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WO2024262604A1 - Composition de résine, produit durci, corps stratifié, procédé de production d'un produit durci, procédé de production d'un corps stratifié, procédé de production d'un dispositif semiconducteur et dispositif semiconducteur - Google Patents

Composition de résine, produit durci, corps stratifié, procédé de production d'un produit durci, procédé de production d'un corps stratifié, procédé de production d'un dispositif semiconducteur et dispositif semiconducteur Download PDF

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Publication number
WO2024262604A1
WO2024262604A1 PCT/JP2024/022527 JP2024022527W WO2024262604A1 WO 2024262604 A1 WO2024262604 A1 WO 2024262604A1 JP 2024022527 W JP2024022527 W JP 2024022527W WO 2024262604 A1 WO2024262604 A1 WO 2024262604A1
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group
formula
resin
resin composition
cured product
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English (en)
Japanese (ja)
Inventor
敦靖 野崎
和也 尾田
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Fujifilm Corp
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Fujifilm Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

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.
  • the resin material can be used as an insulating film, a sealing material, or a protective film for a semiconductor device to be mounted, although the resin material is not particularly limited thereto. It is also used as a base film or coverlay for a flexible substrate.
  • the resin composition can be applied by known coating methods, etc., and therefore has excellent adaptability in manufacturing, for example, there is a high degree of freedom in designing the shape, size, application position, etc., of the resin composition when applied. In view of this excellent adaptability in manufacturing, there are expectations for the development of industrial applications of the above-mentioned resin composition.
  • Patent Document 1 describes a photosensitive resin composition that contains a bismaleimide compound (I) having a cyclic imide bond, which is obtained by reacting a diamine (A) derived from a dimer acid, a tetracarboxylic dianhydride (C) having an alicyclic structure, and maleic anhydride, and a photopolymerization initiator (II), in which the photopolymerization initiator (II) is a compound having an oxime structure or a thioxanthone structure.
  • a bismaleimide compound (I) having a cyclic imide bond which is obtained by reacting a diamine (A) derived from a dimer acid, a tetracarboxylic dianhydride (C) having an alicyclic structure, and maleic anhydride
  • a photopolymerization initiator (II) in which the photopolymerization initiator (II) is a compound having an oxime structure or a thi
  • the present invention aims to provide a resin composition that can produce a cured product with a low dielectric tangent, 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.
  • Resin A is a polyimide, and contains a structure represented by the following formula (A-1) in an amount of 0.20 to 5 mmol/g relative to the mass of Resin A: A polymerization initiator, and A resin composition comprising a polymerizable compound.
  • A-1 L A1 represents a single bond or a linking group having a valence of m+1, R R1 each independently represents a hydrogen atom or an organic group, two R R1 may be linked together, m represents an integer of 1 or more, and * represents a bonding site to another atom.
  • ⁇ 2> The resin composition according to ⁇ 1>, in which the structure represented by the formula (A-1) is contained in a side chain of the resin A.
  • ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the resin A has a radical polymerizable group value of 0.20 to 5 mmol/g.
  • ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein L A1 in formula (A-1) contains an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms.
  • ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, further comprising a resin A2 that is a polyimide precursor.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the resin A contains a repeating unit represented by the following formula (1-1):
  • X1 represents an organic group having 4 or more carbon atoms
  • Y1 represents an organic group having 4 or more carbon atoms
  • R1 each independently represents a structure represented by the following formula (R-1)
  • m represents an integer of 0 to 4
  • n represents an integer of 1 or more.
  • L1 represents a linking group having a valence of a2+1
  • Z1 represents an aromatic group, a cyclic aliphatic group, or a linear or branched aliphatic saturated hydrocarbon group
  • R R1 each independently represents a hydrogen atom or an organic group
  • two R R1 may be linked together
  • a1 represents an integer of 1 or more and not exceeding the maximum number of substituents of Z1
  • a2 represents an integer of 1 or more
  • * represents a bonding site with X1 or Y1 in formula (1-1).
  • X1 and Y1 in the formula (1-1) each include a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulas (V-1) to (V-4):
  • R 1 and X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
  • R 1 X2 and R 1 X3 each independently represent a hydrogen atom or a substituent, and R 1 X2 and R 1 X3 may be bonded to form a ring structure.
  • the resin composition according to ⁇ 6> which contains a repeating unit represented by formula (1-1) and has at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms.
  • Resin B including a repeating unit represented by the following formula (1-1):
  • X1 represents an organic group having 4 or more carbon atoms
  • Y1 represents an organic group having 4 or more carbon atoms
  • Y1 is bonded to a nitrogen atom outside the repeating unit without a linking group
  • R1 each independently represents a structure represented by formula (R-1) below
  • m represents an integer of 0 to 4
  • n represents an integer of 1 or more.
  • L1 represents a linking group having a valence of a2+1
  • Z1 represents an aromatic group, a cyclic aliphatic group, or a linear or branched aliphatic saturated hydrocarbon group
  • R R1 each independently represents a hydrogen atom or an organic group
  • two R R1 may be linked together
  • a1 represents an integer of 1 or more and not exceeding the maximum number of substituents of Z1
  • a2 represents an integer of 1 or more
  • * represents a bonding site with X1 or Y1 in formula (1-1).
  • X2 represents an organic group having 4 or more carbon atoms
  • Y2 represents an organic group having 4 or more carbon atoms
  • R2 each independently represents a group represented by the following formula (R-2), and n represents an integer of 1 or more.
  • X3 represents an organic group having 4 or more carbon atoms
  • Y3 represents an organic group having 4 or more carbon atoms
  • A3 and A4 each independently represent an oxygen atom or -NR N -
  • R N represents a hydrogen atom or a monovalent organic group
  • R3 and R4 each independently represent a hydrogen atom or a monovalent organic group
  • R2 each independently represent a group represented by formula (R-2) below
  • n represents an integer of 0 or more.
  • L2 represents a b2+1 valent linking group
  • Z2 represents a b1+1 valent organic group
  • A2 represents a methacryloxy group, an acryloxy group, a methacrylamide group, an acrylamide group, a vinyl group, a styryl group, an allyl group, or a vinyl ether group
  • b1 represents an integer of 1 or more and not exceeding the maximum number of substituents of Z2
  • b2 represents an integer of 1 or more
  • * represents a bonding site with Y2 in formula (2-1) or Y3 in formula (3-1).
  • R 3 and R 4 are groups having an ethylenically unsaturated bond
  • X 3 includes a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4).
  • X 1 and Y 1 in the formula (1-1) each include a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulas (V-1) to (V-4):
  • R 1 and X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
  • R 1 X2 and R 1 X3 each independently represent a hydrogen atom or a substituent, and R 1 X2 and R 1 X3 may be bonded to form a ring structure.
  • ⁇ 12> The resin composition according to any one of ⁇ 9> to ⁇ 11>, wherein the resin B has at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms.
  • ⁇ 13> The resin composition according to any one of ⁇ 1> to ⁇ 12>, wherein when the resin composition is used to form a film-like cured product having a film thickness of 10 ⁇ m, the cured product has a light transmittance at a wavelength of 365 nm of 15% or more.
  • ⁇ 14> The resin composition according to any one of ⁇ 1> to ⁇ 13>, wherein the polymerizable compound has a melting point of 25° C. or lower.
  • ⁇ 15> The resin composition according to any one of ⁇ 1> to ⁇ 14>, wherein the polymerizable compound has a ClogP of 3 or more.
  • ⁇ 16> The resin composition according to any one of ⁇ 1> to ⁇ 15>, comprising an azole compound and a silane coupling agent.
  • ⁇ 17> The resin composition according to any one of ⁇ 1> to ⁇ 16>, which is used for forming an interlayer insulating film for a redistribution layer.
  • ⁇ 18> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 17>.
  • ⁇ 19> A laminate comprising two or more layers made of the cured product according to ⁇ 18>, and a metal layer between any two adjacent layers made of the cured product.
  • ⁇ 20> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 12> onto a substrate to form a film.
  • the method for producing a cured product according to ⁇ 20> 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.
  • ⁇ 22> A method for producing a cured product according to ⁇ 20> or ⁇ 21>, comprising a heating step of heating the film at 50 to 450° C.
  • ⁇ 23> A method for producing a laminate, comprising the method for producing a cured product according to ⁇ 20>.
  • ⁇ 24> A method for producing a semiconductor device, comprising the method for producing a cured product according to ⁇ 20>.
  • ⁇ 25> A semiconductor device comprising the cured product according to ⁇ 18>.
  • the present invention provides a resin composition that can produce a cured product with a low dielectric tangent, 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.
  • FIG. 1 is a schematic cross-sectional view of a state in which a cured product is formed on a silicon wafer on which copper wiring is formed.
  • 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, ion beams, etc. 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 stated.
  • 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 a resin A which is a polyimide and contains a structure represented by formula (A-1) in an amount of 0.20 to 5 mmol/g relative to the mass of the resin A, a polymerization initiator, and a polymerizable compound.
  • the resin composition according to the second aspect of the present invention contains a resin B containing a repeating unit represented by formula (1-1), a resin C containing at least one of repeating units represented by formula (2-1) and formula (3-1), a polymerization initiator, and a polymerizable compound.
  • the resin A and the resin B will be collectively referred to as the "specific resin”.
  • 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 is used for forming an interlayer insulating film for a rewiring layer.
  • the resin composition of the present invention is preferably used for forming 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 a low dielectric tangent can be obtained.
  • the mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.
  • Resin A which is a polyimide in the first embodiment of the resin composition of the present invention, contains a group represented by formula (A-1) containing a maleimide group in an amount of 0.20 to 5 mmol/g relative to the mass of Resin A.
  • Resin A in the first embodiment of the resin composition of the present invention contains a repeating unit represented by formula (1-1).
  • a composition containing a resin having a polymerizable group such as a (meth)acryloxy group, a polymerizable compound, and a polymerization initiator has been used as a polyimide-containing resin composition to obtain a cured product having excellent physical properties such as chemical resistance.
  • the carbonyl group portion contained in the (meth)acryloxy group is capable of free rotation, and therefore the degree of freedom of movement of the structure in the obtained cured product is high, which may result in an increase in the dielectric tangent.
  • the maleimide group is less likely to rotate freely because the carbonyl group is fixed within the ring structure, and the structure is more likely to be fixed, resulting in a lower dielectric tangent.
  • the maleimide group reacts with various structures in the composition, such as through addition reaction with a phenolic hydroxyl group, in addition to radical polymerization, it is believed that crosslinks are formed between the resin and various components or various sites in the resin in the obtained cured product.
  • the resin when a film made of the resin composition of the present invention is exposed to light and developed to form a pattern, the resin has maleimide groups, which improves the removability of non-image areas with a developer containing an organic solvent, and is also thought to improve resolution.
  • Patent Document 1 does not mention resin compositions that contain specific resins.
  • the first resin composition of the present invention contains a resin A which is a polyimide and contains a structure represented by the following formula (A-1) in an amount of 0.20 to 5 mmol/g relative to the mass of the resin A.
  • A-1 L A1 represents a single bond or a linking group having a valence of m+1
  • R R1 each independently represents a hydrogen atom or an organic group
  • two R R1 may be linked together
  • m represents an integer of 1 or more
  • * represents a bonding site to another atom.
  • a resin having an imidization rate of less than 70% as measured by the method described below is called a polyimide precursor
  • a resin containing an imide structure in a repeating unit and having an imidization rate of 70% or more as described below is called a polyimide.
  • the polyimide is preferably a resin having a repeating unit containing an imide ring structure in the molecular chain.
  • the polyimide is preferably a resin having a repeating unit containing an imide structure in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain.
  • 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 imidization rate of a resin is measured by the following method.
  • the infrared absorption spectrum of the resin is measured to determine the peak intensity P1 near 1377 cm ⁇ 1 , which is an absorption peak derived from the imide structure.
  • the specific resin is heat-treated at 350° C. for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1377 cm ⁇ 1 .
  • the imidization rate of the specific resin is preferably 75% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoints of the film strength, insulating property, flatness, etc. of the resulting organic film.
  • the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
  • the content of the imide structure in the specific resin is preferably 3 mmol/g or less, more preferably 2.5 mmol/g or less, from the viewpoint of decreasing the dielectric loss tangent.
  • the lower limit of the content is not particularly limited, but can be, for example, 0.5 mmol/g or more.
  • Formula (A-1) The structure represented by formula (A-1) is preferably contained in a side chain of resin A.
  • * in formula (A-1) preferably represents a bonding site with an atom contained in the main chain of resin A.
  • at least one of R 1 and R 2 in formula (A-1) may have a structure containing the main chain of a resin.
  • L A1 preferably contains an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms.
  • the aromatic group or the aliphatic saturated hydrocarbon group having 4 or more carbon atoms is preferably bonded to the maleimide group (that is, the nitrogen atom in formula A-1) via a single bond without a linking group.
  • the aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 carbon atoms.
  • Examples of the heteroatom in the aromatic heterocyclic group include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • the number of heteroatoms in the aromatic heterocyclic group is preferably 1 or 2.
  • the aromatic heterocyclic group is preferably a 5-membered or 6-membered ring group containing the above-mentioned heteroatom.
  • the aromatic heterocyclic group may be condensed with another aromatic heterocyclic group or another aromatic hydrocarbon ring group.
  • the aliphatic saturated hydrocarbon group having 4 or more carbon atoms may be linear, branched, cyclic, or may have a structure represented by a combination of these.
  • the aliphatic saturated hydrocarbon group having 4 or more carbon atoms preferably has 4 to 20 carbon atoms, and more preferably has 5 to 10 carbon atoms.
  • L A1 is also preferably represented by the following formula (A-1-1) or formula (A-2-2).
  • Z1 represents -O- or -NR N -;
  • R N represents a hydrogen atom or a monovalent organic group;
  • R A1 represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms;
  • m represents an integer of 1 or more; * has the same meaning as * in formula (A-1); and # represents a bonding site with the nitrogen atom in formula (A-1).
  • Z2 represents -O- or -NR N -;
  • R N represents a hydrogen atom or a monovalent organic group;
  • R A2 represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms;
  • m represents an integer of 1 or more; * has the same meaning as * in formula (A-1); and
  • # represents a bonding site with the nitrogen atom in formula (A-1).
  • Z 1 is preferably —O—.
  • R 1 N 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.
  • R A1 represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms, and preferred embodiments of these groups are as described above.
  • m has the same meaning as m in formula (A-1), and the preferred embodiments are also the same.
  • Z 2 is preferably —O—.
  • Preferred embodiments of R 2 N are as described above.
  • the preferred embodiments of R A2 are the same as the preferred embodiments of R A1 in formula (A-1-1).
  • m has the same meaning as m in formula (A-1), and the preferred embodiments are also the same.
  • n each independently represents an integer of 0 or more, * has the same meaning as * in formula (A-1), and # represents the bonding site with the nitrogen atom in formula (A-1).
  • n is preferably an integer of 0 to 20, and more preferably an integer of 0 to 6.
  • R and R1 each independently represent preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
  • examples of the ring structure formed by combining two R 1 and R 2 include a cyclohexene ring.
  • m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably an integer of 1 to 3, and particularly preferably 1 or 2.
  • m is 1 is also one of the preferred embodiments of the present invention.
  • Resin A contains the structure represented by formula (A-1) in an amount of 0.20 to 5 mmol/g, preferably 0.30 to 4 mmol/g, and more preferably 0.50 to 3 mmol/g, relative to the mass of Resin A.
  • the content of the structure represented by formula (A-1) in Resin A can be confirmed by 1 H-NMR. Specifically, the polymer is dissolved in deuterated DMSO, and 1 H-NMR (integrated 128 times) is measured, and the amount of phenol remaining can be calculated from the amount of phenol used in the polymerization.
  • the radical polymerizable group value in resin A (the molar amount of radical polymerizable groups relative to the mass of resin A) is preferably 0.20 to 5 mmol/g, more preferably 0.30 to 4 mmol/g, and even more preferably 0.50 to 3 mmol/g.
  • the radical polymerizable group value in Resin A can be confirmed by 1 H-NMR.
  • the ratio of the content of the structure represented by formula (A-1) in Resin A to the radical polymerizable group value in Resin A is preferably 50% or more, more preferably 70% or more, and even more preferably 90% or more.
  • the upper limit of the ratio is not particularly limited, and may be 100% or less.
  • Resin A preferably contains a repeating unit represented by the following formula (1-1).
  • X1 represents an organic group having 4 or more carbon atoms
  • Y1 represents an organic group having 4 or more carbon atoms
  • Y1 is bonded to a nitrogen atom outside the repeating unit without a linking group
  • R1 each independently represents a structure represented by formula (R-1) below
  • m represents an integer of 0 to 4
  • n represents an integer of 1 or more.
  • L1 represents a linking group having a valence of a2+1
  • Z1 represents an aromatic group, a cyclic aliphatic group, or a linear or branched aliphatic saturated hydrocarbon group
  • R R1 each independently represents a hydrogen atom or an organic group
  • two R R1 may be linked together
  • a1 represents an integer of 1 or more and not exceeding the maximum number of substituents of Z1
  • a2 represents an integer of 1 or more
  • * represents a bonding site with X1 or Y1 in formula (1-1).
  • R 1 independently represents a structure represented by formula (R-1).
  • L1 is preferably a group represented by the following formula (L-1).
  • R N represents a hydrogen atom or a monovalent organic group, when a2 is 1, L X represents a single bond or a hydrocarbon group, and when a2 is 2 or more, L X represents a hydrocarbon group
  • R N represents a hydrogen atom or a monovalent organic group
  • * represents a bonding site with X1 or Y1 in formula (1-1)
  • # represents a bonding site with Z1 in formula (R-1).
  • R N the preferred embodiments of R N are as described above.
  • Lx is preferably an aromatic hydrocarbon group, an aliphatic saturated hydrocarbon group, or a group represented by a combination thereof.
  • aromatic hydrocarbon group a group in which two or more hydrogen atoms have been removed from a benzene ring is preferable.
  • aliphatic saturated hydrocarbon group an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms is preferable, and an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable.
  • the preferred embodiments of a2 in formula (L-1) are the same as the preferred embodiments of a2 in formula (R-1).
  • Z1 is preferably an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms.
  • the preferred embodiments thereof are the same as the preferred embodiments of these groups in R A1 in formula (A-1-1).
  • R 3 R1 preferred embodiments of R 3 R1 are the same as the preferred embodiments of R 3 R1 in formula (A-1) described above.
  • a1 is preferably an integer of 1 to 4, and more preferably an integer of 1 or 2. Moreover, an embodiment in which a1 is 1 is also one of the preferred embodiments of the present invention.
  • a2 represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.
  • -X1- X1 has 4 or more carbon atoms, preferably 4 to 50 carbon atoms, and more preferably 4 to 40 carbon atoms.
  • X1 preferably represents an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4) below.
  • the organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4) improves the chemical resistance and flatness of the cured product.
  • R 1 and X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
  • R 1 X2 and R 1 X3 each independently represent a hydrogen atom or a substituent, and R 1 X2 and R 1 X3 may be bonded to form a ring structure.
  • R X1 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group or a trifluoromethyl group.
  • the halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom is substituted with a halogen atom. As the halogen atom, F or Cl is preferable, and F is more preferable.
  • R 1 X2 and R 1 X3 each independently represent a hydrogen atom.
  • R X2 and R X3 are bonded to form a ring structure
  • the structure formed by bonding R X2 and R X3 is preferably a single bond, -O- or -C(R) 2 -, more preferably -O- or -C(R) 2 -, and even more preferably -O-.
  • R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.
  • X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-1)
  • X 1 is preferably a group represented by the following formula (V-1-1).
  • * represents a bonding site to the four carbonyl groups to which X 1 in formula (1-1) is bonded
  • n1 represents an integer of 0 to 5, and is also preferably an integer of 1 to 5.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as a hydrocarbon group.
  • X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), X 1 is preferably a group represented by formula (V-2-1) or formula (V-2-2) below, and from the viewpoint of lowering the amine value in the resin, it is preferably a group represented by formula (V-2-2).
  • a bond crossing a side of a ring structure means substituting any of the hydrogen atoms in the ring structure.
  • L X1 represents a single bond or -O-
  • * represents a bonding site with the four carbonyl groups to which X 1 in formula (1-1) is bonded.
  • R X1 are as described above.
  • the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups.
  • X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3)
  • X 1 is preferably a group represented by formula (V-3-1) or formula (V-3-2) below, and from the viewpoint of reducing the dielectric constant of the cured product, it is preferably a group represented by formula (V-3-2).
  • * represents a bonding site with the four carbonyl groups to which X 1 in formula (1-1) is bonded.
  • R X2 and R X3 are as described above.
  • the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups.
  • X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4)
  • X 1 is preferably a group represented by formula (V-4-1) below.
  • * represents a bonding site to the four carbonyl groups to which X 1 in formula (1-1) is bonded
  • n1 represents an integer of 0 to 5.
  • the hydrogen atoms in the structure below may be further substituted with a known substituent such as a hydrocarbon group. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-4-1) is substituted.
  • X1 may be a tetracarboxylic acid residue remaining after removal of the anhydride groups from the tetracarboxylic dianhydride described in paragraphs 0055 to 0057 of JP-A-2023-003421.
  • X1 does not contain an imide bond in the structure. Furthermore, it is preferable that X1 does not contain a urethane bond, a urea bond or an amide bond in the structure.
  • R N 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.
  • X 1 does not contain an imide bond, a urethane bond, a urea bond, or an amide bond, and it is more preferable that X 1 does not contain an imide bond, a urethane bond, a urea bond, an amide bond, or an ester bond.
  • X1 may be a structure represented by the following formula (X-2), or a structure in which a hydrogen atom of a group represented by X2 in the structure represented by (X-2) or a hydrogen atom of a group represented by L3 is substituted with a group represented by R1 in formula (1-1).
  • X2 each independently represents a trivalent linking group
  • L3 represents a divalent linking group
  • * represents a bonding site to another structure.
  • X2 is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, or a group in which two or more of these are linked by a single bond or a linking group.
  • a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferred.
  • the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
  • the halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms.
  • examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.
  • the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms.
  • preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group.
  • the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.
  • X2 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated.
  • the halogenation is preferably chlorination.
  • a compound having three carboxy groups is called a tricarboxylic acid compound.
  • two of the carboxy groups may be converted into acid anhydrides.
  • the tricarboxylic acid compound which may be halogenated include branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.
  • X2 does not contain an imide structure in the structure. Furthermore, it is preferable that X2 does not contain a urethane bond, a urea bond or an amide bond in the structure. Furthermore, it is preferable that X2 does not contain an ester bond in the structure. Among these, X2 preferably does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and more preferably does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.
  • tricarboxylic acid compounds containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group combining two or more of these groups with a single bond or a linking group are preferred, and tricarboxylic acid compounds containing an aromatic group having 6 to 20 carbon atoms, or a group combining two or more aromatic groups having 6 to 20 carbon atoms with a single bond or a linking group are more preferred.
  • tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, -CH2- , -C( CH3 ) 2- , -C( CF3 ) 2- , -SO2- , or a phenylene group.
  • These compounds may be compounds in which two carboxy groups are anhydridized (e.g., trimellitic anhydride) or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).
  • L 3 is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, or a group in which two or more of these are linked by a single bond or a linking group.
  • a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferred.
  • the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
  • the halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms.
  • examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.
  • the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms.
  • preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group.
  • the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.
  • X1 may be a structure represented by the following formula (X-3), or a structure in which a hydrogen atom of a group represented by X2 or a hydrogen atom of a group represented by L3 in the structure represented by (X-3) is substituted with a group represented by R1 in formula (1-1).
  • X2 's each independently represent a trivalent linking group
  • L3 represents a divalent linking group
  • * represents a bonding site to another structure.
  • preferred embodiments of X2 and L3 are the same as those of X2 and L3 in formula (X-2).
  • Y 1 may be a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulae (V-1) to (V-4).
  • the organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4) improves the chemical resistance and flatness of the cured product.
  • Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1)
  • Y1 is preferably a group represented by the following formula (V-1-2).
  • * represents the bonding site to the two nitrogen atoms to which Y1 in formula (1-1) is bonded
  • n1 represents an integer of 1 to 5.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Y 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), Y 1 is preferably a group represented by formula (V-2-3) or formula (V-2-4) below, and from the viewpoint of decreasing the dielectric constant of the cured product, a group represented by formula (V-2-4) is preferable.
  • L X1 represents a single bond or -O-, and * represents a bonding site with the two nitrogen atoms to which Y 1 is bonded in formula (1-1).
  • R X1 are as described above.
  • the hydrogen atoms may be further substituted with known substituents such as hydrocarbon groups.
  • Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3)
  • Y1 is preferably a group represented by formula (V-3-3) or formula (V-3-4) below, and from the viewpoint of decreasing the dielectric constant of the cured product, a group represented by formula (V-3-3) is preferable.
  • * represents the bonding site with the two nitrogen atoms to which Y1 in formula (1-1) is bonded.
  • the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups.
  • Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4)
  • Y1 is preferably a group represented by the following formula (V-4-2) or (V-4-3).
  • * represents a bonding site to the two nitrogen atoms to which Y1 in formula (1-1) is bonded
  • n1 represents an integer of 0 to 5.
  • An embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention.
  • the hydrogen atoms in the following structures may be further substituted with known substituents such as a hydrocarbon group.
  • Y 1 may be a group described in paragraphs 0042 to 0053 of JP-A No. 2023-003421.
  • Y1 does not contain an imide bond in the structure. It is also preferred that Y1 does not contain a urethane bond, a urea bond or an amide bond in the structure. Furthermore, it is preferable that Y1 does not contain an ester bond in the structure.
  • Y1 does not contain an imide bond, a urethane bond, a urea bond, or an amide bond, and it is more preferable that Y1 does not contain an imide bond, a urethane bond, a urea bond, an amide bond, or an ester bond.
  • X1 and Y1 in formula (1-1) are each an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4) above.
  • the preferred aspects of these groups are as described above.
  • n is preferably 1 or 2, and more preferably 2.
  • the second resin composition contains a resin B that includes a repeating unit represented by formula (1-1).
  • Preferred embodiments of Resin B are the same as those of Resin A, except that Resin B must contain a repeating unit represented by formula (1-1).
  • Resin A preferably contains a repeating unit represented by formula (1-1) and has at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms, and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms.
  • Resin B preferably has at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms, and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms.
  • At least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms, and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with linear aliphatic hydrocarbon groups having 4 or more carbon atoms will also be referred to as a "specific substituent"
  • a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms will also be referred to as specific substituent A
  • a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms will also be referred to as specific substituent B.
  • the specific resin has a substituent X which is a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a straight-chain aliphatic hydrocarbon group having 6 or more carbon atoms
  • the straight-chain aliphatic hydrocarbon group having 6 or more carbon atoms of the substituent X can be said to correspond to the specific substituent A
  • the substituent X as a whole can be said to correspond to the specific substituent B.
  • the specific resin preferably has a group corresponding to the specific substituent A from the viewpoint of resolution.
  • the specific resin preferably has, as the specific substituent A, a linear or branched alkyl group having 6 or more carbon atoms.
  • the specific resin preferably has, as the specific substituent A, a linear monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and more preferably has a linear alkyl group having 6 or more carbon atoms.
  • the hydrogen atom in the specific substituent A is preferably unsubstituted or substituted with a halogen atom.
  • the halogen atom is preferably a fluorine atom.
  • the embodiment in which the hydrogen atom in the specific substituent A is unsubstituted is also one of the preferred embodiments of the present invention.
  • the specific substituent A preferably has 6 to 30 carbon atoms, and more preferably has 6 to 20 carbon atoms.
  • the cyclic aliphatic hydrocarbon group in the specific substituent B is preferably a cyclic aliphatic saturated hydrocarbon group.
  • the cyclic aliphatic hydrocarbon group in the specific substituent B is preferably a 5- to 10-membered ring, more preferably a 5- to 8-membered ring, and even more preferably a 6-membered ring.
  • the cyclic aliphatic hydrocarbon group in the specific substituent B may be condensed with another ring structure.
  • the other ring structure is preferably a hydrocarbon ring structure, more preferably an aliphatic hydrocarbon ring structure.
  • the linear aliphatic hydrocarbon group having 4 or more carbon atoms in the specific substituent B is preferably a linear alkyl group having 4 or more carbon atoms.
  • the linear aliphatic hydrocarbon group having 4 or more carbon atoms in the specific substituent B preferably has 4 to 30 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 4 to 8 carbon atoms.
  • the molar amount of the specific substituent relative to the number average molecular weight of the specific resin is preferably 0.01 to 10 mmol/g, more preferably 0.1 to 5 mmol/g, and even more preferably 0.1 to 2 mmol/g.
  • the resin may contain a group having the specific substituent as the above-mentioned substituent of X1 or Y1 , or may contain the group having the specific substituent at the terminal of the specific resin.
  • the specific resin preferably has a structure represented by any one of the following formulas (TA-1) to (TA-3).
  • X 31 represents a tetravalent organic group
  • Y 31 represents a divalent organic group
  • R 31 represents a group having at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms
  • R 31 is a group that does not contain an imide structure
  • * represents a bonding site with another structure.
  • X 31 represents a tetravalent organic group
  • Y 31 represents a divalent organic group
  • R 32 represents a group having at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms
  • R 32 is a group that does not contain an imide structure
  • * represents a bonding site with another structure.
  • X 31 represents a tetravalent organic group
  • Y 31 represents a divalent organic group
  • R 33 and R 34 each independently represent -OH or a monovalent organic group
  • at least one of R 33 and R 34 is a group having at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms
  • R 33 and R 34 are groups not containing an imide structure
  • * represents a bonding site with another structure.
  • the specific resin preferably has a structure represented by any one of formulas (TA-1) to (TA-3) at the main chain terminal.
  • the specific resin preferably has a structure represented by formula (TA-1).
  • R 31 is preferably a group represented by the following formula (R-31).
  • L 31 represents a single bond or a linking group with a valence of a31+1, and when a31 is 2 or greater, L 31 represents a linking group with a valence of a31+1, Z 31 represents a single bond, -O-, or -NR N -, R N represents a hydrogen atom or a monovalent organic group,
  • a 1 represents a group having at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a31 represents an integer of 1 or greater.
  • L 31 is preferably a single bond.
  • the preferred aspects of R N are as described above.
  • Z 31 is preferably a single bond.
  • the preferred embodiments of A 1 are the same as the preferred embodiments of A 1 in formula (R-1) described above.
  • a31 is preferably an integer of 1 to 4, and more preferably 1 or 2.
  • an embodiment in which a31 is 1 is also one of the preferred embodiments of the present invention.
  • R 32 is preferably a group represented by the following formula (R-32).
  • R 32 represents a hydrogen atom or a monovalent organic group; when a32 is 1, L 32 represents a single bond or a linking group with a valence of a32+1; when a32 is 2 or more, L 32 represents a linking group with a valence of a32+1; Z 32 represents a single bond, -O-, or -NR N -; R 32 represents a hydrogen atom or a monovalent organic group;
  • a 1 represents a group having at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms; and a32 represents an integer of 1 or more.
  • R 3 N preferred embodiments of R 3 N are as described above.
  • preferred embodiments of L 32 , Z 32 , A 1 and a32 are the same as the preferred embodiments of L 31 , Z 31 , A 1 and a31 in formula (R-31) described above.
  • R 33 and R 34 are preferably a group represented by the following formula (R-33).
  • Z 33 represents -O- or -NR N -; when a33 is 1, L 33 represents a single bond or a linking group with a valence of a33+1; when a33 is 2 or more, L 33 represents a linking group with a valence of a33+1; Z 34 represents a single bond, -O- or -NR N -; R N represents a hydrogen atom or a monovalent organic group;
  • a 1 represents a group having at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms; and a33 represents an integer of 1 or more.
  • Z 33 is preferably —NR N —. Preferred embodiments of R N are as described above.
  • preferred embodiments of L 33 , Z 34 , A 1 and a33 are the same as the preferred embodiments of L 31 , Z 31 , A 1 and a31 in formula (R-31) described above.
  • one of R 33 and R 34 may be —OH, or an alkoxy group not containing a specific substituent such as —OC 2 H 5 .
  • the specific resin may contain a repeating unit represented by formula (4).
  • the repeating unit represented by formula (1-1) does not fall under the repeating unit represented by formula (4).
  • R 131 represents a divalent organic group
  • R 132 represents a tetravalent organic group.
  • R 131 represents a divalent organic group.
  • Examples of the divalent organic group R 131 include groups described in paragraphs 0042 to 0053 of JP-A-2023-003421. These descriptions are incorporated herein by reference.
  • R 132 represents a tetravalent organic group.
  • R 132 include the compounds described in paragraphs 0055 to 0057 of JP-A-2023-003421. The descriptions therein are incorporated herein by reference.
  • the content of the repeating unit represented by formula (1-1) relative to the total mass of the specific resin is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the specific resin is a polyimide
  • the total content of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (4) relative to the total mass of the specific resin is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the specific resin when the specific resin contains a repeating unit represented by formula (1-1), it may contain two or more repeating units represented by formula (1-1) having different structures. In that case, it is preferable that the total amount is within the above range.
  • the specific resin when the specific resin contains a repeating unit represented by formula (4), it may contain two or more repeating units represented by formula (4) having different structures. In that case, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention preferably contains, as the specific resin, a resin whose film having a thickness of 10 ⁇ m has a dissolution rate in cyclopentanone of 0.01 to 0.2 ⁇ m/sec.
  • the lower limit of the dissolution rate is preferably 0.02 ⁇ m/sec or more, and more preferably 0.05 ⁇ m/sec or more.
  • the upper limit of the dissolution rate is preferably 0.2 ⁇ m/sec or less, and more preferably 0.15 ⁇ m/sec or less.
  • the film used to measure the dissolution rate of a specific resin can be obtained, for example, by preparing a solution in which the specific resin is dissolved in a solvent, applying the solution to a substrate such as a silicon wafer, and drying as necessary. If drying is performed, the film thickness after drying will be 10 ⁇ m.
  • the solvent for dissolving the specific resin used in preparing the above solution may be ⁇ -butyrolactone. If it is difficult to carry out the process because the specific resin does not dissolve in ⁇ -butyrolactone, the solvent may be changed to a solvent that dissolves the specific resin, such as N-methyl-2-pyrrolidone or dimethyl sulfoxide.
  • the content of the specific resin in the solution can be 30% by mass relative to the total mass of the solvent. However, in cases where it is difficult to form a 10 ⁇ m film at the above content, or the solubility of the specific resin is low and preparation is not possible, the content may be appropriately set between 10 and 60% by mass, for example. In addition, in cases where a 10 ⁇ m film cannot be obtained, the film thickness can be measured at a formable film thickness and converted to a film thickness of 10 ⁇ m.
  • a silicon wafer can be used as the substrate. If it is difficult to form a film with a thickness of 10 ⁇ m using a silicon wafer, other substrates with different properties such as surface wettability may be used.
  • the method for applying the resin composition to the substrate is not particularly limited as long as it is a method that results in a film thickness of 10 ⁇ m, and spin coating can be used. If it is difficult to form a film with a thickness of 10 ⁇ m using spin coating, a suitable method may be selected from known methods such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, slit coating, and inkjet coating.
  • the drying is preferably carried out until the amount of the solvent in the film becomes 0.1% by mass or less.
  • the drying conditions are not particularly limited, and drying can be performed by heating. If it is difficult to sufficiently dry the material by heating alone, the pressure may be reduced.
  • the drying can be carried out in the atmosphere, but when the resin composition contains a component that is easily modified by oxygen, the drying can be carried out under an inert gas such as nitrogen or under vacuum.
  • the drying means is not particularly limited, but examples thereof include a hot plate, etc. However, when the above-mentioned reduction in pressure, replacement with an inert gas, etc. are required, an oven equipped with a reduction in pressure function, an oven equipped with a gas replacement function, etc. may also be used.
  • the heating temperature can be, for example, 110° C. However, when drying at 110° C. is difficult, the drying temperature may be appropriately changed between 70° C. and 130° C., preferably between 90° C. and 120° C., depending on the type of solvent contained in the resin composition, etc.
  • the drying time time of exposure to the heating temperature
  • the heating time can be, for example, 5 minutes. However, if drying within 5 minutes is difficult, the drying time may be appropriately changed to between 30 seconds and 20 minutes, preferably between 1 minute and 10 minutes, depending on the type of solvent contained in the resin composition.
  • the heating rate during heating is not particularly limited and can be, for example, 5° C./min. If drying at the above heating rate is difficult, the heating rate may be appropriately changed between 1 to 12° C./min or 2 to 10° C./min depending on the type of solvent contained in the resin composition, etc.
  • the dissolution rate of the film in cyclopentanone can be calculated by immersing a silicon wafer on which a film has been formed in cyclopentanone for 15 seconds and measuring the film thickness before and after immersion using an ellipsometer.
  • the membrane is immersed in cyclopentanone without being subjected to any heating other than the drying described above.
  • the amount of cyclopentanone used for immersion is preferably 30 times the volume of the membrane.
  • the temperatures of cyclopentanone, the film and the silicon wafer during immersion are set to 23°C. In cases where the film is completely dissolved or where the film thickness does not change at all, the immersion time may be appropriately changed to calculate the dissolution rate.
  • the transmittance of the cured product at a wavelength of 365 nm is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more.
  • the upper limit of the transmittance is not particularly limited and may be 100%.
  • the cured product can be obtained, for example, by applying the resin composition of the present invention to a substrate such as a silicon wafer, drying the composition, exposing the entire surface to i-rays with an exposure energy of 500 mJ/ cm2 , and then heating the composition at a heating rate of 10°C/min in a nitrogen atmosphere and at 230°C for 180 minutes.
  • the transmittance can be measured using a spectrophotometer.
  • the above-mentioned substrate, the method of applying the composition to the substrate, the drying method, etc. can be performed in the same manner as in the measurement of the dissolution rate described above, and the preferred embodiments are also the same.
  • the heating means for heating at 230° C. for 180 minutes the same means as the drying means used in the above-mentioned measurement of the dissolution rate can be used.
  • the weight average molecular weight (Mw) of the specific resin is preferably 3,000 to 100,000.
  • the lower limit of the Mw is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more.
  • the upper limit of the Mw is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 25,000 or less.
  • the weight average molecular weight is particularly preferably 5,000 or more.
  • the number average molecular weight (Mn) of the specific resin is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000, and even more preferably from 5,000 to 20,000.
  • the molecular weight dispersity of the specific resin is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the molecular weight dispersity of the polyimide is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, still more preferably 4.5 or less, and particularly preferably 3.0 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 of the resins 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 plurality of resins as one resin are each within the above ranges.
  • the specific resin can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and esterifying it using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting it with a diamine, etc.
  • the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting it with a diamine is more preferable.
  • the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.
  • alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.
  • halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like.
  • the resin obtained by the above method can be completely imidized by a known imidization reaction method, or the imidization reaction is stopped midway to partially introduce an imide structure, or further, a method of blending a completely imidized polymer with a polyimide precursor to partially introduce an imide structure can be used for synthesis. Other known methods for synthesizing polyimides can also be applied.
  • an organic solvent in the reaction it is preferable to use an organic solvent in the reaction.
  • the organic solvent may be one type or two or more types.
  • the organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and ⁇ -butyrolactone.
  • a basic compound may be one type or two or more types.
  • the basic compound can be appropriately determined depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.
  • -End-capping agent- In the method for producing the specific resin, in order to further improve storage stability, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the specific resin.
  • examples of the terminal capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and it is more preferable to use monoalcohols, phenols, or monoamines from the viewpoint of reactivity and film stability.
  • Examples of preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
  • primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol
  • secondary alcohols such as isopropanol, 2-butanol, cyclo
  • Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.
  • 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, Examples of such an acid include 2-carboxy-7-aminonaphthalene, 2-car
  • blocking agents for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides.
  • Preferred compounds of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, and the like.
  • carboxylic acid chloride examples include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.
  • an amino acid in a compound having an amino group and a hydroxy group such as p-aminophenol
  • a hydroxy group such as 6-maleimidohexanoic acid chloride.
  • a maleimide group can also be introduced at the end of the specific resin.
  • a diamine having a polymerizable group such as a maleimide group as a diamine that is a raw material for polymerizing the specific resin, it is also possible to introduce a polymerizable group into the specific resin.
  • formula (T-1) when a31 is 1, L 31 represents a single bond or a linking group with a valence of a31+1, and when a31 is 2 or more, L 31 represents a linking group with a valence of a31+1, Z 31 represents a single bond, -O-, or -NR N -, R N represents a hydrogen atom or a monovalent organic group, A 1 represents a group having at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a31 represents an integer of
  • R T represents a hydrogen atom or a halogen atom
  • R N represents a hydrogen atom or a monovalent organic group
  • a 1 represents a group having at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon
  • R 1 T is preferably a hydrogen atom or a chlorine atom.
  • preferred embodiments of L 32 , Z 32 , A 1 and a32 are the same as the preferred embodiments of L 32 , Z 32 , A 1 and a32 in formula (R-32).
  • the structure represented by the above formula (TA-3) can be introduced into the resin.
  • T-3 when a31 is 1, L 31 represents a single bond or a linking group with a valence of a31+1, and when a31 is 2 or more, L 31 represents a linking group with a valence of a31+1, Z 31 represents a single bond, -O-, or -NR N -, R N represents a hydrogen atom or a monovalent organic group,
  • a 1 represents a group having at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a31 represents an integer of 1 or more.
  • the method for producing the specific resin may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction liquid as necessary, the obtained polymer component is put into a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid, and then dried to obtain the specific resin. In order to improve the degree of purification, the specific resin may be repeatedly subjected to operations such as redissolving, reprecipitating, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.
  • Specific examples of the specific resin include polyimides SP-1 to SP-23 in the examples described below, but the present invention is not limited to these.
  • 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, even more preferably 50% by mass or more, and most preferably 60% 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 type of specific resin, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is 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 resin described below, or may contain two or more types of the specific resin, but it is preferable that the resin composition contains two or more types of the specific resin.
  • the first resin composition preferably further contains a resin A2 which is a polyimide precursor.
  • Resin A2 preferably contains a repeating unit represented by the following formula (3-1).
  • X3 represents an organic group having 4 or more carbon atoms
  • Y3 represents an organic group having 4 or more carbon atoms
  • A3 and A4 each independently represent an oxygen atom or -NR N -
  • R N represents a hydrogen atom or a monovalent organic group
  • R3 and R4 each independently represent a hydrogen atom or a monovalent organic group
  • R2 each independently represent a group represented by formula (R-2) below
  • n represents an integer of 0 or more.
  • L2 represents a b2+1 valent linking group
  • Z2 represents a b1+1 valent organic group
  • A2 represents a methacryloxy group, an acryloxy group, a methacrylamide group, an acrylamide group, a vinyl group, a styryl group, an allyl group, or a vinyl ether group
  • b1 represents an integer of 1 or more and not exceeding the maximum number of substituents of Z2
  • b2 represents an integer of 1 or more
  • * represents a bonding site with Y2 in formula (2-1) or Y3 in formula (3-1).
  • a 3 and A 4 are both oxygen atoms.
  • the preferable embodiments of R 3 N are as described above.
  • R 3 and R 4 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 undergoing a crosslinking reaction by the action of heat, radicals, etc., and is preferably a radically 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, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most 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 repetitions of the polyalkyleneoxy group) 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 R3 is a hydrogen atom or when R4 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 3 and R 4 are groups having an ethylenically unsaturated bond
  • X 3 includes a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4).
  • Preferred embodiments of the structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4) are as described above.
  • L2 is preferably a group represented by the following formula (L-2).
  • Lx2 represents a b2+1 valent linking group
  • b2 represents an integer of 1 or more
  • * represents a bonding site with Y1 in formula (1-1)
  • # represents a bonding site with Z2 in formula (R-2).
  • L x2 is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, further preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group.
  • the preferred embodiments of b2 in formula (L-2) are the same as the preferred embodiments of b2 in formula (R-2).
  • Z2 in formula (R-2) represents an organic group having a valence of b1+1, and is preferably an aromatic group or an aliphatic hydrocarbon ring group, and more preferably an aromatic group.
  • the aromatic group may be either an aromatic hydrocarbon group or a heteroaromatic ring group, but is preferably an aromatic hydrocarbon ring group or a heteroaromatic ring group containing a nitrogen atom as a ring member.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group is preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and even more preferably a benzene ring.
  • heteroaromatic ring in the heteroaromatic ring group examples include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an oxazole ring, a pyridine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an indazole ring, a benzimidazole ring, and a purine ring.
  • Examples of the aliphatic ring in the cyclic aliphatic group include an aliphatic hydrocarbon ring having 5 to 20 carbon atoms, a pyrrolidine ring, a pyrroline ring, a pyrazolidine ring, an imidazolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a piperazine ring, a tetrahydropyran ring, a dioxane ring, and a morpholine ring.
  • Z2 is preferably a benzene ring, a cyclohexane ring or an adamantane ring, and more preferably a benzene ring.
  • A2 in formula (R-2) is preferably a methacryloxy group, an acryloxy group, a vinyl group or a vinyl ether group, more preferably a vinyl group or a vinyl ether group, and even more preferably a vinyl group.
  • b1 is preferably an integer of 1 to 4, and more preferably an integer of 1 or 2. Moreover, an embodiment in which b1 is 1 is also one of the preferred embodiments of the present invention.
  • b2 represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.
  • the number of ester bonds contained in formula (R-2) is preferably 1 or 0.
  • n is preferably an integer from 0 to 4, and more preferably an integer from 0 to 2.
  • Resin A2 may contain one type of repeating unit represented by formula (3-1), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (3-1). Needless to say, Resin A2 may contain other types of repeating units in addition to the repeating unit of formula (3-1).
  • resin A2 in the present invention is one in which the content of the repeating unit represented by formula (3-1) is 50 mol% or more of all repeating units.
  • the content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
  • all repeating units in resin A2 except for the terminals may be repeating units represented by formula (3-1).
  • the weight average molecular weight (Mw) of Resin A2 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) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
  • the molecular weight dispersity of the resin A2 is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the molecular weight dispersity of the resin A2 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 resin composition contains multiple resins A2
  • the weight average molecular weight, number average molecular weight, and dispersity of at least one of the resins A2 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 resins A2 as one resin are each within the above ranges.
  • the content of the resin A2 in the first resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total solid content of the resin composition.
  • the content is preferably 70% by mass or less, and more preferably 60% by mass or less.
  • the content of resin A relative to the total content of resin A and resin A2 is preferably 5 to 70 mass %, and more preferably 20 to 60 mass %.
  • the first resin composition may further contain a resin A3 which is a polyimide not corresponding to the resin A described above.
  • Resin A3 preferably contains a repeating unit represented by the following formula (2-1).
  • X2 represents an organic group having 4 or more carbon atoms
  • Y2 represents an organic group having 4 or more carbon atoms
  • R2 each independently represents a group represented by the following formula (R-2)
  • n represents an integer of 1 or more.
  • L2 represents a b2+1 valent linking group
  • Z2 represents a b1+1 valent organic group
  • A2 represents a methacryloxy group, an acryloxy group, a methacrylamide group, an acrylamide group, a vinyl group, a styryl group, an allyl group, or a vinyl ether group
  • b1 represents an integer of 1 or more and not exceeding the maximum number of substituents of Z2
  • b2 represents an integer of 1 or more
  • * represents a bonding site with Y2 in formula (2-1) or Y3 in formula (3-1).
  • n is preferably an integer from 1 to 4, and more preferably 1 or 2.
  • Resin A3 may contain one type of repeating unit represented by formula (2-1), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2-1). Needless to say, Resin A3 may contain other types of repeating units in addition to the repeating unit of formula (2-1).
  • the content of the repeating unit represented by formula (2-1) is 30 mol % or more of all repeating units.
  • the content is more preferably 50 mol % or more.
  • all repeating units in resin A3 except for the terminals may be repeating units represented by formula (2-1).
  • the resin A3 may have the specific substituent described above. Preferred embodiments of the specific substituent are the same as those of the specific substituent in the resin A. It is also preferable that the resin A3 has a structure represented by any one of the above formulae (TA-1) to (TA-3). Preferred embodiments of the structures represented by these formulae are as described above.
  • the weight average molecular weight (Mw) of Resin A3 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) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
  • the molecular weight dispersity of the resin A3 is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the 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 resin composition contains multiple resins A3 as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one of the resins A3 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 resins A3 as one resin are each within the above ranges.
  • the content of the resin A3 in the first resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total solid content of the resin composition.
  • the content is preferably 70% by mass or less, and more preferably 60% by mass or less.
  • the content of resin A relative to the total content of resin A and resin A3 is preferably 20 to 80 mass %, and more preferably 30 to 70 mass %.
  • the second resin composition contains a resin C containing at least one of the repeating units represented by formula (2-1) and formula (3-1).
  • Resin C is a resin that does not fall under Resin B.
  • the preferred embodiments of the formula (2-1) and the formula (3-1) in the resin C are as described above.
  • Resin C is a polyimide containing a repeating unit represented by formula (2-1)
  • the preferred embodiments of Resin C are the same as the preferred embodiments of Resin A3 described above.
  • Resin C is a polyimide precursor containing a repeating unit represented by formula (3-1)
  • the preferred embodiments of Resin C are the same as the preferred embodiments of Resin A2 described above.
  • the content of the repeating unit represented by formula (3-1) is 50 mol% or more of all 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%.
  • all repeating units in resin C except for the terminals may be repeating units represented by formula (3-1).
  • the weight average molecular weight (Mw) of the resin C 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) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
  • the molecular weight dispersity of the resin C is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the 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 weight average molecular weight, number average molecular weight, and dispersity of at least one type of resin C 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 types of resins C as one resin are each within the above ranges.
  • the content of the resin C in the second resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total solid content of the resin composition.
  • the content is preferably 70% by mass or less, and more preferably 60% by mass or less.
  • the content of resin B relative to the total content of resin B and resin C is preferably 20 to 80 mass %, and more preferably 30 to 70 mass %.
  • the resin composition of the present invention may contain other resins (hereinafter simply referred to as "other resins") different from the above-mentioned specific resin, resin A2, resin A3 and resin C.
  • other resins are resins different from the specific resin, resin A2, resin A3, and resin C, and include resins corresponding to polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, polyamideimides, phenolic 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.
  • polyimide precursors include the compounds described in paragraphs 0017 to 0138 of WO 2022/145355. The above descriptions are incorporated herein by reference.
  • 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 other resins in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, still 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 content of the specific resin relative to the total content of the specific resin and the other resins is preferably 10 to 90 mass%, more preferably 10 to 60 mass%, and even more preferably 20 to 50 mass%.
  • 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 resin composition of the present invention contains a polymerizable compound.
  • the melting point of the polymerizable compound is preferably 25° C. or lower. By adjusting the melting point to 25° C. or less, the coating film becomes more fluid when dried and heated, and the flatness of the cured product can be improved.
  • the polymerizable compound it is preferable for the polymerizable compound to contain a compound with a ClogP value of 3.0 or more, and it is even more preferable for the polymerizable compound to contain a compound with a ClogP value of 3.0 or more and an aromatic ring structure or an aliphatic ring structure with 6 or more carbon atoms.
  • the ClogP value of a compound is defined as follows.
  • the octanol-water partition coefficient (log P value) can generally be measured by the flask shaking method described in JIS Z7260-107 (2000).
  • the octanol-water partition coefficient (log P value) can also be estimated by a computational chemistry method or an empirical method instead of actual measurement.
  • a calculation method it is known to use Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163 (1989)), Broto's fragmentation method (Eur. J. Med. Chem.-Chim.
  • Crippen's fragmentation method J. Chem. Inf. Comput. Sci., 27, 21 (1987)
  • the ClogP value is a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water.
  • Known methods and software can be used for calculating the ClogP value, but unless otherwise specified, the present invention uses the ClogP program incorporated in the PCModels system of Daylight Chemical Information Systems.
  • the ClogP value is preferably 4.0 or more, and more preferably 6.0 or more. Further, the upper limit of the ClogP value is not particularly limited, but is preferably 15.0 or less.
  • the aromatic ring structure may be an aromatic hydrocarbon ring or an aromatic heterocycle, but is preferably an aromatic hydrocarbon ring, more preferably one containing a benzene ring, and is preferably a condensed ring such as a fluorene ring from the viewpoint of reducing the dielectric constant of the cured product.
  • the aliphatic ring structure having 6 or more carbon atoms is preferably an aliphatic ring structure having 6 to 30 carbon atoms, and more preferably an aliphatic ring structure having 6 to 20 carbon atoms.
  • Examples of the aliphatic ring structure having 6 or more carbon atoms include a monocyclic ring such as a cyclohexane ring, and a polycyclic ring such as a dicyclopentane ring or a tricyclo[5.2.1.0 2,6 ]decane ring, with a polycyclic ring being preferred.
  • the polymerizable compound having a ClogP value of 3.0 or more is preferably a compound containing a group having an ethylenically unsaturated bond, more preferably a compound containing two or more groups having an ethylenically unsaturated bond. Also, it is preferably a compound containing two groups having an ethylenically unsaturated bond.
  • the polymerizable compound having a ClogP value of 3.0 or more is preferably a compound corresponding to a radical crosslinking agent described later.
  • polymerizable compound having a ClogP value of 3.0 or more include the following compounds, but are not limited thereto.
  • the polymerizable compound may be a radical crosslinker or another crosslinker.
  • 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 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 polyamine 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 polyamine compounds amides of unsaturated carboxylic acids and polyamine compounds.
  • addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with mono
  • 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.)), and structures in
  • 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.)
  • esters 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 PME 400 (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 production and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.
  • 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 ...
  • EO ethylene oxide
  • PO propylene oxide
  • PO propylene oxide
  • PO propylene oxide
  • 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 contains a polymerization initiator.
  • the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable that the resin composition contains 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.
  • 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 %, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition.
  • 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
  • the chain transfer agent may also be the compound described in paragraphs 0152-0153 of International Publication No. 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 polymerization initiator is preferably a photoacid generator, and the photoacid generator is preferably a photoacid generator that generates radicals.
  • the photoacid generator is a compound that absorbs light, decomposes to generate radicals, and abstracts hydrogen from a solvent or the acid generator itself to generate an acid.
  • Examples of the photoacid generator include quinone diazide compounds, oxime sulfonate compounds, organic halide compounds, organic borate compounds, disulfone compounds, and onium salts, with onium salts being preferred.
  • Examples of the onium salt include diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts.
  • An onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond. That is, the onium salt may be an intramolecular salt having a cationic moiety and an anionic moiety in the same molecular structure, or an intermolecular salt in which a cationic molecule and an anionic molecule, which are separate molecules, are ionic-bonded, but an intermolecular salt is preferable.
  • the cationic moiety or cationic molecule and the anionic moiety or anionic molecule may be bonded by an ionic bond or may be dissociated.
  • the sulfonium salt means a salt of a sulfonium cation and an anion.
  • sulfonium cation a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred.
  • a cation represented by the following formula (103) is preferable.
  • R 8 to R 10 each independently represent a hydrocarbon group.
  • Each of R 8 to R 10 independently represents preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an aryl group having 6 to 12 carbon atoms, and still more preferably a phenyl group.
  • R 8 to R 10 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc.
  • the substituent it is preferable for the substituent to be an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • R 8 to R 10 may be the same group or different groups, but from the viewpoint of synthetic suitability, it is preferable that they are the same group.
  • the anion is not particularly limited and may be selected taking into consideration the acid to be generated.
  • examples of the anion include boron-based anions such as B(C 6 F 5 ) 4 ⁇ and BF 4 ⁇ , phosphorus-based anions such as (Rf) n PF 6-n ⁇ , PF 3 (C 2 F 5 ) 3 ⁇ and PF 6 ⁇ , antimony-based anions such as SbF 6 ⁇ , and other carboxylate anions and sulfonate anions.
  • the iodonium salt refers to a salt of an iodonium cation and an anion.
  • anion include the same anions as those in the sulfonium salt described above, and preferred embodiments are also the same.
  • the iodonium cation is preferably a diaryliodonium cation. Moreover, the iodonium cation is preferably a cation represented by the following formula (104).
  • R 11 and R 12 each independently represent a hydrocarbon group.
  • R 11 and R 12 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an aryl group having 6 to 12 carbon atoms, and even more preferably a phenyl group.
  • R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc.
  • the substituent has an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and further preferably a branched alkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • R 11 and R 12 may be the same group or different groups, but from the viewpoint of synthesis suitability, it is preferable that they are the same group.
  • the phosphonium salt refers to a salt of a phosphonium cation and an anion.
  • anion include the same anions as those in the sulfonium salt described above, and preferred embodiments are also the same.
  • the phosphonium cation is preferably a quaternary phosphonium cation, such as a tetraalkylphosphonium cation or a triarylmonoalkylphosphonium cation. Moreover, the phosphonium cation is preferably a cation represented by the following formula (105).
  • R 13 to R 16 each independently represent a hydrogen atom or a hydrocarbon group.
  • Each of R 13 to R 16 independently represents preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an aryl group having 6 to 12 carbon atoms, and still more preferably a phenyl group.
  • R 13 to R 16 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc.
  • the substituent has an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and further preferably a branched alkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
  • R 13 to R 16 may be the same group or different groups, but from the viewpoint of synthesis suitability, it is preferable that they are the same group.
  • the content of the photoacid generator is preferably 0.1 to 20 mass%, more preferably 0.5 to 18 mass%, even more preferably 0.5 to 10 mass%, still more preferably 0.5 to 3 mass%, and even more preferably 0.5 to 1.2 mass%, based on the total solid content of the resin composition.
  • the photoacid generator may be used alone or in combination of two or more kinds. In the case of using a combination of two or more kinds, the total amount thereof is preferably within the above range. It is also preferable to use a sensitizer in combination to impart photosensitivity to a desired light source.
  • 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%. Only one type of thermal polymerization initiator may be included, or two or more types may be included. 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 preferably contains a solvent.
  • 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, it is preferable that the total amount is 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.
  • 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- Examples of such compounds include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(amin
  • 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 represents a monovalent organic group
  • R 2 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 lower limit above, the adhesion between the pattern and the metal layer will be good, and by making the content equal to or less than the upper limit above, 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 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.
  • the resin composition of the present invention preferably contains an azole compound.
  • the azole compound is a compound containing an azole structure, and the azole structure refers to a five-membered ring structure containing a nitrogen atom as a ring member, and is preferably a five-membered ring structure containing two or more nitrogen atoms as ring members.
  • Specific examples of the azole structure include an imidazole structure, a triazole structure, and a tetrazole structure.These structures may form a polycyclic ring by condensation with another ring structure, such as benzimidazole and benzotriazole.
  • R-1 represents a monovalent organic group
  • * represents a bonding site with the azole structure
  • R-2 represents a hydrogen atom or a monovalent organic group
  • R 3 represents a monovalent organic group
  • * represents a bonding site with the azole structure.
  • the above-mentioned hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
  • the total number of carbon atoms in R 1 is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20.
  • the bonding site of R 1 to the carbonyl group in formula (R-1) is preferably a hydrocarbon group or -NR N -.
  • * represents a bonding site to the azole structure, and is preferably a bonding site to a carbon atom that is a ring member of the azole structure.
  • R 2 is preferably a hydrogen atom.
  • the above-mentioned hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
  • R 2 is a monovalent organic group, the total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20.
  • R 2 is a monovalent organic group
  • R N represents a hydrogen atom or a hydrocarbon group, and is preferably a hydrogen atom.
  • the above-mentioned hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
  • R 3 is a monovalent organic group
  • the total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20.
  • * represents a bonding site to the azole structure, and is preferably a bonding site to a carbon atom that is a ring member of the azole structure.
  • 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 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 resin composition of the present invention further contains the above-mentioned azole compound and the above-mentioned silane coupling agent.
  • 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.
  • 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, and the like. The contents of this specification 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 various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, base 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, base 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 retard
  • inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
  • the average particle size of the inorganic particles is preferably from 0.01 to 2.0 ⁇ m, more preferably from 0.02 to 1.5 ⁇ m, even more preferably from 0.03 to 1.0 ⁇ m, and particularly preferably from 0.04 to 0.5 ⁇ m.
  • the above average particle size of the inorganic particles is the primary particle size and also the volume average particle size.
  • the volume average particle size can be measured by a dynamic light scattering method using, for example, a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). When the above measurements are difficult, the measurements can also be made by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method.
  • Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
  • Specific examples of the organotitanium compound are shown below in I) to VII):
  • I) Titanium chelate compounds Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and provide a good curing pattern.
  • 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), etc.
  • 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 ⁇ ], and the like.
  • 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, and the like.
  • the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds.
  • 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.
  • T-1 a compound represented by the following formula (T-1) as the organotitanium compound or in place of the organotitanium compound.
  • M is titanium, zirconium or hafnium
  • l1 is an integer of 0 to 2
  • l2 is 0 or 1
  • l1+l2 ⁇ 2 is an integer of 0 to 2
  • m is an integer of 0 to 4
  • n is an integer of 0 to 2
  • R 12 is a substituted or unsubstituted hydrocarbon group
  • R 2 is independently a group containing a structure represented by formula (T-2) below
  • R 3 is independently a group containing a structure represented by formula (T-2) below
  • X A is independently
  • M is preferably titanium.
  • l1 and l2 are 0 is also one of the preferred embodiments of the present invention.
  • m is preferably 2 or 4, and more preferably 2.
  • n is preferably 1 or 2, and more preferably 1.
  • l1 and l2 are 0, and m is 0, 2 or 4 in formula (T-1).
  • R 11 is preferably a substituted or unsubstituted cyclopentadienyl ligand.
  • the cyclopentadienyl group, alkoxy group and phenoxy group in R 11 may be substituted, but the unsubstituted embodiment is also one of the preferred embodiments of the present invention.
  • R 12 is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms.
  • the hydrocarbon group for R 12 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with aromatic hydrocarbon groups being preferred.
  • the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, with a saturated aliphatic hydrocarbon group being preferred.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group.
  • R 12 is preferably a monovalent substituent, such as a halogen atom, etc.
  • R 12 is an aromatic hydrocarbon group, it may have an alkyl group as a substituent.
  • R 12 is preferably an unsubstituted phenylene group, and the phenylene group in R 12 is preferably a 1,2-phenylene group.
  • formula (T-1) when m is 2 or more and two or more R 2s are included, the structures of the two or more R 2s may be the same or different. In formula (T-1), when n is 2 or more and two or more R 3s are included, the structures of the two or more R 3s may be the same or different.
  • an organic titanium compound When an organic titanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the specific resin. If the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern will be better, and if it is 10 parts by mass or less, the storage stability of the composition will be superior.
  • an organic titanium compound When an organic titanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the obtained cured pattern become better, and when it is 10 parts by mass or less, the storage stability of the composition becomes more excellent.
  • Other additives include compounds described in paragraphs 0249 to 0282 and 0316 to 0358 of WO 2022/145355. The above descriptions are incorporated herein.
  • 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 breaking elongation 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 transmittance of the cured product at a wavelength of 365 nm is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more.
  • the upper limit of the transmittance is not particularly limited and may be 100%.
  • the transmittance is measured using a known spectrophotometer.
  • the resin composition of the present invention can be prepared by mixing the above-mentioned components.
  • the mixing method is not particularly limited, and can be a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank.
  • the temperature during mixing is preferably from 10 to 30°C, more preferably from 15 to 25°C.
  • the filter pore size is, for example, preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, even more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, it is more preferable that it is HDPE (high density polyethylene).
  • the filter may be used after being washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel.
  • filters with different pore sizes or materials may be used in combination.
  • a connection mode an HDPE filter with a pore size of 1 ⁇ m as the first stage and an HDPE filter with a pore size of 0.2 ⁇ m as the second stage may be connected in series.
  • various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be performed. Filtration may also be performed under pressure.
  • the pressure to be applied is, for example, preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.
  • impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • the adsorbent a known adsorbent may be used.
  • inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used.
  • the resin composition filled in the bottle may be subjected to a degassing step by placing it under reduced pressure.
  • 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. Each step will be described in detail below.
  • the resin composition of the present invention can be used in a film-forming process in which the resin composition is applied onto a substrate to form a film.
  • 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.
  • substrate The type of substrate can be appropriately determined according to the application, and is not particularly limited.
  • substrates include semiconductor-prepared substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals and substrates in which a metal layer is formed by plating, vapor deposition, etc.), paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates of plasma display panels (PDPs).
  • semiconductor-prepared substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals and substrates in which a metal layer is formed by plating,
  • the substrate is preferably a semiconductor-prepared substrate, more preferably a silicon substrate, a Cu substrate, or a mold substrate. These substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface.
  • HMDS hexamethyldisilazane
  • the shape of the substrate is not particularly limited, and may be circular or rectangular.
  • the size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular, and preferably, a short side length of 100 to 1000 mm, more preferably 200 to 700 mm, if it is rectangular.
  • a plate-shaped substrate preferably a panel-shaped substrate (substrate) is used as the substrate.
  • a resin composition When a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer made of a cured material) or to the surface of a metal layer, the resin layer or metal layer serves as the substrate.
  • a resin layer e.g., a layer made of a cured material
  • the resin layer or metal layer serves as the substrate.
  • the resin composition is preferably applied to a substrate by coating.
  • the means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet methods. From the viewpoint of uniformity of the thickness of the film, spin coating, slit coating, spray coating, or inkjet methods are preferred, and from the viewpoint of uniformity of the thickness of the film and productivity, spin coating and slit coating are more preferred.
  • a film of a desired thickness can be obtained by adjusting the solid content concentration and coating conditions of the resin composition according to the means to be applied.
  • the coating method can be appropriately selected depending on the shape of the substrate, and if the substrate is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and if the substrate is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred.
  • the spin coating method for example, it can be applied for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm.
  • a coating film formed by applying the coating material to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate.
  • the transfer method the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No.
  • 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used.
  • a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinsing (EBR) or back rinsing.
  • EBR edge bead rinsing
  • a pre-wetting step may be employed in which, before applying the resin composition to the substrate, the substrate is coated with various solvents to improve the wettability of the substrate, and then the resin composition is applied.
  • the above-mentioned film may be subjected to a step of drying the formed film (layer) (drying step) in order to remove the solvent.
  • the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
  • the drying step is preferably carried out after the film-forming step and before the exposure step.
  • the drying temperature of the film in the drying step is preferably 50 to 150° C., more preferably 70 to 130° C., and even more preferably 90 to 110° C. Drying may be performed under reduced pressure.
  • the drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.
  • the film may be subjected to an exposure step to selectively expose the film to light.
  • the method for producing a cured product may include an exposure step of selectively exposing the film formed in the film formation step to light. Selective exposure means that only a portion of the film is exposed, and selective exposure results in exposed and unexposed areas of the film.
  • the amount of exposure light is not particularly limited as long as it can cure the resin composition of the present invention, but is preferably 50 to 10,000 mJ/cm 2 , and more preferably 200 to 8,000 mJ/cm 2 , calculated as exposure energy at a wavelength of 365 nm.
  • the exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.
  • the exposure wavelength may be, in particular, (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532 nm, third harmonic 355 nm, etc.
  • semiconductor laser wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 3
  • the exposure method is not particularly limited as long as it is a method that exposes at least a part of the film made of the resin composition of the present invention, and examples of the exposure method include exposure using a photomask and exposure by a laser direct imaging method.
  • the film may be subjected to a step of heating after exposure (post-exposure baking step). That is, the method for producing a cured product of the present invention may include a post-exposure baking step of heating the film exposed in the exposure step.
  • the post-exposure baking step can be carried out after the exposure step and before the development step.
  • the heating temperature in the post-exposure baking step is preferably from 50°C to 140°C, and more preferably from 60°C to 120°C.
  • the heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, and more preferably from 1 minute to 10 minutes.
  • the heating rate in the post-exposure heating step is preferably from 1 to 12° C./min, more preferably from 2 to 10° C./min, and even more preferably from 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature.
  • the rate of temperature rise may be appropriately changed during heating.
  • the heating means in the post-exposure baking step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. can be used. It is also preferable that the heating be performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.
  • the film may be subjected to a development step in which the film is developed with a developer to form a pattern.
  • the method for producing a cured product of the present invention may include a development step of developing the film exposed in the exposure step with a developer to form a pattern. Development removes one of the exposed and unexposed areas of the film to form a pattern.
  • development in which the non-exposed portion of the film is removed by the development process is called negative development
  • development in which the exposed portion of the film is removed by the development process is called positive development.
  • the developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.
  • examples of basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
  • TMAH tetramethylammonium hydroxide
  • potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammoni
  • the compounds described in paragraph 0387 of WO 2021/112189 can be used as the organic solvent.
  • the organic solvent examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol
  • examples of amides that are suitable include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.
  • the organic solvent may be used alone or in combination of two or more.
  • a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.
  • the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the content may be 100% by mass.
  • the developer may further comprise other components.
  • other components include known surfactants and known defoamers.
  • the method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and includes a method of immersing the substrate on which the film is formed in the developer, a paddle development method in which the developer is supplied to the film formed on the substrate using a nozzle, and a method of continuously supplying the developer.
  • the type of nozzle is not particularly limited, and includes a straight nozzle, a shower nozzle, a spray nozzle, and the like.
  • a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred.
  • a process may be adopted in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate. This process may be repeated multiple times.
  • Methods of supplying the developer in the development step include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated by ultrasonic waves or the like on the substrate, and a combination of these steps.
  • the development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
  • the temperature of the developer during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18°C to 30°C.
  • the pattern may be washed (rinsed) with a rinse solution. Also, a method may be adopted in which a rinse solution is supplied before the developer in contact with the pattern has completely dried.
  • the rinse liquid may be, for example, water.
  • the rinse liquid may be, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer).
  • the organic solvent include the same organic solvents as those exemplified when the developing liquid contains an organic solvent.
  • the organic solvent contained in the rinse liquid is preferably different from the organic solvent contained in the developer, and more preferably has a lower solubility for the pattern than the organic solvent contained in the developer.
  • the organic solvent may be used alone or in combination of two or more.
  • the organic solvent is preferably cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.
  • the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the rinse solution. Furthermore, the organic solvent may account for 100% by mass, based on the total mass of the rinse solution.
  • the rinse solution may further contain other ingredients.
  • other components include known surfactants and known defoamers.
  • the method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples of the method include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like.
  • the rinse liquid may be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, while from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred.
  • the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.
  • the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle.
  • the method of supplying the rinsing liquid in the rinsing step may include a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially stationary state on the substrate, a step of vibrating the rinsing liquid on the substrate by ultrasonic waves or the like, and a combination of these steps.
  • the rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
  • the temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18°C to 30°C.
  • the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step. The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without carrying out a development step, or a film obtained in a film formation step. In the heating step, the resin such as the polyimide precursor is cyclized to become a resin such as a polyimide.
  • the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.
  • the heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of the base generated from the base generator through heating.
  • the heating step is preferably performed at a temperature rise rate of 1 to 12° C./min from the starting temperature to the maximum heating temperature.
  • the temperature rise rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min.
  • the temperature is increased from the starting temperature to the maximum heating temperature at a rate of preferably 1 to 8° C./sec, more preferably 2 to 7° C./sec, and even more preferably 3 to 6° C./sec.
  • the temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C.
  • the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature begins.
  • the resin composition of the present invention when applied to a substrate and then dried, it is the temperature of the film (layer) after drying, and it is preferable to raise the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.
  • the heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
  • the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher.
  • the upper limit of the heating temperature is preferably 350° C. or less, more preferably 250° C. or less, and even more preferably 240° C. or less.
  • Heating may be performed stepwise. For example, a process may be performed in which the temperature is increased from 25°C to 120°C at 3°C/min, held at 120°C for 60 minutes, increased from 120°C to 180°C at 2°C/min, and held at 180°C for 120 minutes. It is also preferable to perform the process while irradiating ultraviolet rays as described in U.S. Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment process is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps, for example, a first pretreatment process may be performed in the range of 100 to 150°C, and then a second pretreatment process may be performed in the range of 150 to 200°C. Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C./min.
  • the heating step is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by performing the heating step under reduced pressure, etc.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
  • the heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.
  • the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step.
  • the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
  • the post-development exposure step for example, a reaction in which cyclization of a polyimide precursor or the like proceeds due to exposure of a photobase generator to light, or a reaction in which elimination of an acid-decomposable group proceeds due to exposure of a photoacid generator to light, can be promoted.
  • the post-development exposure step it is sufficient that at least a part of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed.
  • the exposure dose in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , and more preferably 100 to 15,000 mJ/cm 2 , calculated as exposure energy at a wavelength to which the photosensitive compound has sensitivity.
  • the post-development exposure step can be carried out, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.
  • the pattern obtained by the development step may be subjected to a metal layer forming step in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the development step (preferably subjected to at least one of a heating step and a post-development exposure step).
  • the metal layer can be made of any existing metal type without any particular limitations, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.
  • the method for forming the metal layer is not particularly limited, and existing methods can be applied.
  • the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used.
  • photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations of these methods are possible.
  • examples of the method include a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating.
  • a preferred embodiment of plating is electrolytic plating using a copper sulfate or copper cyanide plating solution.
  • the thickness of the metal layer at its thickest point is preferably 0.01 to 50 ⁇ m, and more preferably 1 to 10 ⁇ m.
  • 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 having 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 be compositions having 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.
  • the resin was reslurried in 1 L of water, filtered, and then reslurried again in 1 L of methanol, filtered, and dried at 40 ° C. under reduced pressure for 10 hours.
  • the resin dried above was dissolved in 300 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added, and the mixture was stirred for 4 hours.
  • the ion exchange resin was removed by filtration, and then the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes.
  • the polyimide resin was collected by filtration and dried at 45° C. under reduced pressure for 1 day to obtain polyimide (SP-1).
  • polyimide (SP-1) The weight average molecular weight of the obtained polyimide (SP-1) was 23,700 and the number average molecular weight was 8,900.
  • Polyimide (SP-1) is a resin having a repeating unit represented by the following formula SP-1.
  • the structure of the repeating unit was determined from 1 H-NMR spectrum. In the following structures, the subscripts in parentheses represent the molar ratio of each structure.
  • SP-2 to SP-6 Synthesis of Polyimides (SP-2 to SP-6)] SP-2 to SP-6 were synthesized in the same manner as SP-1, except that 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and hexadecylamine were appropriately changed so as to have the structures shown below.
  • Polyimides (SP-2) to (SP-6) are resins having repeating units represented by the following formulas SP-2 to SP-6, respectively. The structure of each repeating unit was determined from 1 H-NMR spectrum. In the structures below, the subscripts in parentheses indicate the molar ratio of each structure. The weight average molecular weight and number average molecular weight of these resins are shown in the table below.
  • the resin was reslurried in 1 L of water, filtered, and then reslurried again in 1 L of methanol, filtered, and dried under reduced pressure at 40° C. for 8 hours.
  • the resin dried above was dissolved in 300 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added, and the mixture was stirred for 4 hours.
  • the ion exchange resin was removed by filtration, and then the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes.
  • the polyimide resin was collected by filtration and dried at 45° C. under reduced pressure for 1 day to obtain polyimide resin (ST-1).
  • Polyimide (ST-1) is a resin having a repeating unit represented by the following formula ST-1.
  • the structure of the repeating unit was determined from 1 H-NMR spectrum. In the following structures, the subscripts in parentheses represent the molar ratio of each structure.
  • the polyimide precursor resin was precipitated in 4 L of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes.
  • the polyimide precursor resin was collected by filtration and dried at 45° C. under reduced pressure for 2 days to obtain a polyimide precursor (SA-1).
  • the weight average molecular weight of the obtained polyimide precursor (SA-1) was 24,600 and the number average molecular weight was 9,400.
  • the imidization rate of the polyimide precursor (SA-1) was 3% or less.
  • reaction solution was diluted with 600 mL of ethyl acetate (CH 3 COOEt), transferred to a separatory funnel, and washed in order with 300 mL of water, 300 mL of saturated sodium bicarbonate water, 300 mL of dilute hydrochloric acid, and saturated saline. After separation and washing, the mixture was dried over 30 g of magnesium sulfate, concentrated using an evaporator, and dried in vacuum to obtain 61.0 g of dinitro compound (A-1). It was confirmed to be dinitro compound (A-1) by NMR spectrum. The dinitro compound (A-1) was analyzed by 1 H-NMR. The results are shown below.
  • the polyimide precursor resin was then precipitated in 3 liters of water, and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes.
  • the polyimide precursor resin was obtained by filtration, stirred again in 3 liters of water for 30 minutes, and filtered again.
  • the obtained polyimide precursor resin was then dried at 45° C. under reduced pressure for 1 day.
  • the structure of the polyimide precursor (SA-2) is represented by the following formula (SA-2):
  • the imidization rate of the polyimide precursor (SA-2) was 3% or less.
  • SA-3 Synthesis of polyimide precursor (SA-3)
  • SA-3 Polyimide precursor (SA-3) was synthesized in the same manner as in the synthesis of polyimide precursor (SA-2).
  • the reaction solution was then cooled to 25°C, diluted with 200 g of tetrahydrofuran, and the reaction solution was dropped into a mixture of 2.0 L of methanol and 0.5 L of water, stirred for 15 minutes, and the polyimide resin was filtered.
  • the resin was reslurried in 1 L of water, filtered, and then reslurried again in 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 10 hours.
  • the resin dried above was dissolved in 300 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added, and the mixture was stirred for 4 hours.
  • polyimide resin (A-1) The weight average molecular weight of the obtained polyimide resin A-1 was 28,800, and the number average molecular weight was 10,900.
  • the obtained white solid was collected and vacuum-dried at a temperature of 40° C. to obtain 71.8 g of A-2.
  • the weight average molecular weight (Mw) of A-2 was 78,500, and the number average molecular weight (Mn) was 30,200. It was confirmed by 1 H-NMR spectrum that the structure of A-2 was mainly composed of the structure represented by the following formula (A-2): From the measurement result of 1 H-NMR, the introduction rate of the crosslinking group was 55%.
  • 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 of each component shown in the table is the amount (parts by mass) shown in the "Amount Added" column of each column in the table. The obtained resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter having a pore width of 0.5 ⁇ m. In the table, "-" indicates that the composition does not contain the corresponding component.
  • SP-1 to SP-23 SP-1 to SP-23 synthesized above correspond to the above-mentioned resin A and resin B.
  • ST-1 to ST-5 ST-1 to ST-5 and ST-1 to ST-15 synthesized above correspond to the above-mentioned resin A3 and resin C.
  • SA-1 to SA-3 SA-1 to SA-3 and SA-1 to SA-3 synthesized above correspond to the above-mentioned resin A2 and resin C.
  • A-1 to A-2 The above synthetic products (comparative examples)
  • B-1 1,12-dodecanediol dimethacrylate (melting point: 25°C or less)
  • B-2 1,9-nonanediol dimethacrylate (melting point: 25°C or lower)
  • B-3 1,10-decanediol dimethacrylate (melting point: 25°C or less)
  • B-4 SR-209 (manufactured by Sartomer, melting point: 25°C or less)
  • B-5 ADPH: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., melting point: 25°C or less)
  • OXE-01 IRGACURE OXE 01 (manufactured by BASF)
  • OXE-02 IRGACURE OXE 02 (manufactured by BASF)
  • OXE-03 IRGACURE OXE 03 (manufactured by BASF)
  • Irgcure 784 Irgacure 784 (manufactured by BASF) ⁇ CPI-310B (manufactured by San-Apro Co., Ltd.)
  • D-1 Benzoyl peroxide (Tokyo Chemical Industry Co., Ltd.)
  • F-1 to F-3 Compounds having the following structures
  • G-1 1,4-benzoquinone
  • G-2 4-methoxyphenol
  • G-3 1,4-dihydroxybenzene
  • G-4 Compound of the following structure
  • G-5 2-nitroso-1-naphthol (Tokyo Chemical Industry Co., Ltd.)
  • the resin compositions used in each Example and Comparative Example were applied in layers by spin coating to the surface of the copper thin layer of the resin substrate on which the copper thin layer was formed, and then dried at 100°C for 5 minutes to form a resin composition layer having a film thickness of 5 ⁇ m after film formation.
  • the layer was then developed for 15 seconds with the developer described in the "Development method (developer)" column of the table, rinsed with PGMEA for 30 seconds, and further heated at a temperature increase rate of 10 °C/min under a nitrogen atmosphere, and heated at the temperature and curing time described in the "Curing conditions” column of the table to obtain a hole pattern having a diameter of 3 to 20 ⁇ m.
  • the formed hole pattern was evaluated according to the following evaluation criteria. The evaluation results are shown in the "resolution” column of the table. Images were analyzed using a SEM (scanning electron microscope), and when the residual film rate at the bottom of the hole was 1% or less, it was judged that resolution was possible.
  • a hole pattern with a diameter of up to 3 ⁇ m was resolvable.
  • B A hole pattern with a diameter of 5 ⁇ m could be resolved, but a hole pattern with a diameter of 3 ⁇ m could not be resolved.
  • C A hole pattern with a diameter of 7 ⁇ m could be resolved, but a hole pattern with a diameter of 5 ⁇ m could not be resolved.
  • D A hole pattern with a diameter of 10 ⁇ m could be resolved, but a hole pattern with a diameter of 7 ⁇ m could not be resolved.
  • E A hole pattern with a diameter of 10 ⁇ m could not be resolved.
  • the resin composition or the comparative composition was applied by spin coating onto a silicon wafer having a 1:1 L/S (line and space) pattern with a height of 15 ⁇ m and a width of 20 ⁇ m and a copper wiring with a taper angle of 85 degrees, to form a resin composition layer.
  • the silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate to obtain a resin composition layer on the silicon wafer, the thickness of which was a uniform thickness of about 20 ⁇ m in the space portion of the copper wiring.
  • the resin composition layer was heated in a nitrogen atmosphere at a temperature increase rate of 10° C./min at the temperature shown in the “Temperature” column under “Curing conditions” in the table for the time shown in the “Curing time” column under “Curing conditions” in the table to obtain a cured product.
  • the resulting cured product was measured for depression X ( ⁇ m) in the space of the copper wiring using a scanning electron microscope (S-4800) (manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following criteria. The evaluation results are shown in the "Flatness" column in the table.
  • a schematic cross-sectional view of a state in which a cured product is formed on a silicon wafer on which copper wiring is formed is shown in Fig. 1.
  • the silicon wafer 16 in Fig. 1 has copper wiring 14, and a cured product 12 is formed on the silicon wafer 16.
  • the cured product 12 in an area on the silicon wafer 16 where the copper wiring 14 is not formed has a depression 18 of X ⁇ m.
  • the width W of the space part of the copper wiring is 20 ⁇ m, and the taper angle ⁇ of the copper wiring is 85°.
  • the depression 18 is observed, for example, as the difference between the total thickness h1 of the cured product and the copper wiring at the center position of the copper wiring and the thickness h2 of the cured product at the center position of the space part of the copper wiring.
  • the smaller the depression 18 (X) the better the flatness, and thus it is preferable.
  • the evaluation is A, B, or C.
  • Each resin composition or comparative composition prepared in each Example and Comparative Example was applied to a 12-inch silicon wafer by spin coating to form a resin composition layer.
  • the silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a resin composition layer of a uniform thickness of 15 ⁇ m on the silicon wafer.
  • the resin composition layer on the silicon wafer was exposed to light with an exposure energy of 500 mJ/cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed resin composition layer (resin layer) was heated at a heating rate of 10° C./min under a nitrogen atmosphere, and heated at the temperature described in the “Temperature” column of the “Curing Conditions” in the table for the time described in the “Curing Time” column of the “Curing Conditions” in the table to obtain a cured layer (resin layer) of the resin composition layer.
  • the cured layer (resin film) after curing was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and the cured film was peeled off from the silicon wafer.
  • the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the film sample at 28 GHz were measured by a resonator perturbation method.
  • Dielectric constant (Dk) A: The relative dielectric constant (Dk) of the film was less than 2.9.
  • B The relative dielectric constant (Dk) of the film was 2.9 to less than 3.0.
  • C The relative dielectric constant (Dk) of the film was 3.0 to less than 3.2.
  • D The film had a relative dielectric constant (Dk) of 3.2 or more.
  • 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, respectively, 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 thickness of 5 ⁇ m and a uniform thickness on the copper substrate.
  • the resin composition layer or comparative composition layer on the copper substrate was exposed to i-rays using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/cm 2 using a photomask having a square unmasked portion of 100 ⁇ m square, and then developed for 60 seconds with the developer described in the “Development method (developer)” column in the table, and rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a square resin layer of 100 ⁇ m square.
  • PGMEA propylene glycol monomethyl ether acetate
  • the resin was heated in a heating oven under a nitrogen atmosphere at the temperature described in the "Temperature” column of the “Curing conditions” in the table for the time described in the “Curing time” column of the “Curing conditions” in the table to form a resin layer (pattern).
  • the resin composition layer and the copper substrate were left in a tank at a temperature of 100° C. and a humidity of 100% RH for 100 hours.
  • a cross-sectional SEM (scanning electron microscope) measurement was performed to evaluate the void area ratio between the copper substrate and the resin layer. The void area ratio was calculated by the following formula.
  • Void area ratio (%) (area of voids observed by SEM measurement)/(total area of resin layer) ⁇ 100 From the obtained void area ratio, evaluation was performed according to the following evaluation criteria. The smaller the void area ratio, the better the PCT (wet heat) resistance of the cured film is, and the less likely voids are to occur between the metal layer and the cured product even after a long period of time has passed.
  • D The void area ratio exceeded 1%.
  • the above results show that the cured product obtained from the resin composition according to the present invention has a low dielectric tangent.
  • Example 101 The resin composition used in Example 1 was applied in a layer form by spin coating to the surface of the copper thin layer of the resin substrate on which the copper thin layer was formed, and dried at 100°C for 4 minutes to form a resin composition layer with a thickness of 20 ⁇ m, and then exposed using a stepper (Nikon Corporation, NSR1505 i6). 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 exposure, the substrate was heated at 100°C for 4 minutes. After the heating, the substrate was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
  • a stepper Nakon Corporation, NSR1505 i6
  • 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 exposure, the substrate was heated at 100°C for 4
  • 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 3 hours to form an interlayer insulating film for a rewiring layer.
  • This interlayer insulating film for a rewiring layer had excellent insulating properties. Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for redistribution layers, it was confirmed that they operated without any problems.
  • Hardened material 14
  • Copper wiring 16
  • Silicon wafer 18 Recess H Height of copper wiring h1 Total thickness of hardened material and copper wiring at the center position of copper wiring h2 Thickness of hardened material at the center position of space part of copper wiring W Width of space part of copper wiring ⁇ Taper angle of copper wiring

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Abstract

La présente invention concerne une composition de résine comprenant : une résine A qui est un polyimide et qui contient une structure représentée par la formule (A-1) en une quantité de 0,20 à 5 mmol/g par rapport à la masse de la résine A ; un initiateur de polymérisation ; et un composé polymérisable. La présente invention concerne également un produit durci obtenu par durcissement de la composition, un corps stratifié comprenant le produit durci, un procédé de production du produit durci, un procédé de production du corps stratifié, un procédé de production d'un dispositif semiconducteur qui comprend le procédé de production du produit durci, et un dispositif semiconducteur comprenant le produit durci. Dans la formule (A-1), LA1 représente une liaison simple ou un groupe de liaison de valence m+1, chaque RR1 représente indépendamment un atome d'hydrogène ou un groupe organique, deux RR1 peuvent être couplés l'un à l'autre, m représente un nombre entier supérieur ou égal à 1, et * représente un site de liaison avec un autre atome.
PCT/JP2024/022527 2023-06-22 2024-06-21 Composition de résine, produit durci, corps stratifié, procédé de production d'un produit durci, procédé de production d'un corps stratifié, procédé de production d'un dispositif semiconducteur et dispositif semiconducteur Pending WO2024262604A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6026033A (ja) * 1983-07-01 1985-02-08 エヌ・ベ−・フイリツプス・フル−イランペンフアブリケン 感光性ポリアミド酸誘導体およびこれを用いて基体上にポリイミドパタ−ンを形成する方法
JPS61296032A (ja) * 1985-06-25 1986-12-26 Asahi Chem Ind Co Ltd 硬化性ポリイミド
JPH11282160A (ja) * 1998-03-31 1999-10-15 Hitachi Chemical Dupont Microsystems Ltd 感光性ポリイミド組成物、これを用いたパターン製造法及び半導体装置
CN101463115A (zh) * 2008-12-30 2009-06-24 华烁科技股份有限公司 一种无胶挠性单面覆铜板用热固性聚酰亚胺树脂及其应用
JP2013083958A (ja) * 2011-09-26 2013-05-09 Nippon Steel & Sumikin Chemical Co Ltd 感光性樹脂組成物、それを用いた硬化物及び半導体素子
JP2020033471A (ja) * 2018-08-30 2020-03-05 三菱瓦斯化学株式会社 樹脂組成物、樹脂シート、多層プリント配線板及び半導体装置
US20200283579A1 (en) * 2019-03-05 2020-09-10 Promerus, Llc Reactive end group containing polyimides and polyamic acids and photosensitive compositions thereof
WO2020203834A1 (fr) * 2019-04-02 2020-10-08 日本化薬株式会社 Composé de bismaléimide, composition de résine photosensible mettant en œuvre celui-ci, objet durci associé, et élément semi-conducteur

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6026033A (ja) * 1983-07-01 1985-02-08 エヌ・ベ−・フイリツプス・フル−イランペンフアブリケン 感光性ポリアミド酸誘導体およびこれを用いて基体上にポリイミドパタ−ンを形成する方法
JPS61296032A (ja) * 1985-06-25 1986-12-26 Asahi Chem Ind Co Ltd 硬化性ポリイミド
JPH11282160A (ja) * 1998-03-31 1999-10-15 Hitachi Chemical Dupont Microsystems Ltd 感光性ポリイミド組成物、これを用いたパターン製造法及び半導体装置
CN101463115A (zh) * 2008-12-30 2009-06-24 华烁科技股份有限公司 一种无胶挠性单面覆铜板用热固性聚酰亚胺树脂及其应用
JP2013083958A (ja) * 2011-09-26 2013-05-09 Nippon Steel & Sumikin Chemical Co Ltd 感光性樹脂組成物、それを用いた硬化物及び半導体素子
JP2020033471A (ja) * 2018-08-30 2020-03-05 三菱瓦斯化学株式会社 樹脂組成物、樹脂シート、多層プリント配線板及び半導体装置
US20200283579A1 (en) * 2019-03-05 2020-09-10 Promerus, Llc Reactive end group containing polyimides and polyamic acids and photosensitive compositions thereof
WO2020203834A1 (fr) * 2019-04-02 2020-10-08 日本化薬株式会社 Composé de bismaléimide, composition de résine photosensible mettant en œuvre celui-ci, objet durci associé, et élément semi-conducteur

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