-オキシルフリーラジカル化合物系化合物、ニトロ系化合物、ニトロソ系化合物、ヘテロ芳香環系化合物、金属化合物などが挙げられる。
 ここでいう重合禁止剤には、上述の化合物X1又は化合物X2に該当する化合物は該当しないものとする。
<Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.
The polymerization inhibitor referred to here does not include compounds corresponding to the above-mentioned compound X1 or compound X2.

 重合禁止剤の具体的な化合物としては、国際公開第2021/112189の段落0310に記載の化合物、p-ヒドロキノン、o-ヒドロキノン、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、フェノキサジン、1,4,4-トリメチル-2,3-ジアザビシクロ[3.2.2]ノナ-2-エン-N,N-ジオキシド等が挙げられる。この内容は本明細書に組み込まれる。 Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. The contents of this document are incorporated herein by reference.

 本発明の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、樹脂組成物の全固形分に対して、0.01~20質量%であることが好ましく、0.02~15質量%であることがより好ましく、0.05~10質量%であることが更に好ましい。 When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 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 one type or two or more types. When two or more types of polymerization inhibitors are used, it is preferable that the total is within the above range.

〔ウレア化合物、カルボジイミド化合物、イソウレア化合物〕
 破断伸び、及び、金属又は樹脂層との密着性の観点から、本発明の樹脂組成物は、ウレア結合を有する化合物(ウレア化合物)、カルボジイミド構造を有する化合物(カルボジイミド化合物)及びイソウレア結合を有する化合物(イソウレア化合物)からなる群より選ばれた少なくとも1種の化合物(以下、「ウレア化合物等」ともいう)を含んでもよい。
 これらの中でも、本発明の樹脂組成物は、ウレア結合を有する化合物を更に含むことが好ましい。
 ここでいうウレア化合物等には、上述の化合物A、上述の重合性化合物、シランカップリング剤に該当する化合物は含まれないものとする。
 ウレア化合物としては、下記式(UR-1)で表される化合物が、カルボジイミド化合物としては、下記(UR-2)で表される化合物が、イソウレア化合物としては、下記式(UR-3)で表される化合物が挙げられる。

Figure JPOXMLDOC01-appb-C000055
[Urea compounds, carbodiimide compounds, isourea compounds]
From the viewpoints of breaking elongation and adhesion to a metal or resin layer, the resin composition of the present invention may contain at least one compound selected from the group consisting of a compound having a urea bond (urea compound), a compound having a carbodiimide structure (carbodiimide compound), and a compound having an isourea bond (isourea compound) (hereinafter also referred to as a "urea compound, etc.").
Among these, it is preferable that the resin composition of the present invention further contains a compound having a urea bond.
The urea compounds and the like referred to here do not include the above-mentioned compound A, the above-mentioned polymerizable compounds, and compounds corresponding to silane coupling agents.
Examples of the urea compound include the compound represented by the following formula (UR-1), examples of the carbodiimide compound include the compound represented by the following formula (UR-2), and examples of the isourea compound include the compound represented by the following formula (UR-3).
Figure JPOXMLDOC01-appb-C000055

 式(UR-1)、式(UR-2)又は式(UR-3)中、R11及びR12はそれぞれ独立に、置換基を有してもよい炭素数1~7の脂肪族炭化水素基を表し、R21及びR22はそれぞれ独立に、置換基を有してもよい炭素数1~7の脂肪族炭化水素基を表し、R31及びR32はそれぞれ独立に、置換基を有してもよい炭素数1~7の脂肪族炭化水素基を表し、R33は置換基を有してもよい炭素数1~7の脂肪族炭化水素基を表す。
 式(UR-1)中、R11及びR12はそれぞれ独立に、無置換の炭素数1~7の脂肪族炭化水素基、又は、置換基として第一級アミン塩構造、第二級アミン塩構造、第三級アミノ基、第三級アミン塩構造、及び、第四級アンモニウム基からなる群より選ばれた少なくとも1種の置換基を有する炭素数1~7の脂肪族炭化水素基が好ましく、無置換の炭素数1~7の脂肪族炭化水素基がより好ましい。
 R11及びR12における無置換の炭素数1~7の脂肪族炭化水素基としては、無置換の炭素数1~7の飽和脂肪族炭化水素基が好ましく、無置換の炭素数2~7の飽和脂肪族炭化水素基がより好ましく、エチル基、イソプロピル基、t-ブチル基又はシクロへキシル基が更に好ましい。
In formula (UR-1), formula (UR-2) or formula (UR-3), R 11 and R 12 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, R 21 and R 22 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, R 31 and R 32 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
In formula (UR-1), R 11 and R 12 each independently represent preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having at least one substituent selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, and a quaternary ammonium group, as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
The unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms for R 11 and R 12 is preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms, and still more preferably an ethyl group, an isopropyl group, a t-butyl group, or a cyclohexyl group.

 式(UR-1)中、R11及びR12はそれぞれ独立に、ヒドロキシ基、アルコキシ基、チオール基、及び、アルキルチオ基からなる群より選ばれた少なくとも1種の置換基を有する炭素数2~7の脂肪族炭化水素基であってもよい。
 上記炭素数2~7の脂肪族炭化水素基は、上記置換基を2以上有してもよいが、上記置換基を1つのみ有することも好ましい。
In formula (UR-1), R 11 and R 12 may each independently be an aliphatic hydrocarbon group having 2 to 7 carbon atoms and having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group.
The aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more of the above-mentioned substituents, but it is also preferable that the aliphatic hydrocarbon group has only one of the above-mentioned substituents.

 式(UR-2)中、R21及びR22はそれぞれ独立に、置換基を有してもよい炭素数1~7の脂肪族炭化水素基を表す。
 式(UR-2)中、R21及びR22は、無置換の炭素数1~7の脂肪族炭化水素基、又は、置換基としてアミノ基又は第四級アンモニウム基を有する炭素数1~7の脂肪族炭化水素基が好ましく、無置換の炭素数1~7の脂肪族炭化水素基がより好ましい。
 式(UR-2)中、R21及びR22における上記無置換の炭素数1~7の脂肪族炭化水素基、又は、上記置換基を有する炭素数1~7の脂肪族炭化水素基の好ましい態様は、それぞれ、R11及びR12の説明において示したものと同様である。
In formula (UR-2), R 21 and R 22 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
In formula (UR-2), R 21 and R 22 are preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
In formula (UR-2), preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R 21 and R 22 are the same as those described above for R 11 and R 12 , respectively.

 式(UR-3)中、R31及びR32は、無置換の炭素数1~7の脂肪族炭化水素基、又は、置換基としてアミノ基又は第四級アンモニウム基を有する炭素数1~7の脂肪族炭化水素基が好ましく、無置換の炭素数1~7の脂肪族炭化水素基がより好ましい。
 式(UR-3)中、R31及びR32における上記無置換の炭素数1~7の脂肪族炭化水素基、又は、上記置換基を有する炭素数1~7の脂肪族炭化水素基の好ましい態様は、それぞれ、R11及びR12の説明において示したものと同様である。
In formula (UR-3), R 31 and R 32 are preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
In formula (UR-3), preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R 31 and R 32 are the same as those described above for R 11 and R 12 , respectively.

 式(UR-3)中、R33は置換基を有してもよい炭素数1~7の脂肪族炭化水素基を表し、無置換の炭素数1~7の脂肪族炭化水素基であることが好ましく、無置換の炭素数1~7の飽和脂肪族炭化水素基であることがより好ましく、無置換の炭素数1~4の飽和脂肪族炭化水素基であることが更に好ましい。
 式(UR-3)中、R33としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基又はt-ブチル基が好ましく、エチル基がより好ましい。
In formula (UR-3), R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and even more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.
In formula (UR-3), R 33 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group, and more preferably an ethyl group.

 ウレア化合物等の具体例としては、ジシクロへキシルウレア、ジイソプロピルウレア、ジシクロへキシルカルボジイミド、ジイソプロピルカルボジイミド、ジシクロへキシルイソウレア、ジイソプロピルイソウレア等が挙げられるが、これに限定されるものではない。 Specific examples of urea compounds include, but are not limited to, dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea.

 ウレア化合物等の合計含有量は、特定樹脂100質量部に対して0.1~10.0質量部が好ましく、0.5~8.0質量部がより好ましく、1.0~6.0質量部が更に好ましい。
 ウレア化合物等は、1種単独で用いてもよいし、2種以上を併用してもよい。塩基含有処理液において2種以上の塩基を併用する場合、それらの合計含有量が上記範囲内であることが好ましい。
The total content of the urea compounds and the like is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and even more preferably 1.0 to 6.0 parts by mass, per 100 parts by mass of the specific resin.
The urea compounds and the like may be used alone or in combination of two or more. When two or more bases are used in combination in the base-containing treatment liquid, it is preferable that the total content thereof is within the above range.

<光吸収剤>
 本発明の樹脂組成物は、露光によりその露光波長の吸光度が小さくなる化合物(光吸収剤)を含むことも好ましい。
 光吸収剤としては、国際公開第2022/202647号の段落0159~0183に記載の化合物、特開2019-206689号公報の段落0088~0108に記載の化合物等が挙げられる。これらの内容は本明細書に組み込まれる。
<Light absorber>
The resin composition of the present invention also preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.
Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022/202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of which are incorporated herein by reference.

 本発明の樹脂組成物の全固形分に対する光吸収剤の含有量は、特に限定されないが、0.1~20質量%であることが好ましく、0.5~10質量%であることがより好ましく、1~5質量%であることが更に好ましい。 The content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.

<その他の添加剤>
 本発明の樹脂組成物は、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、界面活性剤、高級脂肪酸誘導体、熱重合開始剤、無機粒子、紫外線吸収剤、有機チタン化合物、酸化防止剤、光酸発生剤、凝集防止剤、フェノール系化合物、他の高分子化合物、可塑剤及びその他の助剤類(例えば、消泡剤、難燃剤など)等を含んでいてもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、例えば、特開2012-003225号公報の段落番号0183以降(対応する米国特許出願公開第2013/0034812号明細書の段落番号0237)の記載、特開2008-250074号公報の段落番号0101~0104、0107~0109等の記載を参酌でき、これらの内容は本明細書に組み込まれる。これらの添加剤を配合する場合、その合計含有量は本発明の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。
 これらの他の添加剤としては、国際公開第2022/145355号の段落0316~0358に記載の化合物が挙げられる。上記記載は本明細書に組み込まれる。
<Other additives>
The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained. By appropriately incorporating these components, it is possible to adjust the properties of the film physical properties, etc. These components can be referred to, for example, in the descriptions in paragraphs 0183 and after of JP-A-2012-003225 (corresponding to paragraph 0237 of US Patent Application Publication No. 2013/0034812), and in paragraphs 0101 to 0104, 0107 to 0109, etc. of JP-A-2008-250074, the contents of which are incorporated herein. When these additives are blended, the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
These other additives include the compounds described in paragraphs 0316 to 0358 of WO 2022/145355, the disclosures of which are incorporated herein by reference.

<樹脂組成物の特性>
 本発明の樹脂組成物の粘度は、樹脂組成物の固形分濃度により調整できる。塗布膜厚の観点から、1,000mm/s~12,000mm/sが好ましく、2,000mm/s~10,000mm/sがより好ましく、2,500mm/s~8,000mm/sが更に好ましい。上記範囲であれば、均一性の高い塗布膜を得ることが容易になる。1,000mm/s以上であれば、例えば再配線用絶縁膜として必要とされる膜厚で塗布することが容易であり、12,000mm/s以下であれば、塗布面状に優れた塗膜が得られる。
<Characteristics of Resin Composition>
The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and even more preferably 2,500 mm 2 /s to 8,000 mm 2 /s. If it is within the above range, it is easy to obtain a coating film with high uniformity. If it is 1,000 mm 2 /s or more, it is easy to apply it with a film thickness required for, for example, a rewiring insulating film, and if it is 12,000 mm 2 /s or less, a coating film with excellent coating surface condition can be obtained.

<樹脂組成物の含有物質についての制限>
 本発明の樹脂組成物の含水率は、2.0質量%未満であることが好ましく、1.5質量%未満であることがより好ましく、1.0質量%未満であることが更に好ましい。2.0%未満であれば、樹脂組成物の保存安定性が向上する。
 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、保管時の収容容器の空隙率低減などが挙げられる。
<Restrictions on substances contained in resin composition>
The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If the water content is less than 2.0%, the storage stability of the resin composition is improved.
Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.

 本発明の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、銅、クロム、ニッケルなどが挙げられるが、有機化合物と金属との錯体として含まれる金属は除く。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。 From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, it is preferable that the total of these metals is within the above range.

 また、本発明の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。 In addition, methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention, lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.

 本発明の樹脂組成物は、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 of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion.Among them, those present in the form 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.Halogen atoms include chlorine atoms and bromine atoms.It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range.
A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

 本発明の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。収容容器としては、原材料や本発明の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 container can be used as the container for the resin composition of the present invention. As the container, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure of six types of resin, in order to prevent impurities from being mixed into the raw materials or the resin composition of the present invention. An example of such a container is the container described in JP 2015-123351 A.

<樹脂組成物の硬化物>
 本発明の樹脂組成物を硬化することにより、樹脂組成物の硬化物を得ることができる。
 本発明の硬化物は、樹脂組成物を硬化してなる硬化物である。
 樹脂組成物の硬化は加熱によるものであることが好ましく、加熱温度が120℃~400℃がより好ましく、140℃~380℃が更に好ましく、170℃~350℃が特に好ましい。樹脂組成物の硬化物の形態は、特に限定されず、フィルム状、棒状、球状、ペレット状など、用途に合わせて選択することができる。本発明において、硬化物は、フィルム状であることが好ましい。樹脂組成物のパターン加工によって、壁面への保護膜の形成、導通のためのビアホール形成、インピーダンスや静電容量あるいは内部応力の調整、放熱機能付与など、用途にあわせて、硬化物の形状を選択することもできる。硬化物(硬化物からなる膜)の膜厚は、0.5μm以上150μm以下であることが好ましい。
 本発明の樹脂組成物を硬化した際の収縮率は、50%以下が好ましく、45%以下がより好ましく、40%以下が更に好ましい。ここで、収縮率は、樹脂組成物の硬化前後の体積変化の百分率を指し、下記の式より算出することができる。
 収縮率[%]=100-(硬化後の体積÷硬化前の体積)×100
<Cured Product of Resin Composition>
By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing a resin composition.
The resin composition is preferably cured by heating, and the heating temperature is more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and can be selected according to the application, such as a film, a rod, a sphere, or a pellet. In the present invention, the cured product is preferably a film. By pattern processing of the resin composition, the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage percentage refers to the percentage of the volume change before and after curing of the resin composition, and can be calculated by the following formula.
Shrinkage rate [%] = 100 - (volume after curing ÷ volume before curing) x 100

<樹脂組成物の硬化物の特性>
 本発明の樹脂組成物の硬化物のイミド化反応率は、70%以上が好ましく、80%以上がより好ましく、90%以上が更に好ましい。70%以上であれば、機械特性に優れた硬化物となる場合がある。
 本発明の樹脂組成物の硬化物の破断伸びは、30%以上が好ましく、40%以上がより好ましく、50%以上が更に好ましい。
 本発明の樹脂組成物の硬化物のガラス転移温度(Tg)は、180℃以上であることが好ましく、210℃以上であることがより好ましく、230℃以上であることがさらに好ましい。
<Characteristics of the cured product of the resin composition>
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
The elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.

<樹脂組成物の調製>
 本発明の樹脂組成物は、上記各成分を混合して調製することができる。
 樹脂組成物の調製方法としては、例えば国際公開第2022/210532号の段落0283~0284に記載の方法を用いることができる。これらの記載は、本明細書に組み込まれる。
<Preparation of Resin Composition>
The resin composition of the present invention can be prepared by mixing the above-mentioned components.
The resin composition can be prepared, for example, by the method described in paragraphs 0283 to 0284 of WO 2022/210532. The descriptions therein are incorporated herein by reference.

(硬化物の製造方法)
 本発明の硬化物の製造方法は、樹脂組成物を基材上に適用して膜を形成する膜形成工程を含むことが好ましい。
 硬化物の製造方法は、上記膜形成工程、膜形成工程により形成された膜を選択的に露光する露光工程、及び、露光工程により露光された膜を現像液を用いて現像してパターンを形成する現像工程を含むことがより好ましい。
 硬化物の製造方法は、上記膜形成工程、上記露光工程、上記現像工程、並びに、現像工程により得られたパターンを加熱する加熱工程及び現像工程により得られたパターンを露光する現像後露光工程の少なくとも一方を含むことが特に好ましい。
 また、硬化物の製造方法は、上記膜形成工程、及び、上記膜を加熱する工程(加熱工程)を含むことも好ましい。
 上記加熱工程は、上記膜を50~450℃で加熱する加熱工程であることが好ましい。
 また、本発明の硬化物の製造方法は、乾燥工程、露光後加熱工程、現像後露光工程、及び、金属層形成工程等の、国際公開第2022/210532号に記載の工程を更に含んでもよい。
 本発明の硬化物の製造方法における各工程は、例えば国際公開第2022/210532号の段落0285~0325に記載の各工程と同様の方法より行うことができる。これらの記載は、本願明細書に組み込まれる。
(Method for producing the cured product)
The method for producing a cured product of the present invention preferably includes a film formation step of applying the resin composition onto a substrate to form a film.
It is more preferable that the method for producing a cured product includes the above-mentioned film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern.
It is particularly preferable that the method for producing a cured product includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step.
The method for producing a cured product preferably includes the film-forming step and a step of heating the film (heating step).
The heating step is preferably a heating step in which the film is heated at 50 to 450°C.
In addition, the method for producing a cured product of the present invention may further include the steps described in WO 2022/210532, such as a drying step, a post-exposure heating step, a post-development exposure step, and a metal layer forming step.
Each step in the method for producing a cured product of the present invention can be carried out in the same manner as each step described in paragraphs 0285 to 0325 of WO 2022/210532. These descriptions are incorporated herein by reference.

<用途>
 本発明の硬化物の製造方法、又は、硬化物の適用可能な分野としては、電子デバイスの絶縁膜、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。
<Applications>
Examples of the field of application of the method for producing the cured product of the present invention or the cured product include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include etching patterns of sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or insulating films for mounting applications such as those described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd. "High-performance and Applied Technology of Polyimides" April 2008, supervised by Masaaki Kakimoto, CMC Technical Library "Basics and Development of Polyimide Materials" published in November 2011, and Japan Polyimide and Aromatic Polymer Research Association/editor "Latest Polyimides Basics and Applications" NTS, August 2010.

 本発明の硬化物の製造方法、又は、本発明の硬化物は、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。 The method for producing the cured product of the present invention or the cured product of the present invention can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, and for producing protective lacquers and dielectric layers in electronics, especially microelectronics.

(積層体、及び、積層体の製造方法)
 本発明の積層体とは、本発明の硬化物からなる層を複数層有する構造体をいう。
 積層体は、硬化物からなる層を2層以上含む積層体であり、3層以上積層した積層体としてもよい。
 上記積層体に含まれる2層以上の上記硬化物からなる層のうち、少なくとも1つが本発明の硬化物からなる層であり、硬化物の収縮、又は、上記収縮に伴う硬化物の変形等を抑制する観点からは、上記積層体に含まれる全ての硬化物からなる層が本発明の硬化物からなる層であることも好ましい。
(Laminate and method for manufacturing laminate)
The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention.
The laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers.
Of the two or more layers made of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

 すなわち、本発明の積層体の製造方法は、本発明の硬化物の製造方法を含むことが好ましく、本発明の硬化物の製造方法を複数回繰り返すことを含むことがより好ましい。 In other words, the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention multiple times.

 本発明の積層体は、硬化物からなる層を2層以上含み、上記硬化物からなる層同士のいずれかの間に金属層を含む態様が好ましい。上記金属層は、上記金属層形成工程により形成されることが好ましい。
 すなわち、本発明の積層体の製造方法は、複数回行われる硬化物の製造方法の間に、硬化物からなる層上に金属層を形成する金属層形成工程を更に含むことが好ましい。金属層形成工程の好ましい態様は上述の通りである。
 上記積層体としては、例えば、第一の硬化物からなる層、金属層、第二の硬化物からなる層の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。
 上記第一の硬化物からなる層及び上記第二の硬化物からなる層は、いずれも本発明の硬化物からなる層であることが好ましい。上記第一の硬化物からなる層の形成に用いられる本発明の樹脂組成物と、上記第二の硬化物からなる層の形成に用いられる本発明の樹脂組成物とは、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 laminate of the present invention preferably includes two or more layers made of a cured product, and includes a metal layer between any two of the layers made of the cured product. The metal layer is preferably formed by the metal layer forming step.
That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer made of a cured product between the steps for producing a cured product which are performed multiple times. A preferred embodiment of the metal layer forming step is as described above.
As the laminate, for example, a laminate including at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order, can be mentioned as a preferred example.
The layer made of the first cured product and the layer made of the second cured product are preferably layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

<積層工程>
 本発明の積層体の製造方法は、積層工程を含むことが好ましい。
 積層工程とは、パターン(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)加熱工程及び現像後露光工程の少なくとも一方を、この順に行うことを含む一連の工程である。ただし、(a)膜形成工程および(d)加熱工程及び現像後露光工程の少なくとも一方を繰り返す態様であってもよい。また、(d)加熱工程及び現像後露光工程の少なくとも一方の後には(e)金属層形成工程を含んでもよい。積層工程には、更に、上記乾燥工程等を適宜含んでいてもよいことは言うまでもない。
<Lamination process>
The method for producing the laminate of the present invention preferably includes a lamination step.
The lamination process is a series of processes including performing at least one of (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) a heating process and a post-development exposure process again on the surface of the pattern (resin layer) or metal layer in this order. However, at least one of (a) the film formation process and (d) the heating process and the post-development exposure process may be repeated. In addition, after at least one of (d) the heating process and the post-development exposure process, (e) a metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying process and the like as appropriate.

 積層工程後、更に積層工程を行う場合には、上記露光工程後、上記加熱工程の後、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。表面活性化処理の詳細については後述する。 If a further lamination step is performed after the lamination step, a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step. An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

 上記積層工程は、2~20回行うことが好ましく、2~9回行うことがより好ましい。
 例えば、樹脂層/金属層/樹脂層/金属層/樹脂層/金属層のように、樹脂層を2層以上20層以下とする構成が好ましく、2層以上9層以下とする構成が更に好ましい。
 上記各層はそれぞれ、組成、形状、膜厚等が同一であってもよいし、異なっていてもよい。
The lamination step is preferably carried out 2 to 20 times, and more preferably 2 to 9 times.
For example, a structure of 2 to 20 resin layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred.
The layers may be the same or different in composition, shape, film thickness, etc.

 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、上記本発明の樹脂組成物の硬化物(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、(d)加熱工程及び現像後露光工程の少なくとも一方、(e)金属層形成工程、の順序で繰り返す態様、又は、(a)膜形成工程、(d)加熱工程及び現像後露光工程の少なくとも一方、(e)金属層形成工程の順序で繰り返す態様が挙げられる。本発明の樹脂組成物層(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、本発明の樹脂組成物層(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, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer. Specifically, the following may be repeated in this order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step; or (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step. By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) of the present invention and the metal layer can be laminated alternately.

(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むことが好ましい。
 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、上記現像工程の後(好ましくは、加熱工程及び現像後露光工程の少なくとも一方の後)、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組成物層(膜)との密着性を向上させることができる。
 表面活性化処理は、露光後の樹脂組成物層(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、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。特にネガ型現像を行う場合など、樹脂組成物層が硬化されている場合には、表面処理によるダメージを受けにくく、密着性が向上しやすい。
 表面活性化処理は、例えば、国際公開第2021/112189号の段落0415に記載の方法により実施することができる。この内容は本明細書に組み込まれる。
(Surface activation treatment process)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
The surface activation treatment step is usually carried out after the metal layer formation step, but after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be subjected to a surface activation treatment step before the metal layer formation step is carried out.
The surface activation treatment may be performed on at least a part of the metal layer, or on at least a part of the resin composition layer after exposure, or on at least a part of both the metal layer and the resin composition layer after exposure. 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 area of the metal layer on which the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface can be improved.
It is preferable to perform the surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface that has been surface-activated. In particular, when performing negative development, etc., when the resin composition layer is cured, it is less likely to be damaged by the surface treatment, and the adhesion is likely to be improved.
The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021/112189, the contents of which are incorporated herein by reference.

(半導体デバイス及びその製造方法)
 本発明は、本発明の硬化物、又は、積層体を含む半導体デバイスも開示する。
 また、本発明は、本発明の硬化物の製造方法、又は、積層体の製造方法を含む半導体デバイスの製造方法も開示する。
 本発明の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。
(Semiconductor device and its manufacturing method)
The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention.
The present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product or the method for producing the laminate of the present invention.
As specific examples of semiconductor devices using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer, the descriptions in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357 can be referred to, and the contents of these are incorporated herein by reference.

 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 explained in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. "Parts" and "%" are based on mass unless otherwise specified.

<環化樹脂の前駆体の製造方法>
〔合成例1:環化樹脂の前駆体(樹脂1)の合成〕
 4,4’-オキシジフタル酸二無水物(ODPA)23.48gとビスフタル酸二無水物(BPDA)22.27g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)39.69gとテトラヒドロフラン136.83gを入れて室温(25℃)下で撹拌し、撹拌しながらピリジン24.66gを加えて反応混合物を得た。反応による発熱の終了後に室温まで放冷し、16時間放置した。
 次に、氷冷下において、ジシクロヘキシルカルボジイミド(DCC)62.46gをテトラヒドロフラン61.57gに溶解した溶液を撹拌しながら40分かけて反応混合物に加え、続いて4,4’-ジアミノジフェニルエーテル(DADPE)27.42gをテトラヒドロフラン119.73gに懸濁したものを撹拌しながら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7.17gを加えて1時間撹拌し、次に、テトラヒドロフラン136.83g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716.21gのエチルアルコールに加えて粗ポリマーから成る沈殿物を生成した。生成した粗ポリマーを濾別し、テトラヒドロフラン403.49g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8470.26g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別した後、真空乾燥して粉末状の樹脂1を80.3g得た。樹脂1の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は20,000であった。H-NMRにより、樹脂1の構造は、下記式(P-1)で表される構造であることを確認した。また、4,4’-ジアミノジフェニルエーテルの当量を適宜調整することにより、Mwが5,000、10,000、30,000、13,000、14,000、16,000、17,000である樹脂1もそれぞれ合成した。
<Method for producing a precursor of cyclized resin>
[Synthesis Example 1: Synthesis of Cyclized Resin Precursor (Resin 1)]
23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of bisphthalic dianhydride (BPDA) were placed in a separable flask, 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of tetrahydrofuran were added, and the mixture was stirred at room temperature (25°C), and 24.66 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.
Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes while stirring, followed by the addition of a suspension of 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) in 119.73 g of tetrahydrofuran over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethyl alcohol was added and stirred for 1 hour, and then 136.83 g of tetrahydrofuran was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The obtained reaction solution was added to 716.21 g of ethyl alcohol to generate a precipitate consisting of a crude polymer. The generated crude polymer was filtered and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 8470.26 g of water to precipitate the polymer, and the obtained precipitate was filtered and then vacuum dried to obtain 80.3 g of powdered resin 1. When the molecular weight of resin 1 was measured by gel permeation chromatography (standard polystyrene equivalent), the weight average molecular weight (Mw) was 20,000. It was confirmed by 1 H-NMR that the structure of resin 1 was a structure represented by the following formula (P-1). In addition, resins 1 having Mw of 5,000, 10,000, 30,000, 13,000, 14,000, 16,000, and 17,000 were also synthesized by appropriately adjusting the equivalent of 4,4'-diaminodiphenyl ether.

〔合成例2A:環化樹脂の前駆体(樹脂2A)の合成〕
 21.2gの4,4’-オキシジフタル酸無水物と、18.0gの2-ヒドロキシエチルメタクリレートと、23.9gのピリジンと、250mLのジグリム(ダイグライム、ジエチレングリコールジメチルエーテル)とを混合し、60℃の温度で4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とのジエステルを合成した。次いで、反応混合物を-10℃に冷却し、温度を-10±5℃に保ちながら、17.0gの塩化チオニルを60分かけて加えた。50mLのN-メチルピロリドンで希釈した後、100mLのN-メチルピロリドンに12.6gの4,4’-ジアミノジフェニルエーテルを溶解させた溶液を、-10±5℃で60分かけて反応混合物に滴下して、混合物を室温で2時間撹拌した。その後、エタノール10.0gを添加して室温で1時間撹拌した。
 次いで、6000gの水を加えてポリイミド前駆体を沈殿させ、沈殿物(水-ポリイミド前駆体混合物)を15分間撹拌した。撹拌後の沈殿物(ポリイミド前駆体の固体)をろ取し、テトラヒドロフラン500gに溶解させた。得られた溶液に6000gの水(貧溶媒)を加えてポリイミド前駆体を沈殿させ、沈殿物(水-ポリイミド前駆体混合物)を15分間撹拌した。撹拌後の沈殿物(ポリイミド前駆体の固体)を再びろ過して減圧下で、45℃で3日間乾燥した。
 乾燥後の粉体46.6gをテトラヒドロフラン419.6gに溶解させた後に、2.3gのトリエチルアミンを添加して室温で35分間撹拌した。その後、エタノール3000gを添加して、沈殿物をろ取した。得られた沈殿物をテトラヒドロフラン281.8gに溶解した。そこに水17.1gとイオン交換樹脂UP6040(AmberTec社製)46.6gを添加して、4時間撹拌した。その後、イオン交換樹脂をろ過で取り除き、得られたポリマー溶液を5,600gの水に加えて沈殿物を得た。沈殿物をろ取し、減圧下45℃で24時間乾燥させることで、樹脂2Aを45.1g得た。
 H-NMRにより、樹脂2Aの構造は、下記式(P-2)で表される構造であることを確認した。樹脂2Aの分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は20,000であった。
[Synthesis Example 2A: Synthesis of Cyclized Resin Precursor (Resin 2A)]
21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -10±5°C over 60 minutes, and the mixture was stirred at room temperature for 2 hours. Then, 10.0 g of ethanol was added and stirred at room temperature for 1 hour.
Next, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) was added to the obtained solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was filtered again and dried at 45° C. under reduced pressure for 3 days.
After dissolving 46.6 g of the dried powder in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added and stirred at room temperature for 35 minutes. Then, 3000 g of ethanol was added, and the precipitate was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) were added thereto, and the mixture was stirred for 4 hours. Then, the ion exchange resin was removed by filtration, and the obtained polymer solution was added to 5,600 g of water to obtain a precipitate. The precipitate was collected by filtration and dried at 45 ° C. under reduced pressure for 24 hours to obtain 45.1 g of resin 2A.
It was confirmed by 1 H-NMR that the structure of Resin 2A was a structure represented by the following formula (P-2): The molecular weight of Resin 2A was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000.

〔合成例2B:環化樹脂の前駆体(樹脂2B)の合成〕
 使用する化合物を適宜変更した以外は、合成例1と同様の方法により下記式(P-2)で表される構造の樹脂2Bを合成した。H-NMRにより、樹脂2Bの構造は、下記式(P-2)で表される構造であることを確認した。
 樹脂2BのMwは20,000であった。
[Synthesis Example 2B: Synthesis of Cyclized Resin Precursor (Resin 2B)]
Resin 2B having a structure represented by the following formula (P-2) was synthesized in the same manner as in Synthesis Example 1, except for appropriately changing the compounds used. It was confirmed by 1 H-NMR that the structure of Resin 2B was the structure represented by the following formula (P-2).
Resin 2B had a Mw of 20,000.

〔合成例3~9、12~15:環化樹脂の前駆体(樹脂3~樹脂9、樹脂12~樹脂15)の合成〕
 使用する化合物を適宜変更した以外は、合成例1と同様の方法により下記式(P-3)~式(P-9)、式(P-12)~式(P-15)のいずれかで表される構造の樹脂3~樹脂9、樹脂12~樹脂15を合成した。
 樹脂3のMwは20,000、樹脂4のMwは20,000、樹脂5のMwは20,000、樹脂6のMwは20,000、樹脂7のMwは20,000、樹脂8のMwは20,000、樹脂9のMwは20,000、樹脂12のMwは20,000、樹脂13のMwは20,000、樹脂14のMwは20,000、樹脂15のMwは20,000であった。H-NMRにより、樹脂3~樹脂9、樹脂12~樹脂15の構造は、それぞれ、下記式(P-3)~式(P-9)、式(P-12)~式(P-15)で表される構造であることを確認した。
[Synthesis Examples 3 to 9, 12 to 15: Synthesis of Cyclized Resin Precursors (Resins 3 to 9, and 12 to 15)]
Resins 3 to 9 and resins 12 to 15 each having a structure represented by any one of the following formulas (P-3) to (P-9) and formulas (P-12) to (P-15) were synthesized in the same manner as in Synthesis Example 1, except that the compounds used were appropriately changed.
The Mw of resin 3 was 20,000, the Mw of resin 4 was 20,000, the Mw of resin 5 was 20,000, the Mw of resin 6 was 20,000, the Mw of resin 7 was 20,000, the Mw of resin 8 was 20,000, the Mw of resin 9 was 20,000, the Mw of resin 12 was 20,000, the Mw of resin 13 was 20,000, the Mw of resin 14 was 20,000, and the Mw of resin 15 was 20,000. It was confirmed by 1 H-NMR that the structures of resins 3 to 9 and resins 12 to 15 were structures represented by the following formulas (P-3) to (P-9) and formulas (P-12) to (P-15), respectively.

〔合成例10:ポリイミド(樹脂10)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)18.0g(40.5ミリモル)をN-メチルピロリドン(NMP)80.0gに溶解した。次いで、4,4’-ジアミノジフェニルエーテル(東京化成工業(株)製)7.95g(39.7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12.8g(160ミリモル)、無水酢酸10.3g(101ミリモル)、N-メチルピロリドン(NMP)40.0g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。樹脂を濾過して取得し、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、樹脂10を得た。樹脂10の分子量をゲルパーミエーションクロマトグラフィー(標準ポリスチレン換算)で測定したところ、重量平均分子量(Mw)は20,000であった。H-NMRにより、樹脂10の構造は、下記式(P-10)で表される構造であることを確認した。
Synthesis Example 10: Synthesis of polyimide (resin 10)
In a flask equipped with a condenser and a stirrer, 18.0 g (40.5 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP) while removing moisture. Then, 7.95 g (39.7 mmol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 3 hours, and further stirred at 45°C for 3 hours. Then, 12.8 g (160 mmol) of pyridine, 10.3 g (101 mmol) of acetic anhydride, and 40.0 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80°C for 3 hours, and diluted with 50 g of N-methylpyrrolidone (NMP).
The reaction solution was precipitated in 1 liter of methanol and stirred at a speed of 3000 rpm for 15 minutes. The resin was collected by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. The obtained resin was dried at 40°C under reduced pressure for one day to obtain resin 10. The molecular weight of resin 10 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 20,000. It was confirmed by 1 H-NMR that the structure of resin 10 was a structure represented by the following formula (P-10).

〔合成例11、16~18:ポリイミド(樹脂11、16~18)の合成〕
 使用する化合物を適宜変更した以外は、合成例10と同様の方法により下記式(P-11)、(P-16)~(P-18)で表される構造の樹脂11を合成した。H-NMRにより、樹脂11、16~18の構造は、下記式(P-11)、(P-16)~(P-18)で表される構造であることを確認した。
 樹脂11、16~18のMwはいずれも20,000であった。
[Synthesis Examples 11, 16 to 18: Synthesis of Polyimides (Resins 11, 16 to 18)]
Resin 11 having a structure represented by the following formulae (P-11), (P-16) to (P-18) was synthesized in the same manner as in Synthesis Example 10, except for appropriately changing the compounds used. It was confirmed by 1 H-NMR that the structures of resins 11, 16 to 18 were the structures represented by the following formulae (P-11), (P-16) to (P-18).
The Mw of resins 11 and 16 to 18 was all 20,000.



<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、各樹脂組成物を得た。また、比較例において、下記表に記載の成分を混合し、比較用組成物を得た。
 具体的には、溶剤以外の表に記載の各成分の含有量(配合量)は、表の各欄の「質量部」の欄に記載の量(質量部)とした。
 溶剤の含有量(配合量)は、組成物の固形分濃度が表中の「固形分濃度」の値(質量%)となるようにし、溶剤の全質量に対する各溶剤の含有量の比率(質量比)は、表中の「比率」の欄に記載の比率となるようにした。
 得られた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用いて加圧ろ過した。
 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 of the examples, the components shown in the following table were mixed to obtain a resin composition. In each of the comparative examples, the components shown in the following table were mixed to obtain a comparative composition.
Specifically, the content (blended amount) of each component shown in the table other than the solvent is the amount (parts by mass) shown in the "parts by mass" column of each column in the table.
The contents (amounts) of the solvents were set so that the solids concentration of the composition was the value (mass %) of "Solids concentration" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvents was the ratio shown in the "Ratio" column in the table.
The obtained resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter having a pore width of 0.8 μm.
In the table, "-" indicates that the composition does not contain the corresponding component.

 表に記載した各成分の詳細は下記の通りである。 Details of each ingredient listed in the table are as follows:

〔樹脂〕
・樹脂1~樹脂15:上記合成例により得られた樹脂1~樹脂15
〔resin〕
Resins 1 to 15: Resins 1 to 15 obtained by the above synthesis examples

〔モノマー(重合性化合物)〕
・M-1~M-4:下記構造の化合物

・DPHA:ジペンタエリスリトールヘキサアクリレート
[Monomer (polymerizable compound)]
M-1 to M-4: Compounds having the following structures

DPHA: Dipentaerythritol hexaacrylate

〔重合開始剤又は光酸発生剤〕
・I-1~I-9:下記構造の化合物
[Polymerization initiator or photoacid generator]
I-1 to I-9: Compounds having the following structures

〔熱塩基発生剤〕
・A-1~A-5:下記構造の化合物
[Thermal Base Generator]
A-1 to A-5: Compounds having the following structures

〔重合禁止剤〕
・E-9:下記構造の化合物

・B-1~B-4:下記構造の化合物、B-4及びB-5は化合物X2に該当する化合物である。
[Polymerization inhibitor]
E-9: A compound having the following structure:

B-1 to B-4: Compounds having the following structure. B-4 and B-5 are compounds corresponding to compound X2.

〔化合物A又はシランカップリング剤(金属接着性改良剤)〕
・C-1~C-23:下記構造の化合物。C-1~C-23は化合物Aに該当する化合物である(ただし、構造式中、Meはメチル基を、Etはエチル基を表す)。
・CR-1:下記構造の化合物、CR-1は化合物Aに該当しない化合物である(ただし、構造式中、Etはエチル基を表す)。
・CX―1~CX―4:下記構造の化合物、CX-1~CX-4は化合物Aに該当しない化合物である(ただし、構造式中、Meはメチル基を、Etはエチル基を表す)。


[Compound A or silane coupling agent (metal adhesion improver)]
C-1 to C-23: Compounds having the following structure: C-1 to C-23 are compounds corresponding to compound A (wherein, in the structural formula, Me represents a methyl group, and Et represents an ethyl group).
CR-1: A compound having the following structure. CR-1 is a compound that does not fall under Compound A (however, in the structural formula, Et represents an ethyl group).
CX-1 to CX-4: Compounds having the following structures. CX-1 to CX-4 are compounds that do not fall under compound A (however, in the structural formulas, Me represents a methyl group and Et represents an ethyl group).


〔マイグレーション抑制剤〕
・D-1~D-3:下記構造の化合物
[Migration Inhibitor]
D-1 to D-3: Compounds having the following structure

〔添加剤〕
・E-1~E-6、E-9、E-11~E-19:下記構造の化合物

・E-7:2,2’,3,3’-テトラヒドロ-3,3,3’,3’-テトラメチル-1,1’-スピロビ(1H-インデン)-5,5’,6,6’,7,7’ヘキサノールと1,2-ナフトキノン-(2)-ジアゾ-5-スルホン酸とのエステル
・E-8:下記合成品
[Additives]
E-1 to E-6, E-9, E-11 to E-19: Compounds having the following structures

E-7: Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid E-8: The following synthetic product

<添加剤:ジアゾナフトキノン化合物E-8の合成>
 フラスコに4,4’-(1-(2-(4ヒドロキシフェニル)-2-プロピル)フェニル)エチリデン)ビスフェノール(本州化学工業(株)製:Tris-PA)を29.72g(70ミリモル)添加した。続いて、アセトン300gに1,2-ナフトキノンジアジド-5-スルホン酸クロライドを46.93g(174.9ミリモル)、トリエチルアミン17.9gを撹拌溶解し、滴下ロートを用いてフラスコに30分かけて滴下し、内温30℃で30分撹拌した。続いて、塩酸を滴下して、更に30分撹拌した。続いて、ビーカーに純水1640gと塩酸30gの溶解液を準備し、これに、反応液中の塩酸塩をろ過したろ液を滴下し、析出物をろ過、水洗し、40℃で50時間真空乾燥し、ジアゾナフトキノン化合物E-8を得た。
<Additive: Synthesis of diazonaphthoquinone compound E-8>
29.72 g (70 mmol) of 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene)bisphenol (Honshu Chemical Industry Co., Ltd.: Tris-PA) was added to the flask. Then, 46.93 g (174.9 mmol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride and 17.9 g of triethylamine were dissolved in 300 g of acetone with stirring, and the mixture was dropped into the flask using a dropping funnel over 30 minutes, and stirred for 30 minutes at an internal temperature of 30°C. Then, hydrochloric acid was dropped and the mixture was stirred for another 30 minutes. Then, a solution of 1640 g of pure water and 30 g of hydrochloric acid was prepared in a beaker, and the filtrate obtained by filtering the hydrochloride in the reaction solution was dropped into this, and the precipitate was filtered, washed with water, and vacuum dried at 40°C for 50 hours to obtain a diazonaphthoquinone compound E-8.

〔溶剤〕
・NMP:N-メチル-2-ピロリドン
・EL:乳酸エチル
・DMSO:ジメチルスルホキシド
・GBL:γ-ブチロラクトン
・GVL:γ-バレロラクトン
・MDMPA:3-メトキシ-N,N-ジメチルプロパンアミド
・toluene:トルエン
〔solvent〕
NMP: N-methyl-2-pyrrolidone EL: Ethyl lactate DMSO: Dimethyl sulfoxide GBL: γ-butyrolactone GVL: γ-valerolactone MDMPA: 3-methoxy-N,N-dimethylpropanamide Toluene: Toluene

<評価>
〔基板密着性の評価〕
 各実施例及び比較例において調製した樹脂組成物又は比較用組成物を、それぞれ、銅基板上にスピンコート法により層状に適用して、樹脂組成物層又は比較用組成物層を形成した。得られた樹脂組成物層又は比較用組成物層を形成した銅基板をホットプレート上で、100℃で5分間乾燥し、銅基板上に表の「膜厚(μm)」の欄に記載の膜厚であって、均一な厚さの樹脂組成物層又は比較用組成物層とした。
 露光条件の欄に「M」と記載された例においては、銅基板上の樹脂組成物層又は比較用組成物層を、光源としてステッパーを用いて、500mJ/cmの露光エネルギーで、表の「現像液」の欄に「CP」と記載された例においては100μm四方の正方形状の非マスク部が形成されたフォトマスクを、表の「現像液」の欄に「T」と記載された例においては100μm四方の正方形状のマスク部が形成されたフォトマスクをそれぞれ使用して表の「露光波長(nm)」の欄に記載の露光波長(nm)の光により露光した。
 露光条件の欄に「D」と記載された例においては、銅基板上の樹脂組成物層又は比較用組成物層を、光源としてダイレクト露光装置(アドテック DE-6UH III)を用いて、500mJ/cmの露光エネルギーで、フォトマスクは使用せず、表の「露光波長(nm)」の欄に記載の露光波長(nm)の光により100μm四方の範囲にレーザーダイレクトイメージング露光を行った。
 その後、表の「現像液」に記載の現像液で60秒間現像して樹脂層を得た。表の「CP」の記載は、シクロペンタノンを、表の「T」の記載は、テトラメチルアンモニウムヒドロキシドの2.38質量%水溶液をそれぞれ意味している。
 更に、「キュア温度」の欄に数値が記載された例においては、窒素雰囲気下で、10℃/分の昇温速度で昇温し、表の「キュア温度(℃)」の欄に記載の温度に達した後、上記温度を表の「キュア時間(min)」の時間において維持し、硬化物を得た。
 「キュア温度(℃)」の欄に「IR」と記載された例においては、赤外線ランプ加熱装置(アドバンス理工社製、RTP-6)を用いて、各実施例において得られた樹脂膜を、窒素雰囲気下で、10℃/分の昇温速度で昇温し、230℃に達した後、上記温度を表の「キュア時間(min)」の時間において維持し、硬化物を得た。
銅基板上の硬化物に対して、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、下記評価基準に従って評価した。評価結果は表の「基板密着性」の欄に記載した。せん断力が大きければ大きいほど硬化膜の密着性に優れるといえる。
-評価基準-
A:せん断力が30gfを超えた。
B:せん断力が25gfを超えて30gf以下であった。
C:せん断力が20gfを超えて25gf以下であった。
D:せん断力が20gf以下であった。
また、1gfは0.00980665Nである。
<Evaluation>
[Evaluation of Adhesion to Substrate]
The resin composition or comparative composition prepared in each Example and Comparative Example was applied in a layer form on a copper substrate by spin coating to form a resin composition layer or comparative composition layer. The copper substrate on which the obtained resin composition layer or comparative composition layer was formed was dried on a hot plate at 100° C. for 5 minutes to form a resin composition layer or comparative composition layer having a uniform thickness on the copper substrate, the thickness of which is shown in the “Film Thickness (μm)” column in the table.
In the examples marked with "M" in the exposure conditions column, the resin composition layer or the comparative composition layer on the copper substrate was exposed to light with an exposure wavelength (nm) shown in the "Exposure wavelength (nm)" column of the table using a stepper as a light source and an exposure energy of 500 mJ/ cm2 , and using a photomask with a 100 μm square unmasked portion formed therein in the examples marked with "CP" in the "Developer" column of the table, and using a photomask with a 100 μm square masked portion formed therein in the examples marked with "T" in the "Developer" column of the table.
In the examples marked with "D" in the exposure conditions column, the resin composition layer or the comparative composition layer on the copper substrate was subjected to laser direct imaging exposure in an area of 100 μm square with light of the exposure wavelength (nm) shown in the "Exposure wavelength (nm)" column in the table, using a direct exposure device (Adtec DE-6UH III) as a light source with an exposure energy of 500 mJ/cm2, without using a photomask.
Thereafter, the resin layer was developed for 60 seconds with the developer shown in the "Developer" column in the table. "CP" in the table means cyclopentanone, and "T" in the table means a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.
Furthermore, in the examples in which a numerical value is given in the "Cure temperature" column, the temperature was increased at a rate of 10°C/min in a nitrogen atmosphere, and after reaching the temperature given in the "Cure temperature (°C)" column in the table, the above temperature was maintained for the time given in the "Cure time (min)" column in the table to obtain a cured product.
In the examples in which "IR" is written in the "Cure temperature (°C)" column, the resin film obtained in each Example was heated at a heating rate of 10°C/min in a nitrogen atmosphere using an infrared lamp heating device (Advance Riko Co., Ltd., RTP-6). After reaching 230°C, the above temperature was maintained for the time indicated in the "Cure time (min)" in the table, and a cured product was obtained.
The shear force of the cured product on the copper substrate was measured using a bond tester (CondorSigma, manufactured by XYZTEC) under an environment of 25°C and 65% relative humidity (RH), and evaluated according to the following evaluation criteria. The evaluation results are shown in the "Adhesion to substrate" column in the table. It can be said that the greater the shear force, the better the adhesion of the cured film.
-Evaluation criteria-
A: The shear force exceeded 30 gf.
B: The shear force was greater than 25 gf and equal to or less than 30 gf.
C: The shear force was greater than 20 gf and not more than 25 gf.
D: The shear force was 20 gf or less.
Also, 1 gf is 0.00980665 N.

〔耐熱試験後の基板密着性の評価〕
 得られた硬化物付きの銅基板を、温度175℃、大気下の槽内で192時間経過させた後にボンドテスターを用いた評価を行った以外は、上述の基板密着性の評価と同様の方法及び評価基準により、耐熱試験後の基板密着性の評価を行った。評価結果は表の「耐熱試験後の基板密着性」の欄に記載した。せん断力が大きければ大きいほど耐熱試験後の硬化膜の密着性に優れるといえる。
[Evaluation of substrate adhesion after heat resistance test]
The obtained copper substrate with the cured product was left in a tank at 175°C under atmospheric pressure for 192 hours, and then the substrate adhesion after the heat resistance test was evaluated using the same method and evaluation criteria as in the evaluation of substrate adhesion described above, except that the evaluation was performed using a bond tester. The evaluation results are shown in the column "Substrate adhesion after heat resistance test" in the table. It can be said that the greater the shear force, the better the adhesion of the cured film after the heat resistance test.

 以上の結果から、本発明の樹脂組成物から形成される硬化物は、化合物Aに該当する化合物を含むことにより、高温保存試験後の基板密着性に優れることが分かる。
 比較例1に係る比較用組成物は、化合物Aに該当する化合物を含有しない。このような比較用組成物から形成される硬化物については、高温保存試験後の基板密着性に劣ることが分かる。
From the above results, it is evident that the cured product formed from the resin composition of the present invention, which contains a compound corresponding to compound A, has excellent substrate adhesion after high-temperature storage tests.
The comparative composition according to Comparative Example 1 does not contain a compound corresponding to compound A. It is clear that the cured product formed from such a comparative composition has poor substrate adhesion after a high-temperature storage test.

<実施例201>
 実施例1において使用した樹脂組成物を、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5分間乾燥し、膜厚20μmの感光膜を形成した後、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。上記露光後、シクロペンタノンで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180分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 201>
The resin composition used in Example 1 was applied in a layer form by spin coating on the surface of the thin copper layer of the resin substrate on which the thin copper layer was formed, and dried at 100° C. for 5 minutes to form a photosensitive film with a thickness of 20 μm, which was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line and space pattern and a line width of 10 μm). After the exposure, the layer was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
Next, the temperature was increased at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 180 minutes to form an interlayer insulating film for a rewiring layer. This interlayer insulating film for a rewiring layer had excellent insulating properties.
Furthermore, when a semiconductor device was manufactured using this interlayer insulating film for redistribution layers, it was confirmed that the device operated without any problems.

Claims (21)

 環化樹脂及びその前駆体からなる群より選ばれた少なくとも1種の樹脂、並びに、
 式(A1-1)で表される化合物Aを含む
 樹脂組成物。

 式(A1-1)中、Rは酸素原子、窒素原子及び硫黄原子から選ばれる少なくとも1つ以上の原子を有する有機基であり、Rが複数ある場合は同一であってもよいし、異なっていてもよく、Rは水素原子又は前記Rに該当しない任意の有機基であり、Rが複数ある場合は同一であってもよいし、異なっていてもよく、R及びRのうち少なくとも2つが結合して環構造を形成してもよく、nは1~3の整数を表し、mは1以上の整数を表し、Rはm価の有機基を表す。
At least one resin selected from the group consisting of cyclized resins and precursors thereof, and
A resin composition comprising a compound A represented by formula (A1-1):

In formula (A1-1), R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different, R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different, at least two of R 1 and R 2 may be bonded to form a ring structure, n represents an integer of 1 to 3, m represents an integer of 1 or more, and R 3 represents an m-valent organic group.
 化合物Aが、下記式(A1-2)で表される化合物である、請求項1に記載の樹脂組成物。

 式(A1-2)中、Rは酸素原子、窒素原子及び硫黄原子から選ばれる少なくとも1つ以上の原子を有する有機基であり、Rが複数ある場合は同一であってもよいし、異なっていてもよく、Rは水素原子又は前記Rに該当しない任意の有機基であり、Rが複数ある場合は同一であってもよいし、異なっていてもよく、R及びRのうち少なくとも2つが結合して環構造を形成してもよく、nは1~3の整数を表し、Lは2価の連結基を表し、Rは水素原子又は1価の有機基を表す。
The resin composition according to claim 1, wherein compound A is a compound represented by the following formula (A1-2):

In formula (A1-2), R 1 represents an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different, R 2 represents a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different, at least two of R 1 and R 2 may be bonded to form a ring structure, n represents an integer of 1 to 3, L represents a divalent linking group, and R 4 represents a hydrogen atom or a monovalent organic group.
 前記式(A1-1)におけるRのうち少なくとも1つが、アミノ基またはエステル結合を含む、請求項1に記載の樹脂組成物。 The resin composition according to claim 1, wherein at least one of R 1 in the formula (A1-1) contains an amino group or an ester bond.  前記式(A1-1)におけるRが、下記式(R3-1)で表される基である、請求項1に記載の樹脂組成物。

 式(R3-1)中、L31はそれぞれ独立に、2価の連結基を表し、R31はそれぞれ独立に、水素原子が置換基で置換されてもよい芳香族炭化水素基、又は、*-C(=O)R32-#で表される基を表し、*は式(R3-1)中の窒素原子との結合部位を表し、#は式(R3-1)中のL32との結合部位を表し、R32は有機基を表し、mは1以上の整数を表し、mが1である場合L32は水素原子又は置換基を表し、mが2以上である場合L32は単結合又はm価の連結基を表し、*は式(A1-1)中のケイ素原子との結合部位を表す。
The resin composition according to claim 1, wherein R 3 in the formula (A1-1) is a group represented by the following formula (R3-1):

In formula (R3-1), L 31 each independently represents a divalent linking group, R 31 each independently represents an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or a group represented by *-C(═O)R 32 -#, * represents a bonding site to the nitrogen atom in formula (R3-1), # represents a bonding site to L 32 in formula (R3-1), R 32 represents an organic group, m represents an integer of 1 or more, when m is 1, L 32 represents a hydrogen atom or a substituent, and when m is 2 or more, L 32 represents a single bond or an m-valent linking group, and * represents a bonding site to the silicon atom in formula (A1-1).
 環化樹脂及びその前駆体からなる群より選ばれた少なくとも1種の樹脂、並びに、
 式(A2-1)で表される化合物Aを含む
 樹脂組成物。

 式(A2-1)中、R21はHSP値が17.0~27.0MPa1/2である有機基であり、R21が複数ある場合は同一であってもよいし、異なっていてもよく、R22は水素原子又は前記R21に該当しない任意の有機基であり、R22が複数ある場合は同一であってもよいし、異なっていてもよく、R21及びR22のうち少なくとも2つが結合して環構造を形成してもよく、nは1~3の整数を表し、mは1以上の整数を表し、R23はm価の有機基を表す。
At least one resin selected from the group consisting of cyclized resins and precursors thereof, and
A resin composition comprising a compound A represented by formula (A2-1):

In formula (A2-1), R 21 is an organic group having an HSP value of 17.0 to 27.0 MPa 1/2 , and when there is a plurality of R 21 , they may be the same or different, R 22 is a hydrogen atom or any organic group not corresponding to R 21 , and when there is a plurality of R 22 , they may be the same or different, at least two of R 21 and R 22 may be bonded to form a ring structure, n represents an integer of 1 to 3, m represents an integer of 1 or more, and R 23 represents an m-valent organic group.
 前記樹脂がポリイミド又はポリイミド前駆体である、請求項1~5のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, wherein the resin is a polyimide or a polyimide precursor.  前記樹脂がポリイミドである、請求項1~5のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, wherein the resin is a polyimide.  光重合開始剤を更に含む、請求項1~5のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, further comprising a photopolymerization initiator.  増感剤を更に含む、請求項8に記載の樹脂組成物。 The resin composition according to claim 8, further comprising a sensitizer.  ウレア結合を有する化合物を更に含む、請求項1~5のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, further comprising a compound having a urea bond.  ウレア結合及びウレタン結合の少なくとも一方を有する重合性化合物を更に含む、請求項1~5のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, further comprising a polymerizable compound having at least one of a urea bond and a urethane bond.  アミド結合又はヒドロキシ基の少なくとも一つを有する溶剤を更に含む、請求項1~5のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, further comprising a solvent having at least one of an amide bond or a hydroxyl group.  再配線層用層間絶縁膜の形成に用いられる、請求項1~5のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, which is used to form an interlayer insulating film for a redistribution layer.  請求項1~5のいずれか1項に記載の樹脂組成物を硬化してなる硬化物。 A cured product obtained by curing the resin composition according to any one of claims 1 to 5.  請求項14に記載の硬化物からなる層を2層以上含み、前記硬化物からなる層同士のいずれかの間に金属層を含む積層体。 A laminate comprising two or more layers of the cured product according to claim 14, and a metal layer between any of the layers of the cured product.  請求項1~5のいずれか1項に記載の樹脂組成物を基材上に適用して膜を形成する膜形成工程を含む、硬化物の製造方法。 A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of claims 1 to 5 onto a substrate to form a film.  前記膜を選択的に露光する露光工程及び前記膜を現像液を用いて現像してパターンを形成する現像工程を含む、請求項16に記載の硬化物の製造方法。 The method for producing the cured product according to claim 16, comprising an exposure step of selectively exposing the film to light and a development step of developing the film with a developer to form a pattern.  前記膜を50~450℃で加熱する加熱工程を含む、請求項16に記載の硬化物の製造方法。 The method for producing the cured product according to claim 16 includes a heating step in which the film is heated at 50 to 450°C.  請求項16に記載の硬化物の製造方法を含む、積層体の製造方法。 A method for producing a laminate, comprising the method for producing a cured product according to claim 16.  請求項16に記載の硬化物の製造方法を含む、半導体デバイスの製造方法。 A method for manufacturing a semiconductor device, comprising the method for manufacturing the cured product according to claim 16.  請求項14に記載の硬化物を含む、半導体デバイス。 A semiconductor device comprising the cured product according to claim 14.
PCT/JP2024/006352 2023-03-01 2024-02-21 Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, and semiconductor device Pending WO2024181276A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008056897A (en) * 2006-08-03 2008-03-13 Nippon Shokubai Co Ltd Polyamic acid composition and application thereof
WO2014097594A1 (en) * 2012-12-21 2014-06-26 日立化成デュポンマイクロシステムズ株式会社 Polyimide precursor resin composition
JP2016069498A (en) * 2014-09-29 2016-05-09 旭化成イーマテリアルズ株式会社 Resin composition, method for producing cured relief pattern, and semiconductor device
KR20190065866A (en) * 2017-12-04 2019-06-12 삼성에스디아이 주식회사 Photosensitive resin composition, photosensitive resin using the same and electronic device
WO2021100761A1 (en) * 2019-11-21 2021-05-27 富士フイルム株式会社 Curable resin composition, method for producing curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7592393B2 (en) 2019-04-09 2024-12-02 旭化成株式会社 Negative-type photosensitive resin composition, method for producing polyimide, and method for producing cured relief pattern
TW202219092A (en) 2020-09-01 2022-05-16 日商富士軟片股份有限公司 Curable resin composition, cured product, laminate, and method for producing cured product, semiconductor element, and photobase generator

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008056897A (en) * 2006-08-03 2008-03-13 Nippon Shokubai Co Ltd Polyamic acid composition and application thereof
WO2014097594A1 (en) * 2012-12-21 2014-06-26 日立化成デュポンマイクロシステムズ株式会社 Polyimide precursor resin composition
JP2016069498A (en) * 2014-09-29 2016-05-09 旭化成イーマテリアルズ株式会社 Resin composition, method for producing cured relief pattern, and semiconductor device
KR20190065866A (en) * 2017-12-04 2019-06-12 삼성에스디아이 주식회사 Photosensitive resin composition, photosensitive resin using the same and electronic device
WO2021100761A1 (en) * 2019-11-21 2021-05-27 富士フイルム株式会社 Curable resin composition, method for producing curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device

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