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WO2025023280A1 - Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur - Google Patents

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

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Publication number
WO2025023280A1
WO2025023280A1 PCT/JP2024/026489 JP2024026489W WO2025023280A1 WO 2025023280 A1 WO2025023280 A1 WO 2025023280A1 JP 2024026489 W JP2024026489 W JP 2024026489W WO 2025023280 A1 WO2025023280 A1 WO 2025023280A1
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WIPO (PCT)
Prior art keywords
group
resin composition
formula
cured product
resin
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Application number
PCT/JP2024/026489
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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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Publication of WO2025023280A1 publication Critical patent/WO2025023280A1/fr
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Classifications

    • 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
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
    • 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
    • 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
    • G03F7/20—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.
  • resin materials produced from resin compositions containing resins are being used in various fields.
  • heterocycle-containing polymers such as polyimides are applied to various applications due to their excellent heat resistance and insulating properties.
  • the applications include, but are not limited to, materials for insulating films and sealing materials, or protective films for semiconductor devices for mounting. They are also used as base films and coverlays for flexible substrates.
  • a heterocycle-containing polymer such as a polyimide is used in the form of a resin composition containing the heterocycle-containing polymer.
  • a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate.
  • the resin composition can be applied by a known coating method, etc., it can be said to have excellent adaptability in manufacturing, for example, high degree of freedom in designing the shape, size, application position, etc. of the applied resin composition when applied.
  • the industrial application development of the above-mentioned resin composition is expected to continue.
  • Patent Document 1 describes a photosensitive resin composition for forming an insulating portion in a wiring layer that includes an insulating portion having an opening and wiring disposed inside the opening, the photosensitive resin composition containing a structural unit based on a reaction product of a tetracarboxylic dianhydride having a specific structure and an aromatic diamine, a polyimide having a photopolymerizable carbon-carbon double bond, and a photopolymerization initiator.
  • the present invention aims to provide a resin composition that gives 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.
  • ⁇ 1> At least one resin selected from the group consisting of polyimide and polybenzoxazole; a polymerizable compound having an allyl group, an aromatic group, and an aliphatic saturated hydrocarbon group having 4 or more carbon atoms;
  • a resin composition comprising: ⁇ 2> The resin composition according to ⁇ 1>, wherein the polymerizable compound further has a (meth)acryloxy group.
  • ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the polymerizable compound includes a compound represented by the following formula (B-1):
  • X1 's each independently represent a single bond or a divalent linking group
  • Y1 's each independently represent an alkylene group having 6 or more carbon atoms
  • A1 's each independently represent a (meth)acryloxy group
  • W1 's each independently represent a hydrogen atom or a monovalent organic group
  • n's each independently represent an integer of 1 or more
  • m's each independently represent an integer of 1 or more, with the proviso that when n is 2, W1 's each independently represent a single bond or a linking group.
  • ⁇ 5> The resin composition according to ⁇ 4>, in which n in the formula (B-1) is an integer of 2 or more.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the resin 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
  • each R1 independently represents a group containing a polymerizable group
  • m and n represent integers of 0 to 4, provided that m+n is an integer of 1 or more.
  • R 1 in the formula (1-1) is a group represented by formula (R-1).
  • L1 represents a linking group having a valence of a1+1
  • A1 represents a maleimide group, a (meth)acryloxy group or a vinylphenyl group
  • a1 represents an integer of 1 or more
  • * represents a bonding site with X1 or Y1 in formula (1-1).
  • X 1 and Y 1 in 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.
  • ⁇ 10> The resin composition according to any one of ⁇ 1> to ⁇ 9>, wherein the resin has a linear or branched alkyl group having 6 or more carbon atoms.
  • ⁇ 11> The resin composition according to any one of ⁇ 1> to ⁇ 10>, in which the content of the polymerizable compound is 5 to 40 parts by mass, based on 100 parts by mass of the resin.
  • ⁇ 12> The resin composition according to any one of ⁇ 1> to ⁇ 11>, further comprising a polymerizable compound other than the above-mentioned polymerizable compound.
  • ⁇ 13> The resin composition according to any one of ⁇ 1> to ⁇ 12>, wherein the polymerizable compound has a ClogP value of 4 or more.
  • ⁇ 14> The resin composition according to any one of ⁇ 1> to ⁇ 13>, further comprising at least one resin selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor.
  • ⁇ 15> The resin composition according to any one of ⁇ 1> to ⁇ 14>, which is used for forming an interlayer insulating film for a redistribution layer.
  • ⁇ 16> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 15>.
  • ⁇ 17> The cured product according to ⁇ 16>, having a water content of 0.2 mass% or less based on the total mass of the cured product.
  • ⁇ 18> A laminate comprising two or more layers made of the cured product according to ⁇ 16> or ⁇ 17>, and a metal layer between any two adjacent layers made of the cured product.
  • a method for producing a cured product comprising a film-forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 15> onto a substrate to form a film.
  • the method for producing a cured product according to ⁇ 19> 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.
  • ⁇ 21> A method for producing a cured product according to ⁇ 19> or ⁇ 20>, comprising a heating step of heating the film at 50 to 450° C.
  • ⁇ 22> A method for producing a laminate, comprising the method for producing a cured product according to any one of ⁇ 19> to ⁇ 21>.
  • ⁇ 23> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of ⁇ 19> to ⁇ 21>.
  • ⁇ 24> A semiconductor device comprising the cured product according to ⁇ 16> or ⁇ 17>.
  • a compound represented by formula (B-1) In formula (B-1), X1 's each independently represent a single bond or a divalent linking group, Y1 's each independently represent an alkylene group having 6 or more carbon atoms, A1 's each independently represent a (meth)acryloxy group, W1 's each independently represent a hydrogen atom or a monovalent organic group, n's each independently represent an integer of 1 or more, and m's each independently represent an integer of 1 or more, with the proviso that when n is 2, W1 's each independently represent a single bond or a linking group.
  • ⁇ 26> The compound according to ⁇ 25>, having a polymerizable group value of 5.0 mmol/g or more.
  • ⁇ 27> The compound according to ⁇ 25> or ⁇ 26>, having a ClogP value of 4 or more.
  • the present invention provides a resin composition that gives 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.
  • 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 of the present invention (hereinafter also simply referred to as the "resin composition”) contains at least one resin selected from the group consisting of polyimide and polybenzoxazole, a polymerizable compound having an allyl group, an aromatic group, and an aliphatic saturated hydrocarbon group having 4 or more carbon atoms (hereinafter also referred to as the "specific polymerizable compound”), and a polymerization initiator.
  • at least one resin selected from the group consisting of polyimide and polybenzoxazole will also be referred to simply as a "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.
  • the inventors conducted intensive research and found that the dielectric tangent can be reduced by using a polymerizable compound (specific polymerizable compound) having an allyl group, an aromatic group, and an aliphatic saturated hydrocarbon group having 4 or more carbon atoms.
  • a polymerizable compound specifically polymerizable compound
  • the allyl group has a low dielectric tangent of the polymerized structure
  • the aromatic group has high compatibility with resins
  • the aliphatic saturated hydrocarbon group having 4 or more carbon atoms is considered to be highly hydrophobic.
  • the film when the film is designed to have a total of a plurality of allyl groups and other polymerizable groups and a highly hydrophobic aliphatic saturated hydrocarbon group having 4 or more carbon atoms, the film is less susceptible to water penetration and oxidation of the metal layer by water is less likely to occur due to the two points of increased crosslink density and hydrophobicity of the film, and therefore the insulation reliability is also considered to be improved.
  • excellent adhesion between the cured product and the metal layer under high temperature and high humidity conditions is also referred to as "excellent insulation reliability".
  • Patent Document 1 does not describe a resin composition that contains a compound that corresponds to the specific polymerizable compound.
  • the resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide and polybenzoxazole.
  • the specific resin is preferably a polyimide.
  • the specific resin preferably has a repeating unit represented by the formula (1-1) described below.
  • polyimide refers to a resin having a repeating unit containing an imide structure in the molecular chain, and is preferably a resin having a repeating unit containing an imide ring structure in the molecular chain.
  • the polyimide is a linear resin, 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 imide ring structure refers to a ring structure containing, as ring members, two carbon atoms and all of the nitrogen atoms in the imide structure.
  • the imide ring structure is preferably a five-membered ring.
  • the polyimide may be a so-called polyamideimide having an amide structure in the molecular chain in addition to the imide structure.
  • # represents a bonding site with another structure, preferably a bonding site with a hydrogen atom or a carbon atom, more preferably a bonding site with a hydrogen atom.
  • polybenzoxazole refers to a resin having a repeating unit containing a benzoxazole structure in the molecular chain.
  • the specific resin preferably has a repeating unit represented by formula (X) described below.
  • the polybenzoxazole is a straight-chain resin, the polybenzoxazole is preferably a resin having a repeating unit containing a benzoxazole structure in the main chain.
  • the benzoxazole structure refers to a structure represented by the following formula (PBO-1): In formula (PBO-1), * represents a bonding site to other structures.
  • the specific resin preferably has a polymerizable group.
  • the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, and a benzoxazolyl group, and the group having an ethylenically unsaturated bond is preferred.
  • the group having 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.
  • (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, and maleimide group are preferred, and from the viewpoint of reactivity, (meth)acryloyl group is more preferred. Also, from the viewpoint of lowering the dielectric loss tangent, vinylphenyl group and maleimide group are preferred.
  • the content of polymerizable groups relative to the total mass of the specific resin is preferably 0.2 to 5.0 mmol/g, more preferably 0.25 to 4.0 mmol/g, and even more preferably 0.3 to 3.0 mmol/g.
  • the polymerizable group value is defined as the molar amount of polymerizable groups contained in 1 mole of a compound/number average molecular weight of the compound.
  • the specific resin preferably has a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms (hereinafter also referred to as "specific substituent A").
  • the specific substituent A is preferably a linear or branched alkyl group having 6 or more carbon atoms, and more preferably a linear alkyl group having 6 or more carbon atoms.
  • the specific resin preferably has a specific substituent A at the main chain terminal.
  • 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 specific resin preferably contains a repeating unit represented by 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
  • each R1 independently represents a group containing a polymerizable group
  • m and n represent integers of 0 to 4, provided that m+n is an integer of 1 or more.
  • -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 obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulae (V-1) to (V-9), and more preferably represents an organic group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulae (V-1) to (V-4).
  • X 1 is 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-9), the chemical resistance and flatness of the cured product are improved.
  • X1 is 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), it is possible to obtain effects such as suppressing the generation of development residues, lowering the dielectric constant of the cured product, and reducing the thermal expansion coefficient.
  • 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 1 and X5 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
  • 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.
  • R X5 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.
  • 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-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.
  • X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-7)
  • X 1 is preferably a group represented by the following formula (V-7-1).
  • * represents a bonding site with the four carbonyl groups to which X 1 in formula (1-1) is bonded.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-8)
  • X1 is preferably a group represented by the following formula (V-8-1).
  • * represents a bonding site with the four carbonyl groups to which X1 in formula (1-1) is bonded.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as a hydrocarbon group.
  • X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-9)
  • X1 is preferably a group represented by the following formula (V-9-1).
  • * represents a bonding site with the four carbonyl groups to which X1 in formula (1-1) is bonded.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • 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, it is preferable that X2 does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that X2 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 has 4 or more carbon atoms, preferably 4 to 50 carbon atoms, and more preferably 4 to 40 carbon atoms.
  • 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 formulas (V-1) to (V-9).
  • V-1 formula 1-1
  • Y 1 is 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-9)
  • the chemical resistance and flatness of the cured product are improved.
  • 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.
  • Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-5)
  • Y1 is preferably a group represented by the following formula (V-5-2).
  • * represents the bonding site with the two nitrogen atoms to which Y1 in formula (1-1) is bonded.
  • the hydrogen atoms in the following structure 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 the structure represented by formula (V-6), Y1 is preferably a group represented by the following formula (V-6-2).
  • * represents the bonding site with the two nitrogen atoms to which Y1 in formula (1-1) is bonded.
  • the hydrogen atoms in the following structure 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 the structure represented by formula (V-7)
  • Y1 is preferably a group represented by the following formula (V-7-2).
  • * represents the bonding site with the two nitrogen atoms to which Y1 in formula (1-1) is bonded.
  • the hydrogen atoms in the following structure 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 the structure represented by formula (V-8)
  • Y1 is preferably a group represented by the following formula (V-8-2).
  • * represents the bonding site with the two nitrogen atoms to which Y1 is bonded in formula (1-1).
  • the hydrogen atoms in the following structure 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 the structure represented by formula (V-9)
  • Y1 is preferably a group represented by the following formula (V-9-2).
  • * represents the bonding site with the two nitrogen atoms to which Y1 is bonded in formula (1-1).
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • 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.
  • -R 1 - R 1 in formula (1-1) is a group containing a polymerizable group. Preferred embodiments of the polymerizable group are as described above.
  • R 1 in formula (1-1) is preferably a group represented by formula (R-1).
  • L1 represents a linking group having a valence of a1+1
  • A1 represents a maleimide group, a (meth)acryloxy group or a vinylphenyl group
  • a1 represents an integer of 1 or more
  • * represents a bonding site with X1 or Y1 in formula (1-1).
  • L1 is preferably a group represented by the following formula (L-2).
  • R N represents a hydrogen atom or a monovalent organic group, when a1 is 1, Lx represents a single bond or a divalent linking group, when a1 is 2 or more, Lx represents an a1+1 valent linking group, a1 represents an integer of 1 or more, * represents a bonding site to another structure in X1 or Y1 in formula (1-1), and # represents a bonding site to A1 in formula (R-1).
  • R N is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a phenyl group, and still more preferably a hydrogen atom.
  • Lx is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group.
  • Lx is preferably a hydrocarbon group, a heterocyclic group, or a group represented by a combination thereof, more preferably a saturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group having 3 to 15 carbon atoms.
  • a1 has the same meaning as a1 in formula (R-1).
  • a 1 represents a maleimide group, a (meth)acryloxy group or a vinylphenyl group, and preferably represents a maleimide group or a vinylphenyl group.
  • a 1 in formula (R-1) is a vinylphenyl group and L 1 is a group represented by formula (L-2-1).
  • L and X2 represent a hydrocarbon group, and a1 represents an integer of 1 or more.
  • L and X2 are preferably a saturated aliphatic hydrocarbon group.
  • L X2 is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, still more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group.
  • a1 has the same meaning as a1 in formula (R-1).
  • a 1 in formula (R-1) is a maleimide group
  • L 1 is a group represented by formula (L-2)
  • L X is an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms.
  • 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 containing the above-mentioned heteroatom. Furthermore, 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 any of a straight-chain, branched-chain, or cyclic structure, or a structure represented by a combination thereof.
  • 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.
  • a1 is preferably an integer of 1 to 4, and more preferably an integer of 1 to 2.
  • an embodiment in which a1 is 1 is also one of the preferred embodiments of the present invention.
  • the number of ester bonds contained in formula (R-1) is preferably 1 or 0.
  • n is preferably 1 or 2, and more preferably 2.
  • 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.
  • R 131 include groups described in paragraphs 0042 to 0053 of JP-A No. 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 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 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 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 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 imidization rate of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoints of the film strength, insulating properties, 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.
  • the lower limit of the content is not particularly limited, but can be, for example, 0.5 mmol/g or more.
  • the imidization rate is measured, for example, by the following method.
  • the infrared absorption spectrum of the specific 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 specific resin is also preferably a compound containing a repeating unit represented by the following formula (X), and more preferably a compound represented by the following formula (X) having a polymerizable group or a specific substituent A. Preferred aspects of the polymerizable group are as described above.
  • R 133 represents a divalent organic group
  • R 134 represents a tetravalent organic group.
  • the specific substituent A may be located at at least one of R 133 and R 134 , or may be located at the end of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2).
  • the polymerizable group may be located at at least one of R 133 and R 134 , or may be located at the end of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2).
  • R 137 is a specific substituent A or a polymerizable group, and the others are substituents, and the other groups are the same as defined in formula (X).
  • R 133 represents a divalent organic group.
  • the divalent organic group may be an aliphatic group or an aromatic group.
  • R 133 may be the same group as R 131 in the following formula (R133-1) or formula (4).
  • Y 1 represents an organic group having 4 or more carbon atoms
  • each R 1 independently represents a structure represented by formula (R-1) above
  • n represents an integer of 1 or more
  • * represents a bonding site to another structure.
  • preferred embodiments of Y 1 , R 1 and n are the same as the preferred embodiments of Y 1 , R 1 and n shown in formula (1-1) above.
  • R 134 represents a tetravalent organic group.
  • the tetravalent organic group may be an aliphatic group or an aromatic group.
  • R 134 may be the same group as R 132 in the following formula (R134-1) or formula (4).
  • X1 represents an organic group having 4 or more carbon atoms, each R1 independently represents a structure represented by formula (R-1) above, m represents an integer of 0 to 4 or more, and * represents a bonding site to another structure.
  • preferred embodiments of X 1 , R 1 and m are the same as the preferred embodiments of X 1 , R 1 and m shown in formula (1-1) above.
  • the oxazolization rate of polybenzoxazole is preferably 85% or more, more preferably 90% or more.
  • the upper limit is not particularly limited, and may be 100%.
  • the oxazolization rate of 85% or more the film shrinkage due to ring closure that occurs when oxazolized by heating is reduced, and the occurrence of warpage can be more effectively suppressed.
  • the oxazole ratio is measured, for example, by the following method. The infrared absorption spectrum of the polybenzoxazole is measured, and the peak intensity Q1 at about 1650 cm ⁇ 1 , which is an absorption peak derived from the amide structure of the precursor, is determined.
  • the peak intensity Q1 is normalized by the absorption intensity of the aromatic ring observed at about 1490 cm ⁇ 1 .
  • the infrared absorption spectrum is measured again, and the peak intensity Q2 at about 1650 cm ⁇ 1 is determined and normalized by the absorption intensity of the aromatic ring observed at about 1490 cm ⁇ 1 .
  • the polybenzoxazole may contain repeating units of the above formula (X) having the same combination of R 133 and R 134 , or may contain repeating units of the above formula (X) having two or more different combinations of R 133 and R 134.
  • the polybenzoxazole may also contain other types of repeating units in addition to the repeating units of the above formula (X).
  • the weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more types of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one type of polybenzoxazole is in the above range.
  • the number average molecular weight (Mn) of the polybenzoxazole is preferably from 7,200 to 14,000, more preferably from 8,000 to 12,000, and even more preferably from 9,200 to 11,200.
  • the molecular weight dispersity of the polybenzoxazole is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more.
  • the upper limit of the molecular weight dispersity of the polybenzoxazole is not particularly specified, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.
  • the weight average molecular weight, number average molecular weight, and dispersity of at least one polybenzoxazole 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 polybenzoxazoles as one resin are each within the above ranges.
  • the specific resin can be synthesized, for example, by the method described in paragraphs 0134 to 0136 of WO 2022/145355 or by reference to this method. The above description is incorporated herein. In addition, it may be synthesized by reference to other known methods.
  • the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition.
  • the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition.
  • the resin composition of the present invention may contain only one 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 in the above range.
  • the resin composition of the present invention contains at least two types of resins.
  • the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resins described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins.
  • an amide structure or imide structure (preferably an imide structure) is formed between the resins, and the molecular weight of the resin increases, making it possible to obtain a cured product with excellent chemical resistance, etc.
  • the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, simply referred to as "another resin").
  • the other resins include polyimide precursors, polybenzoxazole precursors, phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
  • a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
  • a (meth)acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizable group value for example, the molar amount of polymerizable groups per 1 g of resin is 1 ⁇ 10 ⁇ 3 mol/g or more
  • the coatability of the resin composition and the solvent resistance of the pattern (cured product) can be improved.
  • the resin composition of the present invention preferably further contains at least one resin selected from the group consisting of polyimide precursors and polybenzoxazole precursors, and more preferably further contains a polyimide precursor.
  • Preferred embodiments of these resins include the compounds described in paragraphs 0017 to 0044, 0073 to 0095, and 0104 to 0119 of WO 2022/145355 (in the present invention, this polyamideimide precursor is also included in the polyimide precursor). The above descriptions are incorporated herein.
  • the polyimide precursor is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2).
  • A1 and A2 each independently represent an oxygen atom or -NRz-
  • R111 represents a divalent organic group
  • R115 represents a tetravalent organic group
  • R113 and R114 each independently represent a hydrogen atom or a monovalent organic group
  • Rz represents a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 each independently represent an oxygen atom or —NR z —, and preferably an oxygen atom.
  • Rz represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.
  • R 111 in formula (2) is preferably a group containing a structure obtained by removing two or more hydrogen atoms from any of the structures represented by formulae (V-1) to (V-4) above. Preferred embodiments of the group containing a structure obtained by removing two or more hydrogen atoms from any of the structures represented by formulae (V-1) to (V-4) are as described above as preferred embodiments of Y 1 .
  • R 115 in formula (2) is preferably a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-4) above.
  • Preferred embodiments of the group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-4) are as described above as preferred embodiments of X 1 .
  • R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
  • the polymerizable group is a group capable of crosslinking by the action of heat, radicals, etc., and is preferably a radical polymerizable group.
  • the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
  • a group having an ethylenically unsaturated bond is preferable.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.
  • R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
  • * represents a bonding site with another structure.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
  • R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CH 2 CH(OH)CH 2 -, and polyalkyleneoxy groups, of which alkylene groups such as ethylene group and propylene group, -CH 2 CH(OH)CH 2 -, cyclohexyl group, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy groups are even more preferred.
  • alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-but
  • the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating.
  • the number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent, when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.
  • the alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom.
  • the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.
  • the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.
  • the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiment of the number of repetitions of the ethyleneoxy group in these groups is as described above.
  • the polyimide precursor when R 113 is a hydrogen atom or when R 114 is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond.
  • a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.
  • the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition.
  • the content of the other resins is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, still more preferably 60 mass% or less, and even more preferably 50 mass% or less, relative to the total solid content of the resin composition.
  • the content of the other resin may be low.
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition.
  • the lower limit of the content is not particularly limited, and may be 0% by mass or more.
  • the resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.
  • the resin composition of the present invention contains a polymerizable compound (specific polymerizable compound) having an allyl group, an aromatic group, and an aliphatic saturated hydrocarbon group having 4 or more carbon atoms.
  • the allyl group means a group represented by CH 2 ⁇ CH—CH 2 —*. * represents a bonding site with another structure.
  • the * in the allyl group is preferably bonded to a carbon atom via a single bond without a linking group, and more preferably bonded to the aromatic group via a single bond without a linking group.
  • the number of allyl groups in the specific polymerizable compound is preferably 1 to 10, more preferably 1 to 4, and further preferably 1 or 2.
  • the aromatic group refers to a group obtained by removing one or more hydrogen atoms from an aromatic compound.
  • the aromatic compound may be either an aromatic hydrocarbon compound or a heteroaromatic compound, with aromatic hydrocarbon compounds being preferred.
  • aromatic hydrocarbon compound include benzene, biphenyl, naphthalene, anthracene, pyrene, and azulene, with benzene being preferred.
  • heteroatom in the heteroaromatic compound include a nitrogen atom, an oxygen atom, a sulfur atom, and a silicon atom, with a nitrogen atom being preferred.
  • heteroaromatic compound examples include pyrrole, pyrazole, triazole, tetrazole, furan, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyridazine, pyrimidine, pyrazine, indoline, indole, indazole, and benzimidazole.
  • the specific substituent B is preferably a linear or branched saturated aliphatic hydrocarbon group having 4 or more carbon atoms, and more preferably a linear saturated aliphatic hydrocarbon group having 4 or more carbon atoms.
  • the specific substituent B is preferably an alkyl group or an alkylene group, and more preferably an alkylene group.
  • the hydrogen atom in the specific substituent B is preferably unsubstituted or substituted with a halogen atom.
  • the halogen atom is preferably a fluorine atom.
  • an embodiment in which the hydrogen atom in the specific substituent B is unsubstituted is also one of the preferred embodiments of the present invention.
  • the specific substituent B preferably has 4 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
  • the specific polymerizable compound may further contain a polymerizable group other than the allyl group.
  • examples of other polymerizable groups include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, and a benzoxazolyl group, and the group having an ethylenically unsaturated bond is preferred.
  • examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyloxy group, a maleimide group, and a (meth)acrylamide group.
  • the specific polymerizable compound contains a (meth)acryloxy group as another polymerizable group.
  • the other polymerizable group is preferably bonded to the above-mentioned specific substituent B via a single bond without a linking group.
  • the number of other polymerizable groups in the specific polymerizable compound is preferably 1 to 10, more preferably 1 to 4, and further preferably 1 or 2.
  • the polymerizable group value of the specific polymerizable compound (i.e., the total molar content of allyl groups and the other polymerizable groups in 1 mole of the specific polymerizable compound/number average molecular weight of the specific polymerizable compound) is preferably 5.0 mmol/g or more, more preferably 5.5 mmol/g or more, and even more preferably 6.0 mmol/g or more.
  • the upper limit of the polymerizable group value is not particularly limited, but is preferably 15 mmol/g or less, and more preferably 10 mmol/g or less.
  • the allyl group value of the specific polymerizable compound i.e., the molar amount of allyl groups contained in 1 mole of the specific polymerizable compound/the number average molecular weight of the specific polymerizable compound
  • the allyl group value of the specific polymerizable compound is preferably 2.5 mmol/g or more, more preferably 2.7 to 20 mmol/g, and even more preferably 3.0 to 10 mmol/g.
  • the (meth)acryloxy group value of the specific polymerizable compound i.e., the molar amount of (meth)acryloxy groups contained in 1 mole of the specific polymerizable compound/the number average molecular weight of the specific polymerizable compound
  • the molar amount of (meth)acryloxy groups contained in 1 mole of the specific polymerizable compound/the number average molecular weight of the specific polymerizable compound is preferably 2.5 mmol/g or more, more preferably 2.7 to 20 mmol/g, and even more preferably 3.0 to 10 mmol/g.
  • the ClogP value of the specific polymerizable compound is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Further, the upper limit of the ClogP value is not particularly limited, but is preferably 15.0 or less.
  • 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. As a calculation method, it is known to use Crippen's fragmentation method (J. Chem. Inf.
  • 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 to calculate 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 specific polymerizable compound preferably contains a compound represented by the following formula (B-1).
  • X1 's each independently represent a single bond or a divalent linking group
  • Y1 's each independently represent an alkylene group having 6 or more carbon atoms
  • A1 's each independently represent a (meth)acryloxy group
  • W1 's each independently represent a hydrogen atom or a monovalent organic group
  • n's each independently represent an integer of 1 or more
  • m's each independently represent an integer of 1 or more, provided that when n is 2, W1 's each independently represent a single bond or a linking group.
  • RN represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.
  • each Y 1 independently represents an alkylene group having 6 or more carbon atoms, and more preferably a linear alkylene group having 6 or more carbon atoms.
  • the hydrogen atom in the alkylene group in Y1 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 alkylene group is unsubstituted is also one of the preferred embodiments of the present invention.
  • the alkylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
  • a 1 each independently represents a (meth)acryloxy group, of which an acryloxy group is preferred from the viewpoint of reactivity, and a methacryloxy group is preferred from the viewpoint of the glass transition temperature of the cured product.
  • n is preferably an integer of 2 or more, more preferably an integer of 2 to 4, and even more preferably 2.
  • An embodiment in which n is 1 is also one of the preferred embodiments of the present invention.
  • each m is preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • W 1 is preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, more preferably a hydrogen atom or an alkoxy group, and further preferably a hydrogen atom.
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the aryl group is preferably an aromatic hydrocarbon group, more preferably a phenyl group.
  • the above alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably a methoxy group.
  • the aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms, and more preferably a phenoxy group.
  • the preferred aspects of R N are as described above.
  • the hydrocarbon group is preferably an alkylene group, and the number of carbon atoms in the hydrocarbon group is preferably 1 to 20, and more preferably 2 to 10.
  • the preferred embodiments of R N are as described above.
  • the hydrocarbon group is preferably a saturated hydrocarbon group, and the number of carbon atoms in the hydrocarbon group is preferably 1 to 30, and more preferably 2 to 20.
  • the molecular weight of the specific polymerizable compound is preferably from 250 to 2,000, more preferably from 300 to 1,000, and even more preferably from 320 to 800.
  • the specific polymerizable compound can be synthesized, for example, by the method described in the Examples below. However, the synthesis method is not particularly limited as long as a structure corresponding to the specific polymerizable compound can be obtained.
  • Specific examples of the specific polymerizable compound include BS-1 to BS-10 described in the examples below, but the present invention is not limited to these.
  • the content of the specific polymerizable compound in the resin composition of the present invention is preferably 1 to 30 mass %, more preferably 5 to 25 mass %, and even more preferably 10 to 20 mass %, based on the total solid content of the resin composition.
  • the content of the specific polymerizable compound when the content of the specific resin is 100 parts by mass, is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 25 parts by mass.
  • the resin composition of the present invention further contains a polymerizable compound that does not fall under the category of the specific polymerizable compound (hereinafter, also referred to as "other polymerizable compound").
  • the melting point of the other 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 other polymerizable compounds it is preferable for the other polymerizable compounds to include a compound with a ClogP value of 3.0 or more, and it is even more preferable for the other polymerizable compounds to include 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 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.
  • polymerizable compounds include polymerizable compounds having a radical polymerizable group (radical crosslinking agent) or other crosslinking agents.
  • the resin composition of the present invention preferably contains a radical crosslinking agent.
  • the radical crosslinking agent is a compound having a radical polymerizable group.
  • the radical polymerizable group is preferably a group containing an ethylenically unsaturated bond.
  • Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
  • a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.
  • the radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds.
  • the radical crosslinking agent may have three or more ethylenically unsaturated bonds.
  • a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is even more preferable.
  • the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the above-mentioned compound having three or more ethylenically unsaturated bonds.
  • the molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
  • radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and 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.
  • radical crosslinking agent having an isocyanuric ring structure it is also preferable to use a radical crosslinking agent having an isocyanuric ring structure as the radical crosslinking agent.
  • a radical crosslinking agent having an isocyanuric ring structure a compound having two or three radical polymerizable groups is preferable, and a compound having three radical polymerizable groups is more preferable.
  • radical crosslinking agents having an isocyanuric ring structure include, but are not limited to, tris(2-acryloyloxyethyl) isocyanurate, tris(2-methacryloyloxyethyl) isocyanurate, EO (ethylene oxide)-modified isocyanuric acid diacrylate, EO-modified isocyanuric acid triacrylate, and compounds having the following structures: In the following structures, n each independently represents an integer of 1 to 20, and R represents a divalent linking group.
  • 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 a reaction to form a covalent bond with another compound in the composition or a reaction product thereof under the action of an acid or a base.
  • 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.
  • photopolymerization initiators that can be used include the compounds described in paragraphs 0113 to 0117 of JP 2023-058585 A. The disclosures 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 % relative to the total solid content of the resin composition, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %.
  • the sensitizer may be used alone or in combination of two or more types.
  • the resin composition of the present invention may contain a chain transfer agent.
  • the chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684.
  • Examples of the chain transfer agent include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization.
  • RAFT Reversible Addition Fragmentation Chain Transfer
  • 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 even more 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 in order 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 S1 represents a monovalent organic group
  • R 1 S2 represents a hydrogen atom, a hydroxyl group or an alkoxy group
  • n represents an integer of 0 to 2.
  • R S1 is preferably a structure containing a polymerizable group.
  • Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group.
  • R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
  • n represents an integer of 0 to 2, and is preferably 1.
  • n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and further preferably that n is 1 in at least two.
  • oligomer type compounds commercially available products can be used, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Aluminum-based adhesion promoter examples include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.
  • metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By making the content equal to or greater than the 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.
  • an ion trapping agent that captures anions such as halogen ions can also be used.
  • 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.
  • Organotitanium 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 11 is independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group
  • 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 a substituted or unsub
  • 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 film-like, rod-like, spherical, pellet-like, etc.
  • the cured product is preferably in the form of a film.
  • the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function.
  • the film thickness of the cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
  • the shrinkage percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
  • the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
  • the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
  • the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.
  • the moisture content of the cured product relative to the total mass is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.2% by mass or less.
  • the lower limit of the moisture content is not particularly limited, and may be 0% by mass.
  • the water content is measured by a Karl Fischer moisture meter.
  • 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 various solvents are applied to the substrate before the resin composition is applied to the substrate 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 further washed (rinsed) with a rinse liquid. Also, a method may be adopted in which a rinse liquid is supplied before the developer in contact with the pattern is 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 developing 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. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in the crosslinking agent other than the specific resin also proceeds.
  • 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 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 treat while irradiating with ultraviolet light 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 process 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 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 compound of the present invention is a compound represented by formula (B-1).
  • X1 's each independently represent a single bond or a divalent linking group
  • Y1 's each independently represent an alkylene group having 6 or more carbon atoms
  • A1 's each independently represent a (meth)acryloxy group
  • W1 's each independently represent a hydrogen atom or a monovalent organic group
  • n's each independently represent an integer of 1 or more
  • m's each independently represent an integer of 1 or more, provided that when n is 2, W1 's each independently represent a single bond or a linking group.
  • the preferred embodiment of formula (B-1) is the same as the preferred embodiment of formula (B-1) in the specific polymerizable compound described above.
  • preferred aspects of the polymerizable group value, allyl group value, (meth)acryloxy group value, ClogP value, molecular weight, synthesis method, specific examples, and the like of the compound of the present invention are the same as the preferred aspects of the above-mentioned specific polymerizable compound.
  • reaction solution was transferred to a separatory funnel, diluted with 500 mL of acetic acid, washed twice each with 500 mL of water, 200 mL of dilute hydrochloric acid, 300 mL of saturated sodium bicarbonate water, and 500 mL of saturated saline, in that order, dried over magnesium sulfate, and filtered through filter paper.
  • the solvent was removed from the filtrate with an evaporator to synthesize S-1, a raw material for the crosslinking agent. The identity of this product was confirmed by 1 H-NMR.
  • the reaction solution was then transferred to a separatory funnel, diluted with 500 mL of acetic acid, and washed twice each with 500 mL of water, 200 mL of dilute hydrochloric acid, 300 mL of saturated sodium bicarbonate water, and 500 mL of saturated saline, in that order, and then dried over magnesium sulfate and filtered through filter paper.
  • 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 (SP-1).
  • 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 structure, the subscripts of the repeating units represent the molar ratio of each repeating unit.
  • the weight average molecular weight of the obtained polyimide resin SP-1 was 19,700, and the number average molecular weight was 8,000.
  • the imidization rate was confirmed by 1 H-NMR and was 99% or more.
  • the C ⁇ C introduction rate (that is, the ratio of the number of hydroxy groups in the structure derived from 4,4′-bis(3-aminophenoxy)biphenyl to the number of vinylphenylmethyl groups bonded to 4-(chloromethyl)styrene) was 99%.
  • the weight average molecular weight and the number average molecular weight were measured by the following method.
  • a high-speed GPC apparatus HLC-8420GPC manufactured by Tosoh Corporation
  • a TSK guard column Super AW-H (4.6 mm x 35 mm) was used as a guard column.
  • the GPC measurement was performed using two TSKgel Super AWM-H (4.6 mm x 150 mm) columns connected in series.
  • the eluent used was a solution of 0.01 mol/L lithium bromide in NMP (N-methyl-2-pyrrolidone).
  • Polyimides (SP-2) to (SP-5) Synthesis of Polyimides (SP-2) to (SP-5)> Polyimides (SP-2) to (SP-5) were synthesized in the same manner as in Synthesis Example SP-1, except that the raw materials were appropriately changed.
  • Polyimides (SP-2) to (SP-5) are resins having repeating units represented by the following formulas SP-2 to SA-5, respectively. The structure of each 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 weight average molecular weight, number average molecular weight and imidization rate of these resins are shown in the table below.
  • AA-1 The structure of AA-1 is shown below. The structure was confirmed to be as shown below by 1 H-NMR spectrum.
  • 1 H-NMR (BRUKER, AVANCE NEO 400): ⁇ (ppm, DMSO-d6) 7.53-7.45 (s, 8H), 7. 05-6.98(d,2H), 6.92-6.85(d,2H), 6.79-6.63(4H), 5.89-5.78(d,2H), 5.29-5.22(d,2H), 5.20-5.13(s,4H), 4.92-4.64(4H)
  • the reaction solution was then dropped into a mixture of 1.5L of methanol and 0.5L of water, and the mixture was stirred for 15 minutes, after which the polyimide resin was filtered.
  • the resin was reslurried in 1L of water for 30 minutes, filtered, and then reslurried again in 1L of methanol, filtered, and dried under reduced pressure at 40°C for 10 hours.
  • the resin dried above was then dissolved in 250g of tetrahydrofuran, 40g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added, stirred for 4 hours, and the ion exchange resin was removed by filtration, after which the polyimide resin was precipitated in 2L of methanol and stirred for 15 minutes.
  • polyimide resin was obtained by filtration, and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin (SP-6).
  • Polyimide (SP-6) is a resin having a repeating unit represented by the following formula SP-6.
  • the structure of the repeating unit was determined from 1 H-NMR spectrum. In the following structure, the subscripts of the repeating units indicate the molar ratio of each repeating unit.
  • the resulting polyimide (SP-6) had a weight average molecular weight of 22,500 and a number average molecular weight of 7,200.
  • the imidization rate was confirmed by 1 H-NMR to be 96%.
  • Polyimide (SP-7) is a resin having a repeating unit represented by the following formula SP-7.
  • the structure of the repeating unit was determined from 1 H-NMR spectrum. In the following structures, the subscripts of the repeating units indicate the molar ratio of each repeating unit.
  • the resulting polyimide (SP-7) had a weight average molecular weight of 20,500 and a number average molecular weight of 7,500. The imidization rate was confirmed by 1 H-NMR to be 99% or more.
  • 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 250 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 (SP-8).
  • Polyimide (SP-8) is a resin having a repeating unit represented by the following formula SP-8.
  • the structure of the repeating unit was determined from 1 H-NMR spectrum. In the following structure, the subscripts of the repeating units represent the molar ratio of each repeating unit.
  • the weight average molecular weight of the obtained polyimide resin SP-8 was 23,700 and the number average molecular weight was 8,900.
  • the resin was reslurried in 1 L of water and filtered, and then reslurried again in 1 L of methanol and 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.
  • 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 obtained by filtration and dried at 45° C. under reduced pressure for 1 day to obtain polyimide resin (SP-9).
  • Polyimide (SP-9) is a resin having a repeating unit represented by the following formula SP-9.
  • the structure of the repeating unit was determined from 1 H-NMR spectrum. In the following structure, the subscripts of the repeating units represent the molar ratio of each repeating unit.
  • the weight average molecular weight of the obtained polyimide resin SP-9 was 19,500, and the number average molecular weight was 8,300.
  • the polymerizable group value was 0.70 mmol/g.
  • the imidization rate was 90%, and the C ⁇ C introduction rate was 98%.
  • the obtained white solid was collected and vacuum-dried at a temperature of 40° C. to obtain 85.8 g of A-1.
  • the weight average molecular weight (Mw) of A-1 was 25,100, and the number average molecular weight (Mn) was 11,200. It was confirmed by 1 H-NMR spectrum that the structure of A-1 was mainly composed of the structure represented by the following formula (A-1). From the measurement result of 1 H-NMR, the introduction rate of the crosslinking group was 50%. As a result of confirmation by 1 H-NMR, the imidization rate was 99% or more.
  • the polyimide precursor was obtained by filtration, stirred again in 4 L of water for 30 minutes, and filtered again. Next, the obtained polyimide precursor was dried at 45° C. under reduced pressure for 2 days to obtain polyimide precursor (SA-1).
  • the weight average molecular weight of the obtained polyimide precursor (SA-1) was 18,200, and the number average molecular weight was 7,800. It is assumed that the polyimide precursor (SA-1) is a resin having two repeating units represented by the following formula (SA-1).
  • 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.
  • OXE-01 IRGACURE OXE 01 (manufactured by BASF)
  • OXE-02 IRGACURE OXE 02 (manufactured by BASF)
  • C-1 Omnirad 1312 (manufactured by IGM)
  • C-2 Omnirad TPO H (manufactured by IGM)
  • C-3 CPI-310B (manufactured by San-Apro Co., Ltd.)
  • C-4 Benzoyl peroxide (Tokyo Chemical Industry Co., Ltd.)
  • SR-209 SR-209 (manufactured by Sartomer)
  • D-1 ADPH: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., melting point: 25°C or lower)
  • D-2 Tris(2-acryloyloxyethyl)isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • D-3 The above synthetic product
  • 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.)
  • I-1 N-phenyldiethanolamine (Tokyo Chemical Industry Co., Ltd.)
  • I-2 TC-401 (manufactured by Matsumoto Fine Chemical)
  • I-3 Compound having the following structure
  • the layer was then developed for 15 seconds with the developer described in the "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 of 3 to 20 ⁇ m.
  • the formed hole pattern was evaluated according to the following evaluation criteria. The evaluation results are described in the "Resolution” column of the table. Image analysis was performed using a scanning electron microscope (SEM), and when the residual film rate at the bottom of the hole was 1% or less, it was determined 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 6 ⁇ 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 10 ⁇ m could be resolved, but a hole pattern with a diameter of 6 ⁇ m could not be resolved.
  • D A hole pattern with a diameter of 10 ⁇ m could not be resolved.
  • 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 “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 dielectric constant (Dk) and dielectric loss tangent (Df) of the film sample at 28 GHz were measured by a resonator perturbation method.
  • the measurement device was as follows. The measured dielectric loss tangent values were evaluated according to the following evaluation criteria, and the evaluation results are shown in the "Dielectric loss tangent (Df)" column in the table.
  • B The dielectric loss tangent (Df) was 0.08 to less than 0.10.
  • C The dielectric loss tangent (Df) was 0.10 to less than 0.015.
  • D The dielectric loss tangent (Df) was 0.015 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 “Developer” column of 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 coating was heated in a heating oven under a nitrogen atmosphere at the temperature shown in the "Temperature” column of the “Curing conditions” in the table for the time shown in the "Time” column of the “Curing conditions” in the table to form a resin layer (pattern).
  • a resin layer pattern
  • cross-sectional SEM scanning electron microscope
  • the evaluation results are shown in the "insulation reliability" column in the table.
  • -Evaluation criteria A: The void area ratio was 0.1% or less.
  • C The void area ratio was more than 0.3% and 0.5% or less.
  • D The void area ratio exceeded 0.5%.
  • the exposure was performed at a wavelength of 365 nm through a hole pattern mask formed with a hole pattern having a diameter of 15 ⁇ m.
  • the film was developed for 15 seconds with the developer described in the "developing solution” column of the table, rinsed with PGMEA for 30 seconds, and the film thickness (film thickness B) after development was measured by SEM (scanning electron microscope).
  • the residual film rate after development was calculated as film thickness B / film thickness A ⁇ 100 (%). It can be said that the higher the residual film rate, the better the residual film rate after development. From the obtained film remaining rate value, evaluation was performed according to the following evaluation criteria. The evaluation results are shown in the "film remaining rate" column in the table. -Evaluation criteria- A: The remaining film rate was 90% or more. B: The remaining film rate was more than 85% and less than 90%. C: The remaining film rate was more than 80% and less than 85%. D: The remaining film rate was less than 80%.
  • the resin composition according to the comparative example does not contain a compound corresponding to the specific polymerizable compound. It is understood that the cured product obtained from such a resin composition has a large dielectric loss tangent.
  • Example 101 The resin composition used in Example 1 was applied in a layer form by spin coating on 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.

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Abstract

L'invention concerne une composition de résine comprenant : au moins une résine choisie dans le groupe constitué par des polyimides et des polybenzoxazoles ; un composé polymérisable ayant un groupe allyle, un groupe aromatique et un groupe hydrocarboné saturé aliphatique qui a 4 atomes de carbone ou plus ; et un initiateur de polymérisation. L'invention concerne également : un produit durci obtenu par durcissement de ladite composition de résine ; un stratifié comprenant un produit durci ; un procédé de production d'un produit durci ; un procédé de production d'un stratifié ; un procédé de production d'un dispositif à semi-conducteur, ledit procédé comprenant un procédé de production d'un produit durci ; et un dispositif à semi-conducteur comprenant un produit durci.
PCT/JP2024/026489 2023-07-27 2024-07-24 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur Pending WO2025023280A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005528486A (ja) * 2002-05-31 2005-09-22 エルシコン・インコーポレーテッド 液晶配向層用ハイブリッドポリマー材料

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005528486A (ja) * 2002-05-31 2005-09-22 エルシコン・インコーポレーテッド 液晶配向層用ハイブリッドポリマー材料

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
YOKOTA KAZUAKI, KAKUCHI TOYOJI, NANASAWA ATSUSHI, IWATA JUN-ICHI, TAKADA YOSHIYUKI: "Studies of the Cyclopolymerization in the Presence of Alkylaluminum Chlorides. VI. Cyclopolymerizations of 2-(o-Allylphenoxy)ethyl Methacrylate and the Higher Homologues in the 11—19-Membered-Ring Region", POLYMER JOURNAL, NATURE PUBLISHING GROUP UK, LONDON, vol. 14, no. 7, 1 July 1982 (1982-07-01), London , pages 509 - 516, XP093265211, ISSN: 0032-3896, DOI: 10.1295/polymj.14.509 *
YOKOTA KAZUAKI, TOYOJI KAKUCHL， AND YOSHIYUKI TAKADA : "The Cyclopolymerization in the Presence of Alkylaluminum Chlorides", HOKKAIDO UNIVERSITY COLLECTION OF SCHOLARLY AND ACADEMIC PAPERS : HUSCAP ISSN:0385-602X, BULLETIN OF THE FACULTY OF ENGINEERING, HOKKAIDO UNIVERSITY. NO. 102. ISSN:0385-602X, HOKKAIDO UNIVERSITY, Hokkaido University, pages 1 - 11, XP093265191 *
覚知 豊次 他, ポリマー主鎖に中環状構造を与えるモノマーの有機アルミニウム化合物存在下での環化重合, 旭硝子工業技術奨励会研究報告, 15 December 1980, vol. 37, pp. 49-57, ISSN: 0365-2599, (KAKUCHI, Toyoji et al. Reports of the Asahi Glass Foundation for Industrial Technology.), non-official translation (Cyclopolymerization of monomers that give medium ring structures in the polymer main chain in the presence of organoaluminum compounds) *

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