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WO2025070302A1 - Composition de résine et procédé de production d'un film isolant intercouche pour couche de redistribution - Google Patents

Composition de résine et procédé de production d'un film isolant intercouche pour couche de redistribution Download PDF

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Publication number
WO2025070302A1
WO2025070302A1 PCT/JP2024/033668 JP2024033668W WO2025070302A1 WO 2025070302 A1 WO2025070302 A1 WO 2025070302A1 JP 2024033668 W JP2024033668 W JP 2024033668W WO 2025070302 A1 WO2025070302 A1 WO 2025070302A1
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group
formula
resin composition
carbon atoms
compounds
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PCT/JP2024/033668
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English (en)
Japanese (ja)
Inventor
啓介 野越
倫弘 小川
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Fujifilm Corp
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Fujifilm Corp
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    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to a resin composition and a method for producing an interlayer insulating film for a redistribution layer.
  • Polyimides and polyimide precursors are used in a variety of fields, including semiconductor devices and the aerospace industry.
  • Patent Document 1 describes a varnish composition containing a polyimide resin having a radically polymerizable group or a cationic polymerizable group bonded to the main chain of the polyimide resin and containing a skeleton derived from a bisphenol having a specific structure in the constituent units constituting the main chain of the polyimide resin, and an organic solvent.
  • Patent Document 2 describes a photosensitive resin composition containing a polyimide precursor having a specific structure, a photosensitizer, and a solvent.
  • polyimides and polyimide precursors are a film used in a semiconductor device (for example, an insulating film such as an interlayer insulating film for a redistribution layer).
  • a semiconductor device for example, an insulating film such as an interlayer insulating film for a redistribution layer.
  • resin compositions that are materials for forming films are required to have high resolution and mechanical properties (particularly breaking elongation).
  • the objective of the present invention is to provide a resin composition capable of forming a film having excellent resolution and breaking elongation, and a method for manufacturing an interlayer insulating film for a redistribution layer using the resin composition.
  • a resin composition containing at least one resin selected from the group consisting of polyimides and polyimide precursors The resin composition is formed into a film, exposed to light at 100 mJ/ cm2 , and heated at 230°C for 1 hour, and the breaking elongation of the film after heating is greater than the breaking elongation of the film before heating.
  • a resin composition comprising at least one resin selected from the group consisting of a structure represented by the following formula (1) and a structure represented by the following formula (2):
  • X 1 , X 2 , Y 1 and Y 2 each independently represent an organic group.
  • W 1 , W 2 , W 3 and W 4 each independently represent a single bond or a divalent organic group.
  • P 1 , P 2 , P 3 and P 4 each independently represent a group containing a moiety having an activation energy of 40 to 60 kcal/mol upon dissociation.
  • Q 1 , Q 2 , Q 3 and Q 4 each independently represent a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group or a hydrogen atom.
  • a resin composition comprising at least one resin selected from the group consisting of a structure represented by the following formula (1) and a structure represented by the following formula (2):
  • X 1 , X 2 , Y 1 and Y 2 each independently represent an organic group.
  • W 1 , W 2 , W 3 and W 4 each independently represent a single bond or a divalent organic group.
  • P 1 , P 2 , P 3 and P 4 each independently represent a group having at least one type of structure selected from the group consisting of a structure represented by the following formula (3) and a structure represented by the following formula (4).
  • Q 1 , Q 2 , Q 3 and Q 4 each independently represent a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group or a hydrogen atom.
  • a, b, c, and d each independently represent an integer of 0 or more, provided that at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more.
  • m, n, p and q each independently represent an integer of 1 or more.
  • A1 and B1 each independently represent an oxygen atom or NR4 .
  • R4 represents a hydrogen atom or a monovalent organic group.
  • A2 and B2 each independently represent an oxygen atom or NH.
  • R3 represents a divalent hydrocarbon group.
  • * 1 and * 2 indicate binding positions.
  • At least one of A 1 and B 1 in the above formula (3) represents an oxygen atom;
  • [6] The resin composition according to any one of [3] to [5], wherein the resin has a structure represented by the formula (1).
  • a resin composition comprising at least one resin selected from the group consisting of polyimides and polyimide precursors, and a polymerizable compound,
  • the polymerizable compound is a resin composition containing a moiety having an activation energy of 40 to 60 kcal/mol upon dissociation.
  • a resin composition comprising at least one resin selected from the group consisting of polyimides and polyimide precursors, and a polymerizable compound,
  • the polymerizable compound is a resin composition having at least one structure selected from the group consisting of a structure represented by the following formula (3) and a structure represented by the following formula (4):
  • A1 and B1 each independently represent an oxygen atom or NR4 , where R4 represents a hydrogen atom or a monovalent organic group, provided that at least one of A1 and B1 represents an oxygen atom.
  • R4 represents a hydrogen atom or a monovalent organic group, provided that at least one of A1 and B1 represents an oxygen atom.
  • A2 and B2 each independently represent an oxygen atom or NH.
  • R3 represents a divalent hydrocarbon group.
  • * 1 and * 2 indicate binding positions.
  • the polymerizable compound has a structure represented by formula (4), The resin composition according to any one of [11] to [13], wherein one of A2 and B2 in the formula (4) represents an oxygen atom, and the other represents NH.
  • the polymerizable compound has a structure represented by formula (4), The resin composition according to any one of [11] to [14], wherein R 3 in the formula (4) represents a divalent hydrocarbon group having 6 or less carbon atoms.
  • the resin composition according to any one of [1] to [16] further comprising a light absorbing agent.
  • the method for producing an interlayer insulating film for a redistribution layer includes the steps of:
  • the present invention provides a resin composition capable of forming a film having excellent resolution and breaking elongation, and a method for manufacturing an interlayer insulating film for a redistribution layer using the resin composition.
  • 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.
  • an "organic group” refers to a group containing at least one carbon atom.
  • the resin composition of the present invention will be described.
  • One embodiment (first aspect) of the resin composition of the present invention is a resin composition containing at least one resin selected from the group consisting of polyimides and polyimide precursors,
  • the breaking elongation of the film after heating is greater than the breaking elongation of the film before heating.
  • the breaking elongation of the film after heating is preferably at least 5 percentage points greater than the breaking elongation of the film before heating, more preferably at least 10 percentage points greater, even more preferably at least 15 percentage points greater, and particularly preferably at least 20 percentage points greater.
  • the resin composition of the present invention a film having excellent resolution and breaking elongation can be formed.
  • the present inventors presume as follows. However, the present invention is not limited in any way by the presumed mechanism below.
  • breakage tends to progress from the crosslinking point, and the breaking elongation tends to be small.
  • the film formed from the resin composition of the present invention can progress three-dimensional crosslinking by exposure, while the three-dimensional crosslinking can be released by subsequent heating, so it is considered that the film has excellent resolution and breaking elongation.
  • the breaking elongation is measured by the following method.
  • the resin composition is applied onto a silicon wafer by spin coating to form a coating film, and the silicon wafer having the coating film is dried on a hot plate at 100° C. for 5 minutes to obtain a uniform film having a thickness of 15 ⁇ m on the silicon wafer.
  • the entire surface of the obtained film is exposed to i-line light using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 100 mJ/cm 2.
  • the film at this point is referred to as the "film before heating.”
  • the exposed film is heated at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., is heated at 230° C. for 1 hour.
  • the film at this point is referred to as the "film after heating.”
  • the silicon wafer with the film before heating and the silicon wafer with the film after heating are each immersed in a 3 mass % hydrofluoric acid aqueous solution to peel the film from the silicon wafer.
  • the peeled film is shaped into a dumbbell shape (Type V) according to ASTM D638-00, and pulled at a chuck distance of 20 mm and a speed of 5 mm/min, and the elongation (%) until breakage is defined as the breaking elongation.
  • the resin composition of the present invention preferably contains a resin (also referred to as “resin (A)”) having at least one selected from the group consisting of a structure represented by the following formula (1) and a structure represented by the following formula (2):
  • X 1 , X 2 , Y 1 and Y 2 each independently represent an organic group.
  • W 1 , W 2 , W 3 and W 4 each independently represent a single bond or a divalent organic group.
  • P 1 , P 2 , P 3 and P 4 each independently represent a group containing a moiety having an activation energy of 40 to 60 kcal/mol upon dissociation.
  • Q 1 , Q 2 , Q 3 and Q 4 each independently represent a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group or a hydrogen atom.
  • a, b, c, and d each independently represent an integer of 0 or more, provided that at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more.
  • m, n, p and q each independently represent an integer of 1 or more.
  • the resin (A) is a resin having at least one structure selected from the group consisting of the structure represented by the above formula (1) and the structure represented by the above formula (2).
  • the resin (A) may have a structure represented by formula (1).
  • the resin (A) may have a structure represented by formula (2).
  • the resin (A) may have a structure represented by formula (1) and a structure represented by formula (2).
  • Resin (A) is preferably a resin having two or more of at least one selected from the group consisting of the structure represented by formula (1) and the structure represented by formula (2), and more preferably a resin having at least one selected from the group consisting of the repeating unit represented by formula (1) and the repeating unit represented by formula (2).
  • resin (A) preferably has at least one of the structure represented by formula (1) and the structure represented by formula (2) as a repeating unit.
  • the resin (A) may be a polyimide or a polyamide.
  • the resin (A) may further have a structure other than the structure represented by formula (1) and the structure represented by formula (2).
  • Resin (A) may be a precursor of cyclized resin.
  • the precursor of cyclized resin refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a cyclized resin, and is preferably a resin that undergoes a change in chemical structure due to heat to become a cyclized resin, and more preferably a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a cyclized resin.
  • the precursor of cyclized resin may be, for example, a polyimide precursor, a polybenzoxazole precursor, a polyamideimide precursor, etc., and is preferably a polyimide precursor.
  • resin (A) is a resin having a repeating unit represented by formula (1)
  • resin (A) is a polyimide, and therefore, in the following description, resin (A) having a repeating unit represented by formula (1) is also referred to as "polyimide”.
  • X1 in formula (1) represents an organic group, more specifically, an organic group having a valence of 4+a. Since a represents an integer of 0 or more, the following description will be given taking as an example a case where a represents 0 (i.e., X1 represents a tetravalent organic group ) (when a represents an integer of 1 or more, X1 is obtained by substituting a number of -W1- ( P1 - Q1 ) m for a number of arbitrary hydrogen atoms of X1 described below).
  • the tetravalent organic group represented by X1 is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6):
  • R 112 is a single bond or a divalent linking group, and is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, an aromatic group (which may be an aromatic hydrocarbon group or an aromatic heterocyclic group), -O-, -CO-, -S-, -SO 2 -, -NHCO-, and a combination thereof, more preferably a single bond, or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, -O-, -CO-, -S-, and -SO 2 -, and even more preferably a divalent group selected from the group consisting of -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, a phenylene group,
  • X1 examples include tetracarboxylic acid residues remaining after removal of anhydride groups from tetracarboxylic dianhydride, etc.
  • the structure corresponding to X1 may contain only one type of tetracarboxylic acid residue, or may contain two or more types of tetracarboxylic acid residues.
  • the tetracarboxylic dianhydride is preferably represented by the following formula (O).
  • R 115 represents a tetravalent organic group.
  • the preferred range of R 115 is the same as that of X 1 .
  • tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2, 2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dian
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.
  • X 1 is preferably a tetracarboxylic acid residue having 1 to 4 aromatic rings.
  • Y1 represents an organic group, more specifically, an organic group having a valence of 2+b. Since b represents an integer of 0 or more, the following description will be given taking as an example a case where b represents 0 (i.e., a case where Y1 represents a divalent organic group) (when b represents an integer of 1 or more, Y1 is obtained by substituting b arbitrary hydrogen atoms of Y1 described below with b -W2- ( P2 - Q2 ) n ).
  • Examples of the divalent organic group represented by Y 1 include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group.
  • a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred.
  • the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • the aromatic heterocyclic group preferably contains one or more heteroatoms selected from the group consisting of nitrogen atoms, sulfur atoms, and oxygen atoms in the ring members.
  • the number of ring members of the aromatic group is preferably 5 to 20, and more preferably 6 to 15.
  • the linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom.
  • Y1 include groups represented by -Ar- and -Ar-L-Ar-, and the group represented by -Ar-L-Ar- is preferred.
  • each Ar is independently an aromatic group
  • L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above.
  • the preferred ranges for these are as described above.
  • Y1 is preferably derived from a diamine.
  • the diamine include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types of diamines may be used.
  • Y1 is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms.
  • the linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom
  • the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom.
  • groups containing an aromatic group include the following.
  • * represents a bonding site with other structures.
  • diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diamino
  • diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017/038598.
  • diamines having two or more alkylene glycol units in the main chain are also preferably used.
  • diamines having two or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of WO 2017/038598.
  • Y1 is preferably represented by -Ar-L-Ar-.
  • each Ar is independently an aromatic group
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above.
  • Ar is preferably a phenylene group
  • L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 -.
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • Y1 is preferably a divalent organic group represented by the following formula (51) or formula (61).
  • Y1 is more preferably a divalent organic group represented by formula (61).
  • R 50 to R 57 each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group, at least one of R 50 to R 57 is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with a nitrogen atom.
  • the monovalent organic group for R 50 to R 57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).
  • R 58 and R 59 each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and each * independently represents a bonding site to the nitrogen atom.
  • diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.
  • Y1 is also preferably a diamine residue having at least two alkylene glycol units in the main chain (a group remaining after removal of the amino groups of the diamine) in order to more effectively suppress the occurrence of warping during firing. It is also preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and more preferably a diamine residue of the above diamine that does not contain an aromatic ring.
  • Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc.
  • P1 and P2 each independently represent a group containing a site (bond) having an activation energy (also referred to as "Ea") upon dissociation of 40 to 60 kcal/mol.
  • P1 and P2 have a moiety with Ea of 40 to 60 kcal/mol, and therefore are easily dissociated (decomposed), for example, when heated at 230° C. for 1 hour.
  • a resin composition containing a resin (A) having a structure represented by formula (1) is formed into a film, exposed to light at 100 mJ/cm 2 , and heated at 230° C.
  • P1 and P2 preferably have a moiety with Ea of 42 to 58 kcal/mol, more preferably have a moiety with Ea of 45 to 55 kcal/mol, and even more preferably have a moiety with Ea of 48 to 52 kcal/mol.
  • the method for calculating the activation energy (Ea) will be described below. All calculations were performed using Gaussian 09 (rev. C), and the default settings of Gaussian 09 (rev. C) were used except for the following settings.
  • Ea was obtained from the difference in Gibbs free energy between the stable structure before dissociation of the bond for which Ea was to be calculated and the transition state of dissociation.
  • the dissociation energy of the bond for which Ea is to be calculated calculated using the following method, is used as Ea. All calculations were performed using Gaussian 09 (rev. C), and the default settings of Gaussian 09 (rev. C) were used except for the following settings. Structure optimization and vibration calculations were performed using density functional theory (DFT), and calculations were performed in a vacuum state using ⁇ B97XD as the functional and 6-31G* as the basis function.
  • DFT density functional theory
  • P1 and P2 are not particularly limited as long as they are groups having a moiety with Ea of 40 to 60 kcal/mol, but each of them preferably independently represents a group having at least one selected from the group consisting of a structure represented by the following formula (3) and a structure represented by the following formula (4):
  • the structure represented by the following formula (3) and the structure represented by the following formula (4) preferably have a moiety having Ea of 40 to 60 kcal/mol.
  • A1 and B1 each independently represent an oxygen atom or NR4 .
  • R4 represents a hydrogen atom or a monovalent organic group.
  • A2 and B2 each independently represent an oxygen atom or NH.
  • R3 represents a divalent hydrocarbon group.
  • * 1 and * 2 indicate binding positions.
  • R4 represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group represented by R4 is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group.
  • the number of carbon atoms in the monovalent organic group represented by R4 may be 1 to 20.
  • R4 represents a hydrogen atom.
  • R 3 represents a divalent hydrocarbon group.
  • the divalent hydrocarbon group represented by R 3 is not particularly limited, and examples thereof include an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, and a group formed by combining two or more of these.
  • the number of carbon atoms in the divalent hydrocarbon group represented by R 3 may be 1 to 30, or 1 to 20. It is preferable that R 3 represents a divalent hydrocarbon group having 6 or less carbon atoms.
  • At least one of A 1 and B 1 in formula (3) represents an oxygen atom
  • at least one of A 2 and B 2 in formula (4) represents an oxygen atom
  • the structure represented by formula (3) satisfies at least one of the following (i) and (ii), and the structure represented by formula (4) satisfies at least one of the following (iii) and (iv).
  • A1 represents an oxygen atom, and * 1 indicates the bonding position to the aromatic ring.
  • B1 represents an oxygen atom, and * 2 indicates the bonding position to the aromatic ring.
  • A2 represents an oxygen atom, and * 1 indicates the bonding position to the aromatic ring.
  • B2 represents an oxygen atom, and * 2 indicates the bonding position to the aromatic ring.
  • A1 and B1 in formula (3) represent an oxygen atom, or one of A1 and B1 represents an oxygen atom and the other represents NH, and it is more preferable that one of A1 and B1 represents an oxygen atom and the other represents NH.
  • * 1 may indicate a bonding position closer to W1 or W2 than * 2 .
  • * 1 is closer to W1 or W2 than * 2
  • * 1 represents a bonding position with W1 or W2 , or the minimum value of the number of atoms present between the atom to which * 1 is bonded and the atom constituting W1 or W2 is smaller than the minimum value of the number of atoms present between the atom to which * 2 is bonded and the atom constituting W1 or W2 .
  • * 2 may represent a bonding position closer to W1 or W2 than * 1 .
  • * 2 is closer to W1 or W2 than * 1 " means that * 2 represents a bonding position with W1 or W2 , or that the minimum number of atoms between the atom to which * 2 is bonded and an atom constituting W1 or W2 is smaller than the minimum number of atoms between the atom to which * 1 is bonded and an atom constituting W1 or W2 .
  • one of A2 and B2 in formula (4) is an oxygen atom and the other is NH.
  • A2 represents an oxygen atom
  • B2 represents NH
  • * 1 may indicate a bonding position closer to W1 or W2 than * 2 .
  • * 2 may indicate a bonding position closer to W1 or W2 than * 1 .
  • W 1 and W 2 each independently represent a single bond or a divalent organic group.
  • the divalent organic group represented by W1 and W2 is not particularly limited, and examples thereof include a carbonyl group, an ester group, an amide group, an alkylene group, an arylene group, a cycloalkylene group, an alkyleneoxy group, an aryleneoxy group, a cycloalkyleneoxy group, and a group formed by combining two or more of these groups. These organic groups may further have a substituent.
  • the number of carbon atoms of the divalent organic groups represented by W 1 and W 2 is not particularly limited, and may be, for example, 1 to 100 carbon atoms.
  • Q 1 and Q 2 each independently represent a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group, or a hydrogen atom.
  • the monovalent organic group represented by Q1 and Q2 is not particularly limited, and examples thereof include an alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an acyl group, a heterocyclic group, an alkenyl group, an alkynyl group, and a group formed by combining two or more of these groups. These organic groups may further have a substituent.
  • At least one of Q1 and Q2 in formula (1) preferably represents a monovalent organic group containing at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.
  • the ethylenically unsaturated group 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.
  • a and b each independently represent an integer of 0 or more, provided that at least one of a and b represents an integer of 1 or more.
  • a and b each independently may represent an integer of 0 or more and 100 or less.
  • m and n each independently represent an integer of 1 or more, and may represent an integer of 1 or more and 100 or less.
  • At least one of X 1 and Y 1 has an OH group. More specifically, preferred examples of Y 1 include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18), and more preferred examples of X 1 include the above (DAA-1) to (DAA-5).
  • the polyimide may be an alkali-soluble polyimide, or may be a polyimide that is soluble in a developer containing an organic solvent as a main component.
  • the alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C., and from the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferable, and a polyimide that dissolves at 1.0 g or more is more preferable.
  • the upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less.
  • the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.
  • the 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 polyimide contains fluorine atoms.
  • the fluorine atom is, for example, preferably contained in X1 or Y1 , and more preferably contained in X1 or Y1 as a fluorinated alkyl group.
  • the amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.
  • the polyimide contains a silicon atom. It is more preferable that the silicon atom is contained in, for example, X1 or Y1 as an organically modified (poly)siloxane structure.
  • the silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
  • the amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass % or more, and more preferably 20 mass % or less.
  • the polyimide preferably has an ethylenically unsaturated bond.
  • the ethylenically unsaturated bond preferably has radical polymerizability.
  • An ethylenically unsaturated bond is preferably contained in at least one of X1 and Y1 , and more preferably contained as a group having an ethylenically unsaturated bond in at least one of X1 and Y1 .
  • the ethylenically unsaturated bond is more preferably contained in Y1 , and further preferably contained in Y1 as a group having an ethylenically unsaturated bond.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).
  • R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
  • R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -C( ⁇ O)O-, -O(C ⁇ O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions in the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group consisting of a combination of two or more of these.
  • the alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, and alkylene groups represented by a combination thereof.
  • the alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.
  • R 21 is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).
  • L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together;
  • X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and
  • ⁇ represents a bonding site with the oxygen atom to which R21 in formula (IV) is bonded.
  • formulas (R1) to (R3) preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L are the same as the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as R 21 in formula (IV).
  • X is preferably an oxygen atom.
  • * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
  • the structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).
  • the structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
  • the structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.).
  • * represents a bonding site with another structure, and is preferably a bonding site with the main chain of the polyimide.
  • the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.
  • the polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
  • the polymerizable group other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
  • the polymerizable group other than the group having an ethylenically unsaturated bond is preferably included in Y1 , for example.
  • the amount of polymerizable groups other than groups having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.
  • the polyimide may have a polarity conversion group such as an acid-decomposable group.
  • the acid-decomposable group in the polyimide is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is preferably an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, or the like, and is more preferably an acetal group or a ketal group from the viewpoint of exposure sensitivity.
  • the acid-decomposable group examples include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
  • the polarity conversion group is contained in, for example, X 1 , Y 1 , or the terminal of the polyimide.
  • the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
  • the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
  • the acid value of the polyimide is preferably from 1 to 35 mgKOH/g, more preferably from 2 to 30 mgKOH/g, and even more preferably from 5 to 20 mgKOH/g.
  • the acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
  • the acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability.
  • pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa.
  • pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified.
  • ACD/ChemSketch registered trademark
  • pKa the value listed in "Revised 5th Edition Chemistry Handbook: Basics" compiled by the Chemical Society of Japan may be referred to.
  • the acid group is a polyacid, such as phosphoric acid
  • the pKa is the first dissociation constant.
  • the polyimide preferably contains at least one type selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.
  • the polyimide preferably has a phenolic hydroxy group.
  • the polyimide may have a phenolic hydroxy group at the end of the main chain or on a side chain.
  • the phenolic hydroxy group is preferably contained in, for example, X1 or Y1 .
  • the amount of the phenolic hydroxy group relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.
  • the polyimide has fluorine atoms in its structure.
  • the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.
  • the polyimide may be copolymerized with an aliphatic group having a siloxane structure.
  • diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.
  • the main chain ends of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
  • a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
  • monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amino
  • the imidization rate of the polyimide (also referred to as the "ring closure rate") is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less.
  • the imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm ⁇ 1 , which is an absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350° C.
  • the polyimide may contain only one type of repeating unit represented by formula (1), or may contain two or more types. In addition to the repeating unit represented by formula (1), the polyimide may contain other types of repeating units. Examples of other types of repeating units include repeating units represented by formula (2).
  • Polyimides can be synthesized, for example, by reacting tetracarboxylic dianhydride with diamine (partially substituted with a terminal blocking agent that is a monoamine) at low temperature, by reacting tetracarboxylic dianhydride (partially substituted with a terminal blocking agent that is an acid anhydride, a monoacid chloride compound, or a monoactive ester compound) with diamine at low temperature, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine) in the presence of a condensing agent, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine), or by using a method in which a polyimide precursor is
  • the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties (e.g., breaking elongation), the weight average molecular weight is particularly preferably 15,000 or more.
  • the number average molecular weight (Mn) of the polyimide is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000.
  • the polyimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the polyimide molecular weight dispersity is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the 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 polyimides are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimides as one resin are each within the above ranges.
  • the repeating unit represented by formula (2) will be described.
  • the resin (A) is a resin having a repeating unit represented by formula (2)
  • the resin (A) is a polyamide, and therefore in the following description, the resin (A) having a repeating unit represented by formula (2) is also referred to as "polyamide.”
  • the resin (A) is preferably a polyimide precursor.
  • X2 in formula (2) represents an organic group, more specifically, a 4+c-valent organic group, where c represents an integer of 0 or more, and therefore, hereinafter, a case where c represents 0 (i.e., a case where X2 represents a tetravalent organic group) will be described as an example (when c represents an integer of 1 or more, X2 is obtained by substituting c arbitrary hydrogen atoms of X2 described below with c -W3- ( P3 - Q3 ) p ).
  • the description, specific examples and preferred ranges of the tetravalent organic group represented by X2 are the same as those of the tetravalent organic group represented by X1 in the above-mentioned formula (1).
  • Y2 represents an organic group, more specifically, an organic group having a valence of 2+d. Since d represents an integer of 0 or more, the following description will be given taking as an example a case where d represents 0 (i.e., a case where Y2 represents a divalent organic group) (when d represents an integer of 1 or more, Y2 is obtained by substituting d arbitrary hydrogen atoms of Y2 described below with d -W4- ( P4 - Q4 ) q ). The description, specific examples and preferred range of the divalent organic group represented by Y2 are the same as those for Y1 in the above formula (1).
  • R 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group is preferably a group containing an alkyl group (which may be linear or branched), a cycloalkyl group, an aromatic group, or a polyalkyleneoxy group.
  • the monovalent organic group represented by R 1 and R 2 may further have a substituent.
  • the number of carbon atoms of the monovalent organic group represented by R 1 and R 2 may be 1 to 50 or 1 to 30.
  • R1 and R2 represent a hydrogen atom.
  • At least one of Q1 and Q2 in formula (1) represents a monovalent organic group containing at least one group selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group; At least one of Q 3 and Q 4 in formula (2) preferably represents a monovalent organic group containing at least one group selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.
  • c and d each independently represent an integer of 0 or more, provided that at least one of c and d represents an integer of 1 or more.
  • c and d each independently may represent an integer of 0 or more and 100 or less.
  • p and q each independently represent an integer of 1 or more, and may represent an integer of 1 or more and 100 or less.
  • At least one of X2 and Y2 may have an OH group. More specifically, Y2 may be a residue of a bisaminophenol derivative. It is also possible that at least one of R1 and R2 has an OH group.
  • At least one of X2 and Y2 preferably contains a polymerizable group, and both preferably contain a polymerizable group. It is also preferable that at least one of X2 and Y2 contains two or more polymerizable groups. It is also preferred that at least one of R1 and R2 contains a polymerizable group, or that both of them contain a polymerizable group. It is also preferred that at least one of R1 and R2 contains two or more polymerizable groups.
  • the polymerizable group is a group (crosslinkable group) capable of crosslinking by the action of heat, radicals, etc., and is preferably a radically polymerizable group.
  • the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
  • a group having an ethylenically unsaturated bond is preferable.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.
  • R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
  • * represents a bonding site with another structure.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
  • R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CH 2 CH(OH)CH 2 -, and polyalkyleneoxy groups, of which alkylene groups such as ethylene group and propylene group, -CH 2 CH(OH)CH 2 -, cyclohexyl group, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy groups are even more preferred.
  • alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-but
  • the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating.
  • the number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent, when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, still 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 repetitions of the polyalkyleneoxy group) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.
  • the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.
  • the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiment of the number of repetitions of the ethyleneoxy group in these groups is as described above.
  • At least one of X2 and Y2 may have a polarity conversion group such as an acid-decomposable group.
  • a polarity conversion group such as an acid-decomposable group.
  • the description, specific examples and preferred range of the acid-decomposable group are the same as those for X1 and Y1 described above.
  • the polyamide has fluorine atoms in its structure.
  • the fluorine atom content in the polyamide is preferably 10% by mass or more, and 20% by mass or less.
  • the polyamide may be copolymerized with an aliphatic group having a siloxane structure.
  • Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine.
  • the polyamide may contain only one type of repeating unit represented by formula (2), or may contain two or more types.
  • the polyamide may contain other types of repeating units in addition to the repeating unit represented by formula (2).
  • One embodiment of the polyamide is one in which the content of the repeating units represented by formula (2) is 50 mol% or more of the total repeating units.
  • the total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
  • the weight average molecular weight (Mw) of the polyamide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000.
  • the number average molecular weight (Mn) of the polyamide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
  • the polyamide molecular weight dispersity 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 polyamide molecular weight dispersity is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the weight average molecular weight, number average molecular weight, and dispersity of at least one of the polyamides 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 polyamides as one resin are each within the above ranges.
  • Polyamides can be obtained, for example, by reacting tetracarboxylic dianhydride with a diamine at low temperature, by reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid, and then esterifying the polyamic acid with a condensing agent or an alkylating agent, by obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting the diamine in the presence of a condensing agent, by obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine, etc.
  • the method of obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine is more preferable.
  • the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.
  • alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.
  • halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like.
  • the organic solvent may be one type or two or more types.
  • the organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and ⁇ -butyrolactone.
  • a basic compound may be one type or two or more types.
  • the basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.
  • -End-capping agent- In the method for producing polyamide, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyamide in order to further improve storage stability.
  • examples of the terminal capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and it is more preferable to use monoalcohols, phenols, or monoamines in terms of reactivity and film stability.
  • Examples of preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
  • primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol
  • secondary alcohols such as isopropanol, 2-butanol, cyclo
  • Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.
  • Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of such an acid include 2-carboxy-7-aminonaphthalene, 2-car
  • blocking agents for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides.
  • Preferred compounds of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like.
  • carboxylic acid chloride examples include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.
  • the method for producing polyamide may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction liquid as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof to precipitate the polymer component as a solid, and then dried to obtain polyamide. In order to improve the degree of purification, the polyamide may be repeatedly subjected to operations such as redissolving, reprecipitating, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.
  • At least one terminal of the resin (A) may have at least one crosslinkable group.
  • the crosslinkable group may contain at least one selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.
  • the content of the resin (A) 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 (A) 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 resin (A), or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the resin composition of the present invention may contain a resin (also referred to as “resin (Ab)”) having at least one selected from the group consisting of a structure represented by the following formula (1) and a structure represented by the following formula (2).
  • X 1 , X 2 , Y 1 and Y 2 each independently represent an organic group.
  • W 1 , W 2 , W 3 and W 4 each independently represent a single bond or a divalent organic group.
  • P 1 , P 2 , P 3 and P 4 each independently represent a group having at least one type of structure selected from the group consisting of a structure represented by the following formula (3) and a structure represented by the following formula (4).
  • Q 1 , Q 2 , Q 3 and Q 4 each independently represent a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group or a hydrogen atom.
  • a, b, c, and d each independently represent an integer of 0 or more, provided that at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more.
  • m, n, p and q each independently represent an integer of 1 or more.
  • A1 and B1 each independently represent an oxygen atom or NR4 .
  • R4 represents a hydrogen atom or a monovalent organic group.
  • A2 and B2 each independently represent an oxygen atom or NH.
  • R3 represents a divalent hydrocarbon group.
  • * 1 and * 2 indicate binding positions.
  • Resin (Ab) is the same as Resin (A) described above, except that the definition of P 1 , P 2 , P 3 and P 4 in formulas (1) and (2) of Resin (A) has been changed from "representing a group containing a moiety having an activation energy of 40 to 60 kcal/mol upon dissociation" to "representing a group having at least one selected from the group consisting of a structure represented by formula (3) and a structure represented by formula (4)".
  • the explanation of resin (Ab) is the same as that of resin (A) described above, except for "P 1 , P 2 , P 3 and P 4 " in formulas (1) and (2).
  • the explanation of the structure represented by formula (3) and the structure represented by formula (4) in resin (Ab) is the same as that of the structure represented by formula (3) and the structure represented by formula (4) described in the explanation of resin (A) above.
  • Resin (Ab) is represented by the formula (1), wherein at least one of Q1 and Q2 represents a monovalent organic group containing at least one group selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group; At least one of Q 3 and Q 4 in formula (2) preferably represents a monovalent organic group containing at least one group selected from the group consisting of an ethylenically unsaturated group, a carboxy group, an epoxy group, and a hydroxy group.
  • the content of the resin (Ab) 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 (Ab) 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 resin (Ab), or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • a resin corresponding to at least one of resin (A) and resin (Ab) is also referred to as a "specific resin".
  • 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 specific resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition.
  • the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention contains at least two types of resins.
  • the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resin described below, or may contain two or more types of the specific resin, but it is preferable that the resin composition contains two or more types of the specific resin.
  • the resin composition of the present invention contains two or more specific resins, it is preferable that the resin composition contains, for example, two or more polyamides having different dianhydride-derived structures (X 2 in formula (2)).
  • the resin composition of the present invention may contain the specific resin and another resin different from the specific resin (hereinafter, simply referred to as "another resin").
  • the other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, polybenzoxazoles, polyimides, polyamides, and polyimide amides.
  • 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 content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition.
  • the content of other resins in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, still more preferably 60 mass% or less, and even more preferably 50 mass% or less, based on the total solid content of the resin composition.
  • the content of the other resin may be low.
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition.
  • the lower limit of the content is not particularly limited, and may be 0% by mass or more.
  • the 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 in the above range.
  • the resin composition of the present invention preferably contains a polymerizable compound (crosslinking agent).
  • the polymerizable compound may include a radical crosslinking agent or other crosslinking agents.
  • the resin composition of the present invention preferably contains a radical crosslinking agent.
  • the radical crosslinking agent is a compound having a radical polymerizable group.
  • the radical polymerizable group is preferably a group containing an ethylenically unsaturated bond.
  • Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
  • a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.
  • the radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds.
  • the radical crosslinking agent may have three or more ethylenically unsaturated bonds.
  • a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is even more preferable.
  • the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the above-mentioned compound having three or more ethylenically unsaturated bonds.
  • the molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
  • radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and 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.
  • the radical crosslinking agent a radical crosslinking agent having at least one bond selected from the group consisting of a urea bond and a urethane bond (hereinafter, also referred to as "crosslinking agent U") is also preferred.
  • a urethane bond is a bond represented by *--O--C(.dbd.O)-- NR.sub.N --*, where R.sub.N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom.
  • R.sub.N represents a hydrogen atom or a monovalent organic group
  • * represents a bonding site with a carbon atom.
  • the crosslinking agent U may have only one urea bond or one urethane bond, may have one or more urea bonds and one or more urethane bonds, may have no urethane bonds but two or more urea bonds, or may have no urea bonds but two or more urethane bonds.
  • the total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
  • crosslinking agent U When crosslinking agent U has no urethane bond, the number of urea bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When crosslinking agent U has no urea bond, the number of urethane bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
  • the radical polymerizable group in the crosslinking agent U is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. Of these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred.
  • the crosslinking agent U has two or more radically polymerizable groups, the structures of the respective radically polymerizable groups may be the same or different.
  • the number of radical polymerizable groups in the crosslinking agent U may be only one or may be two or more, and is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
  • the radically polymerizable group value (mass of compound per mole of radically polymerizable group) in the crosslinking agent U is preferably 150 to 400 g/mol.
  • the lower limit of the radically polymerizable group value is more preferably 200 g/mol or more, even more preferably 210 g/mol or more, even more preferably 220 g/mol or more, even more preferably 230 g/mol or more, even more preferably 240 g/mol or more, and particularly preferably 250 g/mol or more.
  • the upper limit of the radically polymerizable group value is more preferably 350 g/mol or less, further preferably 330 g/mol or less, and particularly preferably 300 g/mol or less.
  • the polymerizable group value of the crosslinking agent U is preferably from 210 to 400 g/mol, and more preferably from 220 to 400 g/mol.
  • the crosslinking agent U preferably has a structure represented by the following formula (U-1):
  • R U1 is a hydrogen atom or a monovalent organic group
  • A is -O- or -NR N -
  • R N is a hydrogen atom or a monovalent organic group
  • Z U1 is an m-valent organic group
  • Z U2 is an (n+1)-valent organic group
  • X is a radical polymerizable group
  • n is an integer of 1 or more
  • m is an integer of 1 or more.
  • R U1 is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
  • R 3 N is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
  • the above-mentioned hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms.
  • the above-mentioned hydrocarbon group includes a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
  • R N represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.
  • the hydrocarbon group includes the same ones as those exemplified for ZU1 , and preferred embodiments are also the same.
  • X is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group.
  • a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferable, and a (meth)acryloxy group is more preferable.
  • n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2, and particularly preferably 1.
  • m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and further preferably 1 or 2.
  • the cross-linking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group.
  • the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group.
  • the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, still more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group.
  • the alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U.
  • the number of repetitions of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6.
  • crosslinking agent U has an amide group
  • R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.
  • the crosslinking agent U may have, in the molecule, two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (when a polyalkyleneoxy group is formed, the group is a polyalkyleneoxy group), an amide group, and a cyano group. An embodiment having only one such structure in the molecule is also preferred.
  • the hydroxy group, alkyleneoxy group, amide group and cyano group may be present at any position of the crosslinking agent U.
  • the crosslinking agent U is such that at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, amide group and cyano group and at least one radical polymerizable group contained in the crosslinking agent U are linked via a linking group containing a urea bond or a urethane bond (hereinafter, also referred to as "linking group L2-1").
  • the crosslinking agent U contains only one radically polymerizable group
  • the radically polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").
  • the crosslinking agent U contains an alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2
  • the structure bonded to the side of the alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof.
  • hydrocarbon group a hydrocarbon group having 20 or less carbon atoms is preferable, a hydrocarbon group having 18 or less carbon atoms is more preferable, and a hydrocarbon group having 16 or less carbon atoms is even more preferable.
  • hydrocarbon group a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond thereof can be mentioned.
  • a preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking agent U described above.
  • the structure bonded to the side of the amide group opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof.
  • the hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms.
  • examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a bond between these groups.
  • a preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking agent U described above.
  • the carbon atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2.
  • the crosslinking agent U has a hydroxy group.
  • the crosslinking agent U preferably contains an aromatic group.
  • the aromatic group is preferably directly bonded to a urea bond or a urethane bond contained in the crosslinking agent U.
  • the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.
  • the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure.
  • the aromatic heterocyclic group is preferably a 5-membered or 6-membered aromatic heterocyclic group.
  • aromatic heterocyclic ring in such an aromatic heterocyclic group examples include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be further condensed with other rings, such as indole and benzimidazole.
  • the heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the aromatic group is preferably contained in a linking group that links two or more radically polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radically polymerizable group contained in the crosslinking agent U.
  • the number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10.
  • the crosslinking agent U contains two or more urea bonds or urethane bonds in total, when it contains two or more radically polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radically polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond or urethane bond and the radically polymerizable group may be within the above range.
  • the "number of atoms (linking chain length) between a urea bond or a urethane bond and a polymerizable group” refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked that links these objects with the shortest length (minimum number of atoms).
  • the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.
  • the crosslinking agent U is a compound having a structure that does not have an axis of symmetry.
  • the fact that the crosslinking agent U does not have an axis of symmetry means that the compound is a bilaterally asymmetric compound that does not have an axis that would produce an identical molecule to the original molecule by rotating the entire compound.
  • the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that since the crosslinking agent U does not have an axis of symmetry, aggregation of the crosslinking agents U within the composition film is suppressed.
  • the molecular weight of the crosslinking agent U is preferably 100-2,000, more preferably 150-1500, and even more preferably 200-900.
  • the 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.
  • X represents a single bond or a divalent organic group
  • each of R104 independently represents an alkyl group or an acyl group
  • R103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to produce an alkali-soluble group (for example, a group that is eliminated by the action of an acid, a group represented by -C ( R4 ) 2COOR5 (each of R4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R5 represents a group that is eliminated by the action of an acid)).
  • Each R 105 independently represents an alkyl group or an alkenyl group; each of a, b, and c independently represents 1 to 3; d represents 0 to 4; e represents 0 to 3; f represents 0 to 3; a+d is 5 or less; b+e is 4 or less; and c+f is 4 or less.
  • R 5 in a group that decomposes under the action of an acid to generate an alkali-soluble group, a group that is eliminated by the action of an acid, and a group represented by -C(R 4 ) 2 COOR 5 include -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 ), etc.
  • R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group, and R 36 and R 37 may be bonded to each other to form a ring.
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.
  • the alkyl group may be either linear or branched.
  • the above cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.
  • the cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring.
  • the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
  • the aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms.
  • the above aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
  • the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. These groups may further have known substituents.
  • R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
  • the group that decomposes under the action of an acid to generate an alkali-soluble group, or the group that is eliminated under the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably, it is a tertiary alkyl ester group or an acetal group.
  • a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group a compound having at least one group selected from the group consisting of a urea bond and a urethane bond is also preferred.
  • the preferred aspects of the above compounds are the same as the preferred aspects of the crosslinking agent U described above, except that the polymerizable group is not a radically polymerizable group but is at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group.
  • Specific examples of compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an ethylol group include the following structures.
  • Compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compounds has been changed to an acyloxymethyl group.
  • Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
  • the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group may be a commercially available compound or may be synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.
  • melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.
  • urea-based crosslinking agents include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril; Urea-based crosslinking agents such as
  • benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.
  • a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group a compound in which at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) is also preferably used.
  • Such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidene tris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis
  • crosslinking agents may be commercially available, and suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL.
  • 46DMOC 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.)
  • DML-PC DML-PEP
  • DML-OC DML-OEP
  • DML-34X DML-PTBP
  • the resin composition of the present invention also preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the epoxy group undergoes a crosslinking reaction at 200° C. or less, and does not undergo a dehydration reaction due to the crosslinking, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in curing the resin composition at low temperatures and suppressing warping.
  • the epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping.
  • a polyethylene oxide group refers to a group having 2 or more repeating ethylene oxide units, and the number of repeating units is preferably 2 to 15.
  • epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane.
  • bisphenol A type epoxy resins bisphenol F type epoxy resins
  • alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycid
  • Epicron registered trademark, the same applies below
  • Epicron HP-4032 Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron HP-4770, Epicron EXA-830LVP, Epicron EXA-8183, Epicron EXA-8169, Epicron N-660, Epicron N-665-EXP-S, Epicron N-740 (all trade names, manufactured by DIC Corporation), Likaresin (registered trademark, the same applies below) BEO-20E, Likaresin BEO-60E, Likaresin HBE-100, Likaresin DME-100, Likaresin L-200 (all trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (all trade names, manufactured by ADEKA Corporation), Ceroxa Celoxide (registered trademark, the same applies below) 2021P, Celloxide 2081, Celloxide 2000, EHPE3150,
  • n is an integer from 1 to 5
  • m is an integer from 1 to 20.
  • n 1 to 2 and m is 3 to 7 in order to achieve both heat resistance and improved elongation.
  • --Oxetane compound compound having an oxetanyl group
  • the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, etc.
  • Specific examples include the Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., which may be used alone or in combination of two or more kinds.
  • -Benzoxazine compound compound having a benzoxazolyl group
  • Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and further, they reduce thermal shrinkage and suppress the occurrence of warping.
  • benzoxazine compounds include P-d type benzoxazine, F-a type benzoxazine (all trade names, manufactured by Shikoku Kasei Corporation), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more types.
  • the content of the other crosslinking agent is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass%. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total is preferably within the above range.
  • the polymerizable compound includes a moiety having an activation energy (Ea) of 40 to 60 kcal/mol upon dissociation.
  • the polymerizable compound including a moiety having an Ea of 40 to 60 kcal/mol is also referred to as a "polymerizable compound (K)."
  • the polymerizable compound (K) has a moiety with an Ea of 40 to 60 kcal/mol, and is therefore easily dissociated (decomposed), for example, when heated at 230°C for 1 hour.
  • a resin composition containing the polymerizable compound (K) is made into a film, and when exposed to light at 100 mJ/ cm2 , the polymerizable group is polymerized to form a three-dimensional crosslink. Then, when heated at 230°C for 1 hour, the three-dimensional crosslink is released.
  • This embodiment is preferred because it is easy to make the breaking elongation of the film after heating larger than the breaking elongation of the film before heating.
  • the polymerizable compound (K) preferably has a moiety having an Ea of 42 to 58 kcal/mol, more preferably has a moiety having an Ea of 45 to 55 kcal/mol, and further preferably has a moiety having an Ea of 48 to 52 kcal/mol.
  • the method for measuring Ea is the same as that described above.
  • the polymerizable compound (K) is not particularly limited as long as it has a moiety having Ea of 40 to 60 kcal/mol, but it preferably has at least one structure selected from the group consisting of a structure represented by the following formula (3) and a structure represented by the following formula (4):
  • the structure represented by the following formula (3) and the structure represented by the following formula (4) preferably have a moiety having Ea of 40 to 60 kcal/mol.
  • A1 and B1 each independently represent an oxygen atom or NR4 .
  • R4 represents a hydrogen atom or a monovalent organic group.
  • A2 and B2 each independently represent an oxygen atom or NH.
  • R3 represents a divalent hydrocarbon group.
  • * 1 and * 2 indicate binding positions.
  • the resin composition of the present invention preferably contains a polymerization initiator (also referred to as "initiator").
  • the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to contain a photopolymerization initiator.
  • the photopolymerization initiator may be a photoradical polymerization initiator or a photoacid generator.
  • oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.
  • oxime compounds include oxime compounds having specific substituents as disclosed in JP 2007-269779 A and oxime compounds having thioaryl groups as disclosed in JP 2009-191061 A, the contents of which are incorporated herein by reference.
  • At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound is more preferred, and a metallocene compound or an oxime compound is even more preferred.
  • a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
  • two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity.
  • crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time, and improving the stability of the resin composition over time.
  • bifunctional or trifunctional or higher functional photoradical polymerization initiator include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015/004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017/033680, paragraphs 0039 to 0055; compound (E) and compound (G) described in JP-T-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Publication No.
  • the content is preferably 0.1 to 30 mass% based on the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking caused by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.
  • the polymerization initiator may be a photoacid generator.
  • the photoacid generator refers to a compound that generates at least one of a Bronsted acid and a Lewis acid when irradiated with light having a wavelength of 200 nm to 900 nm.
  • the light to be irradiated is preferably light having a wavelength of 300 nm to 450 nm, more preferably light having a wavelength of 330 nm to 420 nm.
  • the photoacid generator is preferably capable of generating an acid by being exposed to light, either alone or in combination with a sensitizer.
  • Preferred examples of the acid to be generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acids, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.
  • photoacid generators examples include quinone diazide compounds, oxime sulfonate compounds, organic halide compounds, organic borate compounds, disulfone compounds, and onium salt compounds. From the viewpoints of sensitivity and storage stability, organic halogen compounds, oxime sulfonate compounds, and onium salt compounds are preferred, and from the viewpoints of the mechanical properties of the film to be formed, oxime esters are preferred.
  • Quinone diazide compounds include those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent hydroxy compound, those in which the sulfonic acid of quinone diazide is ester-bonded to a monovalent or polyvalent amino compound, and those in which the sulfonic acid of quinone diazide is ester-bonded and/or sulfonamide-bonded to a polyhydroxy polyamino compound.
  • hydroxy compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropanol, octanol, t-Bu alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, and BisOC P-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-P CHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-HAP
  • the quinone diazide compound contains an ester of a phenol compound and a 4-naphthoquinone diazide sulfonyl group. This allows for higher sensitivity to i-line exposure and higher resolution.
  • the photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as an "oxime sulfonate compound").
  • the oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably a compound represented by the following formula (OS-1), formula (OS-103), formula (OS-104), or formula (OS-105).
  • X3 represents an alkyl group, an alkoxy group, or a halogen atom. When a plurality of X3s are present, they may be the same or different.
  • the alkyl group and alkoxy group in X3 may have a substituent.
  • the alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • the halogen atom is preferably a chlorine atom or a fluorine atom.
  • m3 represents an integer of 0 to 3, and is preferably 0 or 1. When m3 is 2 or 3, multiple X3s may be the same or different.
  • R 34 represents an alkyl group or an aryl group, and is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W.
  • W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.
  • a compound in which m3 is 3, X3 is a methyl group, the substitution position of X3 is the ortho position, and R34 is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group, or a p-tolyl group is particularly preferred.
  • oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs [0064] to [0068] of JP2011-209692A and paragraphs [0158] to [0167] of JP2015-194674A, the contents of which are incorporated herein by reference.
  • R s1 represents an alkyl group, an aryl group, or a heteroaryl group
  • R s2 which may be present in plurality, each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom
  • R s6 which may be present in plurality, each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group
  • Xs represents O or S
  • ns represents 1 or 2
  • ms represents an integer of 0 to 6.
  • the alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R s1 may have a substituent.
  • R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), more preferably a hydrogen atom or an alkyl group.
  • R s2 which may be present in two or more, it is preferable that one or two are an alkyl group, an aryl group or a halogen atom, more preferably one is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the remaining are hydrogen atoms.
  • the alkyl group or aryl group represented by R s2 may have a substituent.
  • Xs represents O or S, and is preferably O. In the above formulae (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered or 6-membered ring.
  • ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2.
  • the alkyl group (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) represented by R s6 may have a substituent.
  • ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.
  • the compound represented by formula (OS-103) is preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by formula (OS-104) is preferably a compound represented by the following formula (OS-107), and the compound represented by formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109).
  • R u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group.
  • R u9 is preferably a cyano group or an aryl group, and more preferably a cyano group, a phenyl group, or a naphthyl group.
  • R u2a represents an alkyl group or an aryl group.
  • Xu represents —O—, —S—, —NH—, —NR u5 —, —CH 2 —, —CR u6 H— or —CR u6 R u7 —, and R u5 to R u7 each independently represent an alkyl group or an aryl group.
  • R u1 to R u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, or an aryl group.
  • Two of R u1 to R u4 may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring with the benzene ring.
  • R u1 to R u4 are preferably a hydrogen atom, a halogen atom, or an alkyl group.
  • R u1 to R u4 may be bonded to each other to form an aryl group.
  • R u1 to R u4 are all hydrogen atoms. Any of the above-mentioned substituents may further have a substituent.
  • the compound containing at least one oxime sulfonate group is more preferably a compound represented by formula (OS-102).
  • the stereochemical structures (E, Z, etc.) of the oxime and benzothiazole rings may each be either one or a mixture.
  • Specific examples of the compound represented by formula (OS-101) include the compounds described in paragraphs [0102] to [0106] of JP-A-2011-209692 and paragraphs [0195] to [0207] of JP-A-2015-194674, the contents of which are incorporated herein by reference.
  • the following b-9, b-16, b-31, and b-33 are preferable.
  • WPAG-336 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • WPAG-443 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • MBZ-101 manufactured by Midori Chemical Industries, Ltd.
  • organic halogenated compounds include the compounds described in paragraphs 0042 to 0043 of JP 2015-087409 A, the contents of which are incorporated herein by reference.
  • 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 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.
  • dimethyl sulfoxide is preferred.
  • 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 compounds described in paragraph 0316 of International Publication No. 2021/112189 and compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference. 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 compound as the silane coupling agent. In the following formula, Me represents a methyl group and Et represents an ethyl group.
  • 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 -(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethy
  • 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 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, and phenoxazine. The contents of this specification are incorporated herein.
  • 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 acid scavenger has an onium structure
  • the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid having a lower acidity than the acid generated by the acid generator.
  • acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole.
  • acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene.
  • acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxides having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris(t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylsulfonium hydroxide, and 2-oxopropylthiophenium hydroxide.
  • Examples of acid scavengers having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine.
  • Examples of acid scavengers having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline.
  • Examples of acid scavengers having a pyridine structure include pyridine and 4-methylpyridine.
  • Examples of alkylamine derivatives having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine.
  • Examples of aniline derivatives having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.
  • preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N- Examples include methylhexylamine, N-methyldicyclohex,
  • the acid scavenger may be used alone or in combination of two or more types.
  • the composition according to the present invention may or may not contain an acid scavenger, but if it does contain one, the content of the acid scavenger is preferably 0.001 to 10 mass %, and more preferably 0.01 to 5 mass %, based on the total solid content of the composition.
  • the acid generator/acid scavenger (molar ratio) is preferably 5.0 to 200, and more preferably 7.0 to 150.
  • 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, aggregation inhibitors, phenolic compounds, other polymer compounds, light absorbers, 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, aggregation inhibitors, phenolic compounds, other polymer compounds, light absorbers, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained.
  • auxiliaries e.g., defoamers, flame retardants, etc.
  • surfactant various surfactants such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc.
  • the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
  • the liquid properties (particularly fluidity) when the coating liquid composition is prepared can be further improved, and the uniformity of the coating thickness and liquid saving can be further improved.
  • the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and improving the coatability of the surface to be coated. This makes it possible to more suitably form a uniform film with minimal thickness unevenness.
  • fluorosurfactants examples include compounds described in paragraph 0328 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • a fluorine-based surfactant a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used, and examples thereof include the following compounds.
  • the weight average molecular weight of the above compound is preferably from 3,000 to 50,000, and more preferably from 5,000 to 30,000.
  • a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorosurfactant.
  • Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein by reference.
  • examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., manufactured by DIC Corporation.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorine surfactants with a fluorine content within this range are effective in terms of uniformity of the coating film thickness and liquid saving, and also have good solubility in the composition.
  • silicone surfactants examples include the compounds described in paragraphs 0329 to 0334 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • Higher fatty acid derivative In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the resin composition of the present invention, and the higher fatty acid derivative may be unevenly distributed on the surface of the resin composition of the present invention during drying after application.
  • the higher fatty acid derivative may be a compound described in paragraph 0155 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.
  • the content of the higher fatty acid derivative is preferably 0.1 to 10 mass% based on the total solid content of the resin composition. There may be only one type of higher fatty acid derivative, or two or more types. When there are two or more types of higher fatty acid derivatives, the total is preferably within the above range.
  • 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.
  • 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.
  • the content of the antioxidant is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
  • the content of the antioxidant is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
  • the anti-aggregating agents may be used alone or in combination of two or more.
  • the content of the anti-aggregating agent is preferably 0.01 mass % or more and 10 mass % or less, and more preferably 0.02 mass % or more and 5 mass % or less, relative to the total solid mass of the resin composition.
  • the phenol-based compounds may be used alone or in combination of two or more.
  • the content of the phenol-based compound is preferably 0.01 mass % or more and 30 mass % or less, and more preferably 0.02 mass % or more and 20 mass % or less, relative to the total solid mass of the resin composition.
  • Examples of the other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof, etc.
  • the other polymer compounds may be modified by introducing a crosslinking group such as a methylol group, an alkoxymethyl group, or an epoxy group.
  • the other polymer compounds may be used either individually or in combination of two or more.
  • the content of the other polymer compounds is preferably 0.01 mass % or more and 30 mass % or less, and more preferably 0.02 mass % or more and 20 mass % or less, relative to the total solid mass of the resin composition.
  • the resin composition of the present invention may further contain a light absorber (a compound whose absorbance at the exposure wavelength decreases upon exposure).
  • a light absorber a compound whose absorbance at the exposure wavelength decreases upon exposure.
  • Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022/202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of which are incorporated herein by reference.
  • a photochromic compound is a compound whose absorption spectrum changes as a result of the molecular geometric structure being changed by the absorption of light. Specific examples of photochromic compounds are shown below, but the present invention is not limited to these.
  • the light absorber is preferably at least one selected from the group consisting of naphthoquinone diazide compounds, spiropyran compounds, diarylethene compounds, azobenzene compounds, nifedipine compounds, and coumarin compounds.
  • the content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.
  • One embodiment (second aspect) of the resin composition of the present invention is a resin composition containing at least one resin selected from the group consisting of a structure represented by the following formula (1) and a structure represented by the following formula (2).
  • X 1 , X 2 , Y 1 and Y 2 each independently represent an organic group.
  • W 1 , W 2 , W 3 and W 4 each independently represent a single bond or a divalent organic group.
  • P 1 , P 2 , P 3 and P 4 each independently represent a group containing a moiety having an activation energy of 40 to 60 kcal/mol upon dissociation.
  • Q 1 , Q 2 , Q 3 and Q 4 each independently represent a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group or a hydrogen atom.
  • a, b, c, and d each independently represent an integer of 0 or more, provided that at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more.
  • m, n, p and q each independently represent an integer of 1 or more.
  • the resin in the resin composition of the second embodiment is the resin (A) in the first embodiment.
  • the resin (A) is as described above.
  • the resin composition of the second embodiment may contain components other than the resin (A), and the explanation of the components other than the resin (A) is the same as that in the first embodiment described above.
  • One embodiment (third aspect) of the resin composition of the present invention is a resin composition containing at least one resin selected from the group consisting of a structure represented by the following formula (1) and a structure represented by the following formula (2).
  • X 1 , X 2 , Y 1 and Y 2 each independently represent an organic group.
  • W 1 , W 2 , W 3 and W 4 each independently represent a single bond or a divalent organic group.
  • P 1 , P 2 , P 3 and P 4 each independently represent a group having at least one type of structure selected from the group consisting of a structure represented by the following formula (3) and a structure represented by the following formula (4).
  • Q 1 , Q 2 , Q 3 and Q 4 each independently represent a monovalent organic group, a halogen atom, a nitro group, an amino group, a hydroxyl group, a thiol group or a hydrogen atom.
  • a, b, c, and d each independently represent an integer of 0 or more, provided that at least one of a and b represents an integer of 1 or more, and at least one of c and d represents an integer of 1 or more.
  • m, n, p and q each independently represent an integer of 1 or more.
  • A1 and B1 each independently represent an oxygen atom or NR4 .
  • R4 represents a hydrogen atom or a monovalent organic group.
  • A2 and B2 each independently represent an oxygen atom or NH.
  • R3 represents a divalent hydrocarbon group.
  • * 1 and * 2 indicate binding positions.
  • the resin in the resin composition of the third embodiment is the resin (Ab) in the first embodiment.
  • the resin (Ab) is as described above.
  • the resin composition of the third embodiment may contain components other than the resin (Ab), and the description of the components other than the resin (Ab) is the same as that in the first embodiment described above.
  • One embodiment (fourth aspect) of the resin composition of the present invention is a resin composition containing at least one resin selected from the group consisting of polyimides and polyimide precursors, and a polymerizable compound,
  • the polymerizable compound is a resin composition containing a moiety having an activation energy of 40 to 60 kcal/mol upon dissociation.
  • the polymerizable compound in the resin composition of the fourth embodiment is preferably the polymerizable compound (K) described in the first embodiment.
  • the resin composition of the fourth embodiment may contain at least one resin selected from the group consisting of polyimides and polyimide precursors, and a component other than the polymerizable compound.
  • the at least one resin selected from the group consisting of polyimides and polyimide precursors, and the component other than the polymerizable compound are the same as those in the first embodiment described above.
  • the content of at least one resin selected from the group consisting of polyimide and polyimide precursor in the resin composition of the fourth embodiment 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 at least one resin selected from the group consisting of polyimide and polyimide precursor in the resin composition of the fourth embodiment 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 fourth aspect may contain only one of the above resins, or may contain two or more of them. When two or more of them are contained, it is preferable that the total amount is in the above range.
  • the content of the polymerizable compound containing a moiety having an activation energy of 40 to 60 kcal/mol upon dissociation is preferably more than 0% by mass and not more than 60% by mass, based on the total solid content of the resin composition.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
  • the polymerizable compound containing a moiety having an activation energy of 40 to 60 kcal/mol upon dissociation may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.
  • the content of at least one resin selected from the group consisting of polyimide and polyimide precursor in the resin composition of the fifth embodiment 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 at least one resin selected from the group consisting of polyimide and polyimide precursor in the resin composition of the fifth embodiment 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 fifth aspect may contain only one of the above resins, or may contain two or more of them. When two or more of them are contained, it is preferable that the total amount is in the above range.
  • 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, 1,000 mm 2 /s to 12,000 mm 2 /s is preferable, 2,000 mm 2 /s to 10,000 mm 2 /s is more preferable, and 2,500 mm 2 /s to 8,000 mm 2 /s is even more preferable. If it is within the above range, it is easy to obtain a coating film with high uniformity.
  • 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 be a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept substantially stationary on the substrate, a step in which the rinsing liquid is vibrated on the substrate by ultrasonic waves or the like, or 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 development process may include a step of contacting the pattern with a processing liquid after the treatment with the developer or after the pattern is washed with a rinsing liquid. Also, a method may be adopted in which the processing liquid is supplied before the developer or rinsing liquid in contact with the pattern is completely dried.
  • the treatment liquid includes a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator.
  • Preferred aspects of the organic solvent, and at least one of the basic compound and the base generator are the same as the preferred aspects of the organic solvent, and at least one of the basic compound and the base generator used in the above-mentioned rinse solution.
  • the method of supplying the processing liquid to the pattern can be the same as the above-mentioned method of supplying the rinsing liquid, and the preferred embodiments are also the same.
  • the content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the treatment liquid.
  • the lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
  • the content of the basic compound or base generator is preferably 70 to 100 mass % based on the total solid content of the treatment liquid.
  • the treatment liquid may contain only one kind of at least one of the basic compound and the base generator, or may contain two or more kinds.
  • the total amount thereof is preferably within the above range.
  • the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) is preferably 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 preferably includes 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. In the heating step, the resin such as the polyimide precursor is cyclized to become a resin such as a polyimide.
  • the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.
  • the heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of the base generated from the base generator through heating.
  • the heating step is preferably performed at a temperature rise rate of 1 to 12° C./min from the starting temperature to the maximum heating temperature.
  • the temperature rise rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min.
  • the temperature is increased from the starting temperature to the maximum heating temperature at a rate of preferably 1 to 8° C./sec, more preferably 2 to 7° C./sec, and even more preferably 3 to 6° C./sec.
  • the temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C.
  • the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature begins.
  • the resin composition of the present invention when applied to a substrate and then dried, it is the temperature of the film (layer) after drying, and it is preferable to raise the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.
  • the heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
  • the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher.
  • the upper limit of the heating temperature is preferably 350° C. or less, more preferably 250° C. or less, and even more preferably 240° C. or less.
  • Heating may be performed stepwise. For example, a process may be performed in which the temperature is increased from 25°C to 120°C at 3°C/min, held at 120°C for 60 minutes, increased from 120°C to 180°C at 2°C/min, and held at 180°C for 120 minutes. It is also preferable to perform the process while irradiating ultraviolet rays as described in U.S. Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment process is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps, for example, a first pretreatment process may be performed in the range of 100 to 150°C, and then a second pretreatment process may be performed in the range of 150 to 200°C. Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C./min.
  • the heating step is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by performing the heating step under reduced pressure, etc.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
  • the heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.
  • the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step.
  • the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
  • the post-development exposure step for example, a reaction in which cyclization of a polyimide precursor or the like proceeds due to exposure of a photobase generator to light, or a reaction in which elimination of an acid-decomposable group proceeds due to exposure of a photoacid generator to light, can be promoted.
  • the post-development exposure step it is sufficient that at least a part of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed.
  • the exposure dose in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , and more preferably 100 to 15,000 mJ/cm 2 , calculated as exposure energy at a wavelength to which the photosensitive compound has sensitivity.
  • the post-development exposure step can be carried out, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.
  • the pattern obtained by the development step may be subjected to a metal layer forming step in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the development step (preferably subjected to at least one of a heating step and a post-development exposure step).
  • the metal layer can be made of any existing metal type without any particular limitations, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.
  • the method for forming the metal layer is not particularly limited, and existing methods can be applied.
  • the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used.
  • photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations of these methods are possible.
  • examples of the method include a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating.
  • a preferred embodiment of plating is electrolytic plating using a copper sulfate or copper cyanide plating solution.
  • the thickness of the metal layer at its thickest point is preferably 0.01 to 50 ⁇ m, and more preferably 1 to 10 ⁇ m.
  • Examples of the field of application of the method for producing the cured product of the present invention or the cured product include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc.
  • Other examples include etching patterns of sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or insulating films for mounting applications such as those described above.
  • the method for producing the cured product of the present invention or the cured product of the present invention can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, and for producing protective lacquers and dielectric layers in electronics, especially microelectronics.
  • the laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention.
  • the laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers.
  • at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.
  • the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention multiple times.
  • the laminate of the present invention preferably includes two or more layers made of a cured product, and includes a metal layer between any two of the layers made of the cured product.
  • the metal layer is preferably formed by the metal layer forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer made of a cured product between the steps for producing a cured product which are performed multiple times.
  • a preferred embodiment of the metal layer forming step is as described above.
  • a laminate having at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order can be mentioned as a preferred example.
  • the layer made of the first cured product and the layer made of the second cured product are preferably layers made of the cured product of the present invention.
  • the resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions.
  • the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
  • the method for producing the laminate of the present invention preferably includes a lamination step.
  • the lamination process is a series of processes including performing at least one of (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) a heating process and a post-development exposure process again on the surface of the pattern (resin layer) or metal layer in this order.
  • at least one of (a) the film formation process and (d) the heating process and the post-development exposure process may be repeated.
  • a metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying process and the like as appropriate.
  • a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step.
  • An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.
  • the lamination step is preferably carried out 2 to 20 times, and more preferably 2 to 9 times.
  • a structure of 2 to 20 resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred.
  • the layers may be the same or different in composition, shape, film thickness, etc.
  • a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.
  • a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.
  • the following may be repeated in this order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step; or (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step.
  • the method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
  • the surface activation treatment step is usually carried out after the metal layer formation step, but after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be subjected to a surface activation treatment step before the metal layer formation step is carried out.
  • the surface activation treatment may be performed on at least a part of the metal layer, or on at least a part of the resin composition layer after exposure, or on at least a part of both the metal layer and the resin composition layer after exposure.
  • the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the area of the metal layer on which the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface can be improved. It is preferable to perform the surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface that has been surface-activated.
  • the resin composition layer when performing negative development, etc., when the resin composition layer is cured, it is less likely to be damaged by the surface treatment, and the adhesion is likely to be improved.
  • the surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • the present invention also discloses a method for manufacturing an interlayer insulating film for a redistribution layer.
  • the method for producing an interlayer insulating film for a rewiring layer of the present invention comprises the steps of: a photosensitive film forming step of applying the resin composition of the present invention onto a substrate to form a photosensitive film; an exposure step of exposing the photosensitive film to light to form an exposed film; a pattern forming step of developing the exposed film with a developer to form an insulating pattern; a heating step of heating the insulating pattern; Includes.
  • the photosensitive film forming step is the same as the film forming step in the above-mentioned method for producing a cured product.
  • the exposure step is the same as the exposure step in the above-mentioned method for producing a cured product.
  • the exposure step can promote three-dimensional crosslinking of the resin.
  • the pattern forming step is the same as the developing step in the above-mentioned method for producing a cured product.
  • the heating step is the same as the heating step in the above-mentioned method for producing a cured product.
  • the heating step can release the three-dimensional crosslinking of the resin promoted in the exposure step.
  • the method for producing an interlayer insulating film for a redistribution layer of the present invention may include steps other than those described above. Examples of the steps other than those described above include the steps described in the method for producing a cured product.
  • 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 present invention also relates to the above-mentioned resin (Ab).
  • the resin (Ab) has been described above.
  • TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl
  • 4-aminostyrene 1.66 g (1.66 mmol) of 4-aminostyrene were added at room temperature (23°C) and stirred for 2 hours, after which 49.0 g (354 mmol) of pyridine and 13.9 g (142 mmol) of maleic anhydride were added and stirred at 60°C for 3 hours.
  • EDCI 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide
  • the mixture was extracted with 150 ml of ethyl acetate, and the organic layer was removed.
  • 500 ml of ethyl acetate was added, and the mixture was extracted with concentrated hydrochloric acid to adjust the pH to 2 to 3.
  • the obtained ethyl acetate solution was washed three times with saturated saline and dried over magnesium sulfate. After filtering to remove magnesium sulfate, 0.1 TEMPO was added, and the ethyl acetate was concentrated under reduced pressure to obtain a carboxylic acid.
  • the resulting carboxylic acid was then dissolved in 50 ml of acetonitrile, and 69.0 g (360 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDCI) hydrochloride and 60.1 g (360 mmol) of aminoethoxy methacrylate hydrochloride were added.
  • the mixture was cooled to 0°C, and 36.4 g (360 mmol) of triethylamine was added dropwise over 15 minutes, followed by stirring at room temperature for 3 hours.
  • the ethyl acetate solution was washed three times with saturated saline and dried over magnesium sulfate. After filtering to remove the magnesium sulfate, 0.1 g of TEMPO was added and the ethyl acetate was concentrated under reduced pressure to obtain G-2.
  • Examples and Comparative Examples> In each of the Examples and Comparative Examples, the components shown in Tables 1 to 3 below were mixed to obtain a resin composition. Specifically, the content of each component other than the solvent shown in Tables 1 to 3 was the amount (parts by mass) shown in the "parts by mass” row. When two or more compounds were used as each component, the "type” and “parts by mass” were listed separated by "/". In these columns, the order of listing separated by "/" corresponds to each other. The amount of the solvent used was adjusted so that the solid content concentration was as shown in the "Solid content concentration (mass %)" column of Tables 1 to 3. The "type” and “mass ratio” of the solvents used are shown in Tables 1 to 3.
  • the “mass ratio” of the solvent is the content (mass %) of each type of solvent relative to the total solvent.
  • the notation "-" indicates that the resin composition does not contain the corresponding component.
  • the obtained resin composition was pressure filtered using a polytetrafluoroethylene filter having a pore width of 0.5 ⁇ m.
  • A-1 is a polyimide having a main chain made up of repeating units bracketed in [ ].
  • A-1 has a crosslinkable group represented by formula (EC1) and a crosslinkable group represented by formula (EC2) at the ends of the main chain.
  • *a to *d represent bonding positions.
  • the repeating units are bonded to each other at *a and *b.
  • the crosslinkable group represented by formula (EC1) is bonded to *a at *c.
  • the crosslinkable group represented by formula (EC2) is bonded to *b at *d.
  • A-2 is a polyimide having a main chain made up of repeating units bracketed in [ ].
  • A-2 has a crosslinkable group represented by formula (EC3) and a crosslinkable group represented by formula (EC4) at the ends of the main chain.
  • *a to *d represent bonding positions.
  • the repeating units are bonded to each other at *a and *b.
  • the crosslinkable group represented by formula (EC3) is bonded to *a at *c.
  • the crosslinkable group represented by formula (EC4) is bonded to *b at *d.
  • A-3 is a polyimide having a main chain made up of repeating units bracketed in [ ].
  • A-3 has a crosslinkable group represented by formula (EC5) and a crosslinkable group represented by formula (EC6) at the ends of the main chain.
  • *a to *d represent bonding positions.
  • the repeating units are bonded to each other at *a and *b.
  • the crosslinkable group represented by formula (EC5) is bonded to *a at *c.
  • the crosslinkable group represented by formula (EC6) is bonded to *b at *d.
  • A-4 is a polyamide (polyimide precursor) with a main chain consisting of repeating units enclosed in [ ].
  • *a and *b represent bonding positions. Repeating units are bonded to each other at *a and *b.
  • A-5 is a polyamide (polyimide precursor) with a main chain consisting of repeating units enclosed in [ ].
  • *a and *b represent bonding positions. Repeating units are bonded to each other at *a and *b.
  • A-6 is a polyimide having a main chain made up of repeating units bracketed in [ ].
  • A-6 has a crosslinkable group represented by formula (EC7) and a crosslinkable group represented by formula (EC8) at the ends of the main chain.
  • *a to *d represent bonding positions.
  • the repeating units are bonded to each other at *a and *b.
  • the crosslinkable group represented by formula (EC7) is bonded to *a at *c.
  • the crosslinkable group represented by formula (EC8) is bonded to *b at *d.
  • A-7 is a polyamide (polyimide precursor) with a main chain in which repeating units enclosed in [ ] are randomly bonded.
  • *a to *d represent the bonding positions. Repeating units are bonded together at *a or *c and *b or *d.
  • A-8 is a polyamideimide having a main chain in which repeating units enclosed in [ ] are randomly bonded, and is also a polyimide precursor.
  • *a to *d represent the bonding positions. Repeating units are bonded together at *a or *c and *b or *d.
  • A-9 is a polyimide having a main chain made up of repeating units bracketed in [ ].
  • A-9 has a crosslinkable group represented by formula (EC9) and a crosslinkable group represented by formula (EC10) at the ends of the main chain.
  • *a to *f represent bonding positions.
  • the repeating units are bonded to each other at *a or *c and *b or *d.
  • the crosslinkable group represented by formula (EC9) is bonded to *a or *c at *e.
  • the crosslinkable group represented by formula (EC10) is bonded to *b or *d at *f.
  • B-1 is a polyimide with a main chain in which repeating units enclosed in [ ] are randomly bonded.
  • *a to *d represent the bonding positions. Repeating units are bonded together at *a or *c and *b or *d.
  • B-2 is a polyamide with a main chain made up of repeating units enclosed in [ ].
  • *a and *b represent bonding positions. Repeating units are bonded to each other at *a and *b.
  • B-4 is a polyamide (polyimide precursor) with a main chain consisting of repeating units enclosed in [ ].
  • *a and *b represent bonding positions. Repeating units are bonded to each other at *a and *b.
  • the Mn and Mw of each resin are shown in Table 4 below.
  • thermo base generator The structural formula of the compound used as the thermal base generator is shown below.

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Abstract

L'invention concerne : une composition de résine contenant au moins une résine choisie dans le groupe constitué par les polyimides et les précurseurs de polyimides, la composition de résine étant formée en un film, et lorsque le film est exposé à de la lumière à 100 mJ/cm2 et chauffé à 230 °C pendant 1 heure, l'allongement à la rupture du film après chauffage est supérieur à l'allongement à la rupture du film avant chauffage ; et un procédé de production d'un film isolant intercouche pour une couche de redistribution à l'aide de la composition de résine.
PCT/JP2024/033668 2023-09-29 2024-09-20 Composition de résine et procédé de production d'un film isolant intercouche pour couche de redistribution Pending WO2025070302A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05232701A (ja) * 1992-02-20 1993-09-10 Hitachi Chem Co Ltd 感光性樹脂組成物
JPH07196917A (ja) * 1993-12-28 1995-08-01 Shin Etsu Chem Co Ltd 感光性樹脂組成物及びそれを用いるパターン化されたポリイミド皮膜の形成方法
JPH07207026A (ja) * 1993-12-17 1995-08-08 Internatl Business Mach Corp <Ibm> 感光性ポリイミド前駆体
JP2011180571A (ja) * 2010-03-01 2011-09-15 Eternal Chemical Co Ltd 感光性樹脂組成物およびその用途
WO2021075305A1 (fr) * 2019-10-18 2021-04-22 富士フイルム株式会社 Composition durcissable négative, film durci, stratifié, procédé de fabrication de film durci, et dispositif à semi-conducteur
JP2021123652A (ja) * 2020-02-05 2021-08-30 富士フイルム株式会社 樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05232701A (ja) * 1992-02-20 1993-09-10 Hitachi Chem Co Ltd 感光性樹脂組成物
JPH07207026A (ja) * 1993-12-17 1995-08-08 Internatl Business Mach Corp <Ibm> 感光性ポリイミド前駆体
JPH07196917A (ja) * 1993-12-28 1995-08-01 Shin Etsu Chem Co Ltd 感光性樹脂組成物及びそれを用いるパターン化されたポリイミド皮膜の形成方法
JP2011180571A (ja) * 2010-03-01 2011-09-15 Eternal Chemical Co Ltd 感光性樹脂組成物およびその用途
WO2021075305A1 (fr) * 2019-10-18 2021-04-22 富士フイルム株式会社 Composition durcissable négative, film durci, stratifié, procédé de fabrication de film durci, et dispositif à semi-conducteur
JP2021123652A (ja) * 2020-02-05 2021-08-30 富士フイルム株式会社 樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス

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