JP7836801B2 - Resin compositions, cured products, laminates, methods for manufacturing cured products, and semiconductor devices, and compounds - Google Patents

Description

This invention relates to resin compositions, cured products, laminates, methods for producing cured products, semiconductor devices, and compounds.

Cyclic resins such as polyimide are used in a variety of applications due to their excellent heat resistance and insulation properties. While not limited to these applications, examples in semiconductor devices for packaging include their use as insulating films, encapsulants, or protective films. They are also used as base films and coverlays for flexible substrates.

For example, in the applications described above, cyclized resins such as polyimide are used in the form of a resin composition containing at least one of the cyclized resin such as polyimide and a precursor of the cyclized resin.
Such a resin composition can be applied to a substrate, for example by coating, to form a photosensitive film, and then, if necessary, exposure, development, heating, etc., can be performed to form a cured product on the substrate.
The precursors of the cyclized resin, such as polyimide precursors, are cyclized, for example, by heating, and become cyclized resins such as polyimide in the cured product.
Since the resin composition can be applied by known coating methods, it can be said to have excellent manufacturing adaptability, such as a high degree of freedom in designing the shape, size, and application location of the resin composition when applied. In addition to the high performance of cyclized resins such as polyimides, the industrial application development of the above-mentioned resin composition is increasingly expected from the standpoint of such excellent manufacturing adaptability.

For example, Patent Document 1 describes a method for producing a patterned cured film, which includes the steps of: applying a photosensitive resin composition containing (A) a polyimide precursor having polymerizable unsaturated bonds, (B) a polymerizable monomer, (C) a photopolymerization initiator, and (D) a thermal radical generator onto a substrate and drying it to form a photosensitive resin film; pattern exposing the photosensitive resin film to obtain a resin film; developing the resin film after pattern exposure using an organic solvent to obtain a patterned resin film; and heat-treating the patterned resin film.

Japanese Patent Publication No. 2020-056934

In resin compositions for obtaining cured products, excellent storage stability of the resin composition is required.

The present invention aims to provide a resin composition with excellent storage stability, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, a semiconductor device containing the cured product or the laminate, and a novel compound.

Examples of typical embodiments of the present invention are shown below.
<1> Contains a cyclized resin or its precursor,
A resin composition in which the content of carboxylic acid anhydride relative to the total mass of the resin composition is 0.5% by mass or less.
<2> The resin composition according to <1>, comprising a silane coupling agent.
<3> The resin composition according to <2>, wherein the silane coupling agent comprises compound A having at least one group selected from the group consisting of a hydroxyl group, an amino group, and a thiol group, at least one group consisting of an amide group and an ester group, and a group represented by the following formula (S-1).
In formula (S-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, x represents an integer between 1 and 3, and * represents a bonding site with another structure.
<4> Cyclic resins or their precursors,
Compound A comprises at least one group selected from the group consisting of hydroxyl groups, amino groups, and thiol groups, at least one group consisting of an amide group and an ester group, and a group represented by the following formula (S-1).
Resin composition.
In formula (S-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, x represents an integer between 1 and 3, and * represents a bonding site with another structure.
<5> The resin composition according to <3> or <4>, wherein compound A is a compound represented by formula (1-1).
In formula (1-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, L represents an m+n valence linking group containing an amide group or an ester group, x represents an integer between 1 and 3, m represents an integer of 1 or more, and n represents an integer of 1 or more.
<6> The resin composition according to <5>, wherein the carbon atom contained in L in formula (1-1), which is directly bonded to the hydroxyl group in formula (1-1), is a carbon atom that constitutes an aliphatic hydrocarbon group.
<7> The resin composition according to any one of <3> to <6>, wherein compound A is a compound represented by formula (2-1).
In formula (2-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, ^L1 represents a single bond or a divalent linking group, Z represents an amide group, the orientation of the amide group in Z is not particularly limited, ^L2 represents a single bond or a divalent linking group, Ar represents an aromatic group, X represents an alkylene group, and x represents an integer between 1 and 3.
<8> The resin composition according to any one of <3> to <7>, wherein the molecular weight of compound A is 300 to 1,000.
<9> A resin composition according to any one of <1> to <8>, comprising a photopolymerization initiator.
<10> A resin composition according to any one of <1> to <9>, comprising a polymerizable compound.
<11> A resin composition according to any one of <1> to <10>, comprising a base generating agent.
<12> A resin composition according to any one of <1> to <11>, used for forming an interlayer insulating film for a redistribution layer.
<13> A cured product obtained by curing any one of the resin compositions described in <1> to <12>.
<14> A laminate comprising two or more layers made of the cured material described in <13>, wherein a metal layer is included between any of the layers made of the cured material.
<15> A method for producing a cured product, comprising a film-forming step of applying a resin composition described in any one of <1> to <12> onto a substrate to form a film.
<16> A method for producing a cured product according to <15>, comprising an exposure step of selectively exposing the above film and a developing step of developing the above film using a developer to form a pattern.
<17> A method for producing a cured product according to <15> or <16>, comprising a heating step of heating the above film to 50 to 450°C.
<18> A semiconductor device comprising the cured product described in <13> or the laminate described in <14>.
<19> A compound represented by formula (2-1).
In formula (2-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, ^L1 represents a single bond or a divalent linking group, Z represents an amide group, the orientation of the amide group in Z is not particularly limited, ^L2 represents a single bond or a divalent linking group, Ar represents an aromatic group, X represents an alkylene group, and x represents an integer between 1 and 3.

According to the present invention, a resin composition with excellent storage stability, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, a semiconductor device containing the cured product or the laminate, and a novel compound are provided.

The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments specified.
In this specification, a numerical range represented by the symbol "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively.
In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes insofar as they achieve their intended function.
In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both groups (atomic groups) with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups.
In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation.
In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate,""(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl."
In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, total solids refers to the total mass of all components of the composition excluding the solvent. In this specification, solids concentration refers to the mass percentage of the components other than the solvent relative to the total mass of the composition.
In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220 GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, if THF is unsuitable as an eluent, such as in cases of low solubility, NMP (N-methyl-2-pyrrolidone) can be used. Furthermore, unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector.
In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that the other layer is above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward.
In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component. Furthermore, unless otherwise specified, the content of each component in a composition means the total content of all compounds corresponding to that component.
In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.
In this specification, a preferred combination of embodiments is a more preferred embodiment.

(Resin composition)
The resin composition according to the first aspect of the present invention comprises a cyclized resin or a precursor thereof, wherein the content of carboxylic acid anhydride relative to the total mass of the resin composition is 0.5% by mass or less.
A resin composition according to a second aspect of the present invention comprises a cyclized resin or a precursor thereof, and a compound A having at least one group selected from the group consisting of a hydroxyl group, an amino group, and a thiol group, at least one group consisting of an amide group and an ester group, and a group represented by the following formula (S-1).
Hereinafter, the resin composition according to the first embodiment and the resin composition according to the second embodiment will be collectively referred to simply as "resin composition".

The resin composition of the present invention is preferably used to form a photosensitive film subjected to exposure and development, and more preferably used to form a film subjected to exposure and development using a developer solution containing an organic solvent.
The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for redistribution layers.
Furthermore, the resin composition of the present invention may be used to form a photosensitive film for positive-type development, or for forming a photosensitive film for negative-type development.
In the present invention, negative development refers to development in which unexposed areas are removed by development, and positive development refers to development in which exposed areas are removed by development.
As the above-mentioned exposure method, developer, and developing method, for example, the exposure method, developer, and developing method described in the exposure step, developing step, and developing steps described in the description of the manufacturing method of the cured product described later may be used.

The resin composition of the present invention exhibits excellent storage stability.
The mechanism by which the above effects are achieved is unknown, but it is speculated to be as follows.

Conventionally, resin compositions containing cyclized resins or their precursors have been used in various fields.
The present inventors have found that a resin composition with excellent storage stability can be obtained by having a carboxylic acid anhydride content of 0.5% by mass or less relative to the total mass of the resin composition, or by including a cyclized resin or its precursor, and compound A having at least one group selected from the group consisting of a hydroxyl group, an amino group, and a thiol group, at least one of an amide group and an ester group, and a group represented by formula (S-1), or by including a compound represented by formula (2-1) in the resin composition.
Although the mechanism by which the above effects are obtained is unknown, it is presumed that the reaction between the carboxylic acid anhydride and other components, such as cyclizing resins or their precursors, is suppressed because the carboxylic acid anhydride content is 0.5% by mass or less, and that the content of carboxylic acid anhydride introduced into the composition can be reduced by using compound A or the compound represented by formula (2-1) as a silane coupling agent.
Furthermore, it is presumed that a composition containing compound A or the compound represented by formula (2-1) will yield a cured film with excellent adhesion to metal or silicon wafers.

Here, Patent Document 1 does not describe the content of carboxylic acid anhydride, compound A, or the compound represented by formula (2-1).

The components contained in the resin composition of the present invention and their physical properties will be described in detail below.
Hereinafter, cyclized resins and their precursors will also be referred to as "specific resins."

<Carboxylic acid anhydride content>
The resin composition according to the first aspect of the present invention has a carboxylic acid anhydride content of 0.5% by mass or less relative to the total mass of the resin composition.
Here, the carboxylic acid anhydride content is measured by the method shown in the examples described later.
The above content is preferably 0.3% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less. The lower limit of the above content is not particularly limited and may be 0% by mass.
Furthermore, if the resin composition contains a silane coupling agent, the content of carboxylic acid anhydride relative to the total mass of the silane coupling agent is preferably 0.3% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less. The lower limit of the above content is not particularly limited and may be 0% by mass.
In the second aspect of the present invention, the resin composition preferably contains 0.5% by mass or less of carboxylic acid anhydride relative to the total mass of the resin composition.
In the resin composition according to the second aspect of the present invention, the preferred ranges for the content of carboxylic acid anhydride relative to the total mass of the resin composition and the content of carboxylic acid anhydride relative to the total mass of the silane coupling agent are the same as the preferred ranges for these contents in the resin composition according to the first aspect of the present invention described above.

<Specific resins>
The resin composition of the present invention comprises at least one resin (specific resin) selected from the group consisting of cyclized resins and their precursors.
The cyclized resin is preferably a resin that contains an imide ring structure or an oxazole ring structure in its main chain structure.
In this invention, the main chain refers to the relatively longest bonding chain within the resin molecule.
Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide.
A precursor of a cyclized resin is a resin that undergoes a change in chemical structure due to external stimuli to become a cyclized resin. Resins that undergo a change in chemical structure due to heat to become a cyclized resin are preferred, and resins that undergo a ring-closing reaction due to heat to form a ring structure to become a cyclized resin are more preferred.
Examples of precursors for cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors.
In other words, the resin composition of the present invention preferably contains, as a specific resin, at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor.
The resin composition of the present invention preferably contains polyimide or a polyimide precursor as a specific resin.
Furthermore, the specific resin preferably has polymerizable groups, and more preferably contains radical polymerizable groups.
When a specific resin has radical polymerizable groups, the resin composition of the present invention preferably contains a radical polymerization initiator as described below, and more preferably contains a radical polymerization initiator as described below and a radical crosslinking agent as described below. Furthermore, it may optionally contain a sensitizer as described below. A negative-type photosensitive film can be formed from such a resin composition of the present invention.
Furthermore, the specific resin may have polarity-converting groups such as acid-degradable groups.
When a specific resin has an acid-degradable group, the resin composition of the present invention preferably contains a photoacid generator as described below. From such a resin composition of the present invention, for example, a chemically amplified positive-type or negative-type photosensitive film can be formed.

[Polyimide precursor]
The polyimide precursor used in this invention is not particularly limited in terms of type, but it is preferably made up of repeating units represented by the following formula (2).
In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, with the oxygen atom being preferred.
In formula (2), R ¹¹¹ represents a divalent organic group. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, the group consists of 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 combination thereof, with groups containing an aromatic group having 6 to 20 carbon atoms being more preferred. The linear or branched aliphatic group may have hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. As a preferred embodiment of the present invention, the group is exemplified by groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably by groups represented by -Ar-L-Ar-. However, Ar is an aromatic group independently, and L is a single bond, or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -CO-, -S-, _-SO2- , or -NHCO-, or a group consisting of two or more of the above. The preferred ranges for these are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. One or more diamines may be used.
Specifically, the diamine 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 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 hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. Examples of groups containing aromatic groups are listed below.

In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond or a C1 to C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, _-SO₂- , -NHCO-, or a group selected from a combination thereof; more preferably a single bond or a C1 to C3 alkylene group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or _-SO₂- ; and even more preferably _-CH₂- , _-O- , -S-, -SO₂-, -C( _CF₃ ) _₂- , or -C( _CH₃ ) _₂- .
In the formula, * represents a bonding site with another structure.

Specifically, diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 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'-diaminobiphen Nyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-amino Phenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Ropan, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoganaamine, 2,3,5,6-tetramethyl Tyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis( 4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3- Examples include at least one diamine selected from trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotidine, and 4,4'-diaminoquaterphenyl.

Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferred.

Furthermore, diamines having two or more alkylene glycol units as the main chain, as described in paragraphs 0032 to 0034 of International Publication No. 2017/038598, are also preferably used.

R ¹¹¹ is preferably represented as -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film. However, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, _-SO₂- , or -NHCO-, or a group consisting of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, or _-SO₂- . Here, the aliphatic hydrocarbon group is preferably an alkylene group.

Furthermore, R ¹¹¹ is preferably a divalent organic group represented by formula (51) or formula (61) below, from the viewpoint of i-ray transmittance. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferably a divalent organic group represented by formula (61).
Formula (51)
In formula (51), R ⁵⁰ to R ⁵⁷ are each independently 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 * represents each independently a bonding site with the nitrogen atom in formula (2).
Examples of monovalent organic groups R ⁵⁰ to R ⁵⁷ include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).
In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (2).
Examples of diamines that give the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

In formula (2), R ¹¹⁵ represents a tetravalent organic group. A tetravalent organic group containing an aromatic ring is preferred, and a group represented by formula (5) or (6) below is more preferred.
In formula (5) or formula (6), * independently represents a bonding site with another structure.
In formula (5), R ¹¹² is a single bond or a divalent linking group, preferably a single bond or a group selected from a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -CO-, -S-, _-SO₂- , and -NHCO-, and combinations thereof; more preferably a group selected from a single bond or a C1-C3 alkylene group which may be substituted with a fluorine atom, -O-, -CO-, -S-, and _-SO₂- ; and even more preferably a divalent group selected from the group consisting of _-CH₂- , -C( _CF₃ ) _₂- , -C( _CH₃ ) _₂- , -O-, -CO-, -S-, and _-SO₂- .

Specifically, R ¹¹⁵ refers to tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. The polyimide precursor may contain only one tetracarboxylic dianhydride residue as the structure corresponding to R ¹¹⁵ , or it may contain two or more.
Tetracarboxylic acid dianhydrides are preferably represented by the following formula (O).
In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range for R ¹¹⁵ is the same as that for R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, and 2,2 ',3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, Examples include 3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl and alkoxy derivatives of these having 1 to 6 carbon atoms.

Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also preferred examples.

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may have an OH group. More specifically, R ¹¹¹ may be a residue of a bisaminophenol derivative.

In formula (2), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group. Furthermore, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and more preferably both contain polymerizable groups. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, radicals, etc., and radical polymerizable groups are preferred. Specific examples of polymerizable groups include groups having an ethylenically unsaturated bond, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups in the polyimide precursor, groups having an ethylenically unsaturated bond are preferred.
Groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl groups), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.
In equation (III), * represents a bonding site with another structure.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, _-CH₂CH (OH) _CH₂- , a cycloalkylene group, or a polyalkylene oxy group.
Examples of suitable R ²⁰¹ include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, _-CH₂CH (OH) _CH₂- , and polyalkylene oxy groups. More preferably, alkylene groups such as ethylene and propylene, _-CH₂CH (OH) _CH₂- , cyclohexyl, and polyalkylene oxy groups are preferred, and even more preferably, alkylene groups such as ethylene and propylene, or polyalkylene oxy groups.
In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different.
When a polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of alkylene oxy groups in the polyalkylene oxy group may be random, block-like, or have alternating patterns.
The number of carbon atoms in the alkylene group (including the number of carbon atoms of substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, still more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.
Furthermore, the alkylene group may have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like.
Furthermore, the number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the above-mentioned group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating or other patterned arrangements. The preferred configuration of the number of repeating ethylene oxy groups in these groups is as described above.

In formula (2), if R ¹¹³ is a hydrogen atom, or if R ¹¹⁴ is a hydrogen atom, the polyimide precursor may form a pair salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity-converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of an acid to produce alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups, but acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl ester groups are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred.
Specific examples of acid-degradable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, and trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl group or tetrahydrofuranyl group are preferred.

Furthermore, the polyimide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

Furthermore, to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane as the diamine.

The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the exposure latitude.
Formula (2-A)
In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 each independently represent divalent organic groups, ^R113 and ^R114 each independently represent hydrogen atoms or monovalent organic groups, and at least one of ^R113 and ^R114 is a polymerizable group, and preferably both are polymerizable groups.

^A1 , ^A2 , ^R111 , ^R113 , and ^R114 are each independently equivalent to ^A1 , ^A2 , ^R111 , ^R113 , and ^R114 in formula (2), and the preferred ranges are also the same.
R ¹¹² is synonymous with R ¹¹² in formula (5), and the preferred range is also the same.

The polyimide precursor may contain one type of repeating unit represented by formula (2), or it may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). Furthermore, it goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
The degree of molecular weight dispersion of the polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit to the degree of molecular weight dispersion of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower.
In this specification, the degree of molecular weight dispersion is the value calculated by dividing the weight-average molecular weight by the number-average molecular weight.
Furthermore, if the resin composition contains multiple types of polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyimide precursors as a single resin are, respectively, within the above ranges.

[Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide, or a polyimide soluble in a developer mainly composed of an organic solvent.
In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium at 23°C. From the viewpoint of pattern formation, it is preferable that the polyimide dissolves at 0.5 g or more, and more preferably at 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less.
Furthermore, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain.
In this specification, "main chain" refers to the relatively longest bonding chain in the polymer compound molecule constituting the resin, and "side chain" refers to the other bonding chains.

- Fluorine atom -
From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains fluorine atoms.
The fluorine atom is preferably included in R ¹³² or R 131 in the repeating unit represented by formula (4) described later, and more preferably included as an alkyl fluoride in R ¹³² or ^{R 131 in} the repeating unit represented by formula (4) described later.
The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and preferably 20% by mass or less.

-Silicon atom-
From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains silicon atoms.
The silicon atom is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably included in R ¹³¹ in the repeating unit represented by formula (4) described later as an organically modified (poly)siloxane structure described later.
Furthermore, the silicon atoms or the organically modified (poly)siloxane structure may be included in the side chains of the polyimide, but it is preferable that they be included in the main chain of the polyimide.
The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

- Ethylene unsaturated bond -
From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has ethylenically unsaturated bonds.
Polyimides may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but it is preferable that they be in the side chains.
The above ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably included in R ¹³² or R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably in R ¹³² or R ¹³¹ in the repeating unit represented by formula (4) described later as a group having an ethylenically unsaturated bond.
Among these, the ethylenically unsaturated bond is preferably included in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably included as a group having an ethylenically unsaturated bond in R ¹³¹ in the repeating unit represented by formula (4) described later.
Groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, and other groups having a vinyl group that is directly bonded to an aromatic ring and may be substituted, (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (IV).

In formula (IV), R ²⁰ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.

In formula (IV), R ²¹ represents an alkylene group having 2 to 12 carbon atoms, -O- _CH₂CH (OH) _CH₂- , -C(=O)O-, -O(C=O)NH-, a (poly)alkylene oxy 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 is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group obtained by combining two or more of these.
Furthermore, the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination thereof.
Of the alkylene groups having 2 to 12 carbon atoms, alkylene groups having 2 to 8 carbon atoms are preferred, and alkylene groups having 2 to 4 carbon atoms are more preferred.

Among these, ^R21 is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1).
In formulas (R1) to (R3), L represents a single bond, or an alkylene group having 2 to 12 carbon atoms, a (poly)alkylene oxy group having 2 to 30 carbon atoms, or a group having two or more of these bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ● represents a bonding site with the oxygen atom to which ^R21 in formula (IV) is bonded.
In formulas (R1) to (R3), the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkylene oxy group having 2 to 30 carbon atoms in L is the same as the preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkylene oxy group having 2 to 30 carbon atoms in ^R21 described above.
In formula (R1), X is preferably an oxygen atom.
In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the same applies to the preferred embodiment.
The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate).
The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate).
The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group, such as a phenolic hydroxyl group, with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

The amount of ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.

-Polymerizable groups other than those containing ethylenically unsaturated bonds-
Polyimides may have polymerizable groups other than those having ethylenically unsaturated bonds.
Polymerizable groups other than those having ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups.
Polymerizable groups other than those having an ethylenically unsaturated bond are preferably included, for example, in R ¹³¹ in the repeating unit represented by formula (4) described later.
The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

- Polarity-converting group -
Polyimides may have polarity-changing groups such as acid-degradable groups. The acid-degradable groups in polyimides are the same as the acid-degradable groups described in R ¹¹³ and R ¹¹⁴ of formula (2) above, and the preferred embodiments are also the same.
Polarity-converting groups are found, for example, in ^R131 and ^R132 in the repeating unit represented by formula (4) described later, and at the ends of the polyimide.

- Acid Value -
When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mg KOH/g or higher, more preferably 50 mg KOH/g or higher, and even more preferably 70 mg KOH/g or higher.
Furthermore, the above acid value is preferably 500 mg KOH/g or less, more preferably 400 mg KOH/g or less, and even more preferably 200 mg KOH/g or less.
Furthermore, when polyimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mg KOH/g, more preferably 2 to 30 mg KOH/g, and even more preferably 5 to 20 mg KOH/g.
The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
Furthermore, regarding the acid groups contained in polyimide, from the viewpoint of achieving both storage stability and developability, acid groups with a pKa of 0 to 10 are preferred, and acid groups with a pKa of 3 to 8 are more preferred.
pKa is the negative common logarithm of the equilibrium constant Ka, expressed as pKa, when considering a dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa values shall be those calculated using ACD/ChemSketch®. Alternatively, values published in the "Revised 5th Edition Chemical Handbook, Basic Edition" edited by the Chemical Society of Japan may be referred to.
Furthermore, if the acidic group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant.
The polyimide preferably contains at least one such acidic group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

- Phenolic hydroxyl group -
From the viewpoint of ensuring an appropriate development speed with an alkaline developer, it is preferable that the polyimide has a phenolic hydroxyl group.
Polyimides may have phenolic hydroxyl groups at the ends of their main chains or in their side chains.
The phenolic hydroxyl group is preferably included, for example, in R ¹³² or R ¹³¹ in the repeating unit represented by formula (4) described later.
The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains repeating units represented by the following formula (4).
In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.
If polymerizable groups are present, the polymerizable groups may be located at least one of R ¹³¹ and R ¹³² , or they may be located at the ends of the polyimide as shown in formula (4-1) or formula (4-2) below.
Formula (4-1)
In formula (4-1), R ¹³³ is a polymerizable group, and the other groups are equivalent to those in formula (4).
Formula (4-2)
At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is equivalent to formula (4).

Examples of polymerizable groups include groups containing the ethylenically unsaturated bond described above, or crosslinkable groups other than those having the ethylenically unsaturated bond described above.
R ¹³¹ represents a divalent organic group. Examples of divalent organic groups are the same as those for R ¹¹¹ in formula (2), and the preferred range is also the same.
Furthermore, R ¹³¹ can be the diamine residue remaining after the removal of the amino group of the diamine. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. A specific example is R ¹¹¹ in formula (2) of the polyimide precursor.

R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in its main chain, as this more effectively suppresses warping during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule, and even more preferably, it is the above-mentioned diamine residue that does not contain an aromatic ring.

Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule include, but are not limited to, Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

R ¹³² represents a tetravalent organic group. Examples of tetravalent organic groups are similar to those of R ¹¹⁵ in formula (2), and the preferred range is also the same.
For example, the four bonds of the tetravalent organic group exemplified as R ¹¹⁵ bond with the four -C(=O)- portions in formula (4) above to form a fused ring.

Furthermore, R ¹³² can be a tetracarboxylic acid residue remaining after the removal of the anhydride group from a tetracarboxylic dianhydride. A specific example is R ¹¹⁵ in formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, as R ¹³¹ , preferred examples 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 as R ¹³² , the above (DAA-1) to (DAA-5) are more preferred examples.

Furthermore, it is preferable that the polyimide contains fluorine atoms in its structure. The fluorine atom content in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

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

Furthermore, to improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are encapsulated with end-capturing agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. Of these, the use of monoamines is more preferable, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy Examples include -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants.

-Imidization rate (ring closure rate)-
The imidization rate (also called the "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film.
There is no particular upper limit to the above imidization rate; it is acceptable as long as it is 100% or less.
The above imidization rate can be measured, for example, by the following method.
The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1, which is the absorption peak derived from the imide structure, is determined around 1377 ^cm⁻¹ . Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P2, which is also around 1377 ^cm⁻¹ . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be determined based on the following formula.
Imidization rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

Polyimide may contain repeating units represented by formula (4) above, all of which contain one type of R ¹³¹ or R ¹³² , or it may contain repeating units represented by formula (4) above, each containing two or more different types of R ¹³¹ or R ^132. In addition to the repeating units represented by formula (4), polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by formula (2) above.

Polyimides can be synthesized by obtaining polyimide precursors using methods such as: reacting tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-captive) at low temperatures; reacting tetracarboxylic dianhydride (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-captive) with a diamine at low temperatures; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a monoamine end-captive) in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-chloridizing the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine end-captive); completely imidizing the precursor using a known imidation reaction method; stopping the imidation reaction midway to introduce a partial imide structure; or introducing a partial imide structure by blending a fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

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 setting the weight-average molecular weight to 5,000 or more, the flexural resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or more is particularly preferred.
Furthermore, the number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
The degree of molecular weight dispersion of the polyimide is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit to the degree of molecular weight dispersion of the polyimide, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower.
Furthermore, if the resin composition contains multiple types of polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion 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 degree of dispersion calculated when the multiple types of polyimides are treated as a single resin are, respectively, within the above ranges.

[Polybenzoxazole precursor]
The polybenzoxazole precursor used in this invention does not have any particular structure, but preferably contains repeating units represented by the following formula (3).
In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ are equivalent to R ¹¹³ in formula (2), and their preferred ranges are also the same. That is, it is preferable that at least one of them is a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. The divalent organic group is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a linear aliphatic group. R ¹²¹ is preferably a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more may be used.

As the dicarboxylic acid residue, dicarboxylic acid residues containing an aliphatic group and dicarboxylic acid residues containing an aromatic group are preferred, and dicarboxylic acid residues containing an aromatic group are more preferred.
As for dicarboxylic acids containing an aliphatic group, dicarboxylic acids containing a linear or branched (preferably linear) aliphatic group are preferred, and dicarboxylic acids consisting of a linear or branched (preferably linear) aliphatic group and two -COOH groups are more preferred. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Examples of dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succicic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylpimelic acid. Examples include suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formulas.

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

As for dicarboxylic acids containing aromatic groups, those having the following aromatic groups are preferred, and those consisting only of the following aromatic groups and two -COOH groups are more preferred.

In the formula, A represents a divalent group selected from the group consisting of _-CH₂- , -O-, -S-, _-SO₂- , -CO-, -NHCO-, -C( _CF₃ ) _₂- , and -C( _CH₃ ) _₂- , and * represents a binding site with another structure independently.

Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, it is equivalent to R ¹¹⁵ in formula (2) above, and the preferred range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative, and examples of groups derived from bisaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-A Examples include (mino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used individually or in combination.

Among bisaminophenol derivatives, those having the following aromatic groups are preferred.

In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , and -NHCO-, and * and # represent bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Furthermore, ^R122 may also be the structure represented by the above formula. When R ¹²² has the structure represented by the above formula, it is preferable that two of the four * and # symbols are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, and the other two are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded, and it is more preferable that two * symbols are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded, and two # symbols are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, or two * symbols are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, and two # symbols are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded, and it is even more preferable that two * symbols are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded, and two # symbols are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded.

The bisaminophenol derivative is also preferably a compound represented by formula (A-s).

In formula (A-s), _R1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, _-SO₂- , -CO-, -NHCO-, a single bond, or an organic group selected from the group of formulas (A-sc) below. _R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different. _R3 is a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.

(In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bis-aminophenol derivative represented by formula (A-s) above.)

In the above formula (A-s), having a substituent at the ortho position of the phenolic hydroxyl group, i.e., _R3 , is considered to bring the carbonyl carbon of the amide bond and the hydroxyl group closer together, and is particularly preferable because it further enhances the effect of high cyclization rate when cured at low temperatures.

Furthermore, in the above formula (A-s), it is preferable that _R2 is an alkyl group and _R3 is an alkyl group, as this maintains the effects of high transparency to the i-line and a high cyclization rate when cured at low temperatures.

Furthermore, it is even more preferable that _R1 in the above formula (A-s) is an alkylene or a substituted alkylene. Specific examples of alkylenes and substituted alkylenes related to _R1 include linear or branched alkyl groups having 1 to 8 carbon atoms. Among these, _-CH2- , -CH( _CH3 )-, and -C( _CH3 ) _2- are more preferable because they allow for the production of a well-balanced polybenzoxazole precursor that maintains high transparency to i-lines and a high cyclization rate when cured at low temperatures, while also having sufficient solubility in solvents.

As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506 can be referenced, and the contents of these are incorporated herein.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506, and these contents are incorporated herein by reference. Of course, it goes without saying that the structure is not limited to these examples.

The polybenzoxazole precursor may include other types of repeating units in addition to the repeating unit of formula (3) above.
The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit, in that it can suppress the occurrence of warping associated with ring closure.

In formula (SL), Z has an a structure and a b structure, ^R1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, ^R2s is a hydrocarbon group having 1 to 10 carbon atoms, at least one of ^R3s , ^R4s , ^R5s , and ^R6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. Polymerization of the a structure and the b structure may be block polymerization or random polymerization. The mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.

In formula (SL), preferred Z is one in which R ^5s and R ^6s in the b structure are phenyl groups. Furthermore, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight within the above range, it is possible to more effectively reduce the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor, thereby achieving both the effect of suppressing warping and the effect of improving solvent solubility.

When the repeating unit includes a diamine residue represented by formula (SL), it is also preferable to include a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride as a repeating unit. An example of such a tetracarboxylic acid residue is R ¹¹⁵ in formula (2).

The weight-average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. The number-average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of molecular weight dispersion of the polybenzoxazole precursor is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no upper limit to the degree of molecular weight dispersion of the polybenzoxazole precursor, but for example, it is preferably 2.6 or lower, more preferably 2.5 or lower, even more preferably 2.4 or lower, even more preferably 2.3 or lower, and even more preferably 2.2 or lower.
Furthermore, if the resin composition contains multiple types of polybenzoxazole precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polybenzoxazole precursors are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polybenzoxazole precursors as a single resin are, respectively, within the above range.

[Polybenzoxazole]
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) that has a polymerizable group. A radical polymerizable group is preferred as the polymerizable group. Alternatively, it may be a compound represented by the following formula (X) that has a polarity conversion group such as an acid-degradable group.
In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.
If the polybenzoxazole has a polymerizable group or an acid-degradable group, the polymerizable group or the acid-degradable group may be located at least one of R ¹³³ and R ¹³⁴ , or it may be located at the terminal end of the polybenzoxazole as shown in formula (X-1) or formula (X-2) below.
Formula (X-1)
In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polarity conversion group such as a polymerizable group or an acid-degradable group, and if it is not a polarity conversion group such as a polymerizable group or an acid-degradable group, it is an organic group, and the other group is equivalent to that in formula (X).
Formula (X-2)
In formula (X-2), R ¹³⁷ is a polarity-changing group such as a polymerizable group or an acid-degradable group, the others are substituents, and the other groups are equivalent to those in formula (X).

Polarity-converting groups such as polymerizable groups or acid-degradable groups are synonymous with the polymerizable groups described above in relation to the polymerizable groups of the polyimide precursor.

R ¹³³ represents a divalent organic group. Examples of divalent organic groups include aliphatic groups and aromatic groups. A specific example is R ¹²¹ in formula (3) of the polybenzoxazole precursor. A preferred example is similar to R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. An example of a tetravalent organic group is R ¹²² in formula (3) of the polybenzoxazole precursor. A preferred example is the same as R ¹²² .
For example, the four bonds of the tetravalent organic group exemplified as R ¹²² bond with the nitrogen and oxygen atoms in formula (X) above to form a fused ring. For example, if R ¹³⁴ is the following organic group, it forms the following structure. In the following structure, * represents the bonding site with the nitrogen or oxygen atom in formula (X).

The polybenzoxazole preferably has an oxazole conversion rate of 85% or more, and more preferably 90% or more. There is no particular upper limit, and it may be 100%. By having an oxazole conversion rate of 85% or more, the membrane shrinkage due to ring closure that occurs when oxazole is converted by heating is reduced, and the occurrence of warping can be suppressed more effectively.
The above oxazole conversion rate can be measured, for example, by the following method.
The infrared absorption spectrum of polybenzoxazole is measured, and the peak intensity Q1, which originates from the amide structure of the precursor, is determined around 1650 ^cm⁻¹ . Next, this is normalized by the absorption intensity of the aromatic ring observed around 1490 ^cm⁻¹ . After heat-treating the polybenzoxazole at 350°C for 1 hour, the infrared absorption spectrum is measured again, and the peak intensity Q2, which originates around 1650 ^cm⁻¹ , is determined and normalized by the absorption intensity of the aromatic ring observed around 1490 ^cm⁻¹ . Using the normal values of the obtained peak intensities Q1 and Q2, the oxazole conversion rate of polybenzoxazole can be determined based on the following formula.
Oxazole conversion rate (%) = (Specific value of peak intensity Q1 / Specific value of peak intensity Q2) × 100

Polybenzoxazoles may contain repeating units of formula (X) that all contain one type of R ¹³¹ or R ¹³² , or they may contain repeating units of formula (X) that contain two or more different types of R ¹³¹ or R ^132. In addition, polybenzoxazoles may contain other types of repeating units besides the repeating units of formula (X).

Polybenzoxazoles can be obtained, for example, by reacting a bisaminophenol derivative with a dicarboxylic acid containing R ¹³³ or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above-mentioned dicarboxylic acid to obtain a polybenzoxazole precursor, and then oxazoleizing this precursor using a known oxazole reaction method.
In the case of dicarboxylic acids, in order to increase the reaction yield, etc., an active ester-type dicarboxylic acid derivative that has been pre-reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used.

The weight-average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight-average molecular weight to 5,000 or higher, the bending resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. Furthermore, when two or more types of polybenzoxazole are contained, it is preferable that the weight-average molecular weight of at least one of the polybenzoxazoles is within the above range.
Furthermore, the number-average molecular weight (Mn) of the polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of molecular weight dispersion of the polybenzoxazole is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no upper limit to the degree of molecular weight dispersion of the polybenzoxazole, but for example, it is preferably 2.6 or lower, more preferably 2.5 or lower, even more preferably 2.4 or lower, even more preferably 2.3 or lower, and even more preferably 2.2 or lower.
Furthermore, if the resin composition contains multiple types of polybenzoxazole as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polybenzoxazoles are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polybenzoxazole are treated as a single resin are, respectively, within the above range.

[Polyamide-imide precursors]
The polyamide-imide precursor preferably contains repeating units represented by the following formula (PAI-2).
In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

In formula (PAI-2), R ¹¹⁷ is exemplified by linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, R is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these by single bonds or linking groups. More preferably, R is an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.
The above-mentioned linking groups are preferably -O-, -S-, -C(=O)-, -S(=O) _2- , alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked, and more preferably -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group described above is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atoms in the halogenated alkylene group may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. An example of a preferred halogenated alkylene group is the (ditrifluoromethyl)methylene group.
The above-mentioned arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

Furthermore, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. Chlorination is preferred as the halogenation.
In this invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound.
Two of the three carboxyl groups in the above tricarboxylic acid compound may be converted to acid anhydrides.
Examples of tricarboxylic acid compounds that may be halogenated and used in the production of polyamide-imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds.
These tricarboxylic acid compounds may be used individually or in combination of two or more.

Specifically, preferred tricarboxylic acid compounds include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. More preferred tricarboxylic acid compounds include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

Furthermore, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalentricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked by a single bond, -O-, _-CH2- , -C( _CH3 ) _2- , -C( _CF3 ) _2- , _-SO2- , or a phenylene group.
These compounds may be compounds in which two carboxyl groups have been converted to anhydrides (e.g., trimellitic anhydride), or compounds in which at least one carboxyl group has been converted to a halogen (e.g., trimellitic anhydride chloride).

In formula (PAI-2), R ¹¹¹ , A ² , and R ¹¹³ are the same as R ¹¹¹ , A ² , and R ¹¹³ in formula (2) above, and the preferred embodiment is the same.

The polyamide-imide precursor may further contain other repeating units.
Other repeating units include the repeating unit represented by equation (2) above, and the repeating unit represented by equation (PAI-1) below.

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group.
In formula (PAI-1), R ¹¹⁶ is exemplified by linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, R is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these by single bonds or linking groups. More preferably, R is an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.
The above-mentioned linking groups are preferably -O-, -S-, -C(=O)-, -S(=O) _2- , alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked, and more preferably -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group described above is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atoms in the halogenated alkylene group may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. An example of a preferred halogenated alkylene group is the (ditrifluoromethyl)methylene group.
The above-mentioned arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

Furthermore, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
In the present invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide compound.
The carboxyl group in a dicarboxylic acid dihalide compound may be halogenated, but it is preferable that it is chlorinated, for example. In other words, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
Examples of halogenated dicarboxylic acid compounds or dicarboxylic acid dihalide compounds used in the production of polyamide-imide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds.
These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used individually or in combination of two or more.

Specifically, preferred dicarboxylic acid compounds or dicarboxylic acid dihalide compounds include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. More preferred are dicarboxylic acid compounds or dicarboxylic acid dihalide compounds that include an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups.

Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succicic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebaic acid, and hexadeca. Examples include fluorosebacic acid, 1,9-nonanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosandioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc.
Specific examples of dicarboxylic acid dihalide compounds include compounds in which the two carboxyl groups in the above-mentioned specific examples of dicarboxylic acid compounds are halogenated.

In formula (PAI-1), R ¹¹¹ is the same as R ¹¹¹ in formula (2) described above, and the preferred embodiment is the same.

Furthermore, the polyamide-imide precursor may also preferably contain fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

Furthermore, to improve adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc., as the diamine component.

One embodiment of the polyamideimide precursor in the present invention is one in which the total content of repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1), and repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor, excluding the terminals, may be any of the repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1), and repeating units represented by formula (2).
Another embodiment of the polyamideimide precursor in the present invention is one in which the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor, excluding the terminals, may be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

The weight-average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number-average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
The degree of dispersion of the molecular weight of the polyamide-imide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit for the degree of dispersion of the molecular weight of the polyamide-imide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyamide-imide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyamide-imide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyamide-imide precursors are treated as a single resin are, respectively, within the above ranges.

[Polyamide-imide]
The polyamide-imide used in the present invention may be an alkali-soluble polyamide-imide, or a polyamide-imide that is soluble in a developer mainly composed of an organic solvent.
In this specification, alkali-soluble polyamide-imide refers to a polyamide-imide that dissolves at 0.1 g or more in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium at 23°C. From the viewpoint of pattern formation, it is preferable that the polyamide-imide dissolves at 0.5 g or more, and more preferably at 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less.
Furthermore, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyamide-imide is preferably a polyamide-imide having multiple amide bonds and multiple imide structures in its main chain.

- Fluorine atom -
From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyamide-imide contains fluorine atoms.
The fluorine atom is preferably included in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described later, and more preferably included as an alkyl fluoride in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described later.
The amount of fluorine atoms relative to the total mass of the polyamide-imide is preferably 5% by mass or more, and preferably 20% by mass or less.

- Ethylene unsaturated bond -
From the viewpoint of the film strength of the resulting organic film, the polyamide-imide may have ethylenically unsaturated bonds.
Polyamide-imides may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but it is preferable that they be in the side chains.
The above ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably included in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described later, and more preferably in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described later as a group having an ethylenically unsaturated bond.
A preferred embodiment of the group having an ethylenically unsaturated bond is the same as the preferred embodiment of the group having an ethylenically unsaturated bond in the polyimide described above.

The amount of ethylenically unsaturated bonds relative to the total mass of polyamide-imide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

- Polymerizable groups other than ethylenically unsaturated bonds -
Polyamide-imides may have polymerizable groups other than ethylenically unsaturated bonds.
Polymerizable groups other than ethylenically unsaturated bonds in polyamide-imides include the same groups as those described above for polymerizable groups other than ethylenically unsaturated bonds in polyimides.
Polymerizable groups other than ethylenically unsaturated bonds are preferably included, for example, in R ¹¹¹ in the repeating unit represented by formula (PAI-3) described later.
The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamide imide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g.

- Polarity-converting group -
Polyamide-imide may have polarity-changing groups such as acid-degradable groups. The acid-degradable groups in polyamide-imide are the same as the acid-degradable groups described in R ¹¹³ and R ¹¹⁴ in formula (2) above, and the preferred embodiment is the same.

- Acid Value -
When polyamide-imide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyamide-imide is preferably 30 mg KOH/g or higher, more preferably 50 mg KOH/g or higher, and even more preferably 70 mg KOH/g or higher.
Furthermore, the above acid value is preferably 500 mg KOH/g or less, more preferably 400 mg KOH/g or less, and even more preferably 200 mg KOH/g or less.
Furthermore, when polyamide-imide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyamide-imide is preferably 2 to 35 mg KOH/g, more preferably 3 to 30 mg KOH/g, and even more preferably 5 to 20 mg KOH/g.
The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
Furthermore, examples of acid groups contained in polyamideimides include the same groups as those in the polyimides described above, and the preferred embodiments are also the same.

- Phenolic hydroxyl group -
From the viewpoint of ensuring an appropriate development speed with an alkaline developer, it is preferable that the polyamide-imide has a phenolic hydroxyl group.
Polyamide-imides may have phenolic hydroxyl groups at the ends of their main chains or in their side chains.
The phenolic hydroxyl group is preferably included, for example, in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described later.
The amount of phenolic hydroxyl groups relative to the total mass of the polyamide imide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it is preferable that it contains a repeating unit represented by the following formula (PAI-3).
In formula (PAI-3), R ¹¹¹ and R ¹¹⁷ are the same as R ¹¹¹ and R ¹¹⁷ in formula (PAI-2), and the same applies to the preferred embodiment.
If polymerizable groups are present, the polymerizable groups may be located at least one of R ¹¹¹ and R ¹¹⁷ , or at the terminal end of the polyamide-imide.

Furthermore, to improve the storage stability of the resin composition, it is preferable to encapsulate the main chain ends of the polyamide-imide with an end-capturing agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. The preferred embodiment of the end-capturing agent is the same as the preferred embodiment of the end-capturing agent for polyimide described above.

-Imidization rate (ring closure rate)-
The imidization rate (also called the "ring closure rate") of polyamide-imide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film.
There is no particular upper limit to the above imidization rate; it is acceptable as long as it is 100% or less.
The above imidization rate is measured by the same method as the ring closure rate of the polyimide described above.

Polyamide-imides may contain repeating units represented by the above formula (PAI-3) ^that all contain one type of R ¹¹¹ or R ¹¹⁷ , or they may contain repeating units represented by the above formula (PAI-3) that contain two or more different types of R 131 or R ^132. In addition to the repeating units represented by the above formula (PAI-3), polyamide-imides may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (PAI-1) or formula (PAI-2).

Polyamide-imides can be synthesized, for example, by obtaining a polyamide-imide precursor by a known method and then completely imidizing it using a known imidation reaction method, or by stopping the imidation reaction midway and introducing a partial imide structure, or by blending a fully imidized polymer with its polyamide-imide precursor to introduce a partial imide structure.

The weight-average molecular weight (Mw) of the polyamide-imide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight-average molecular weight to 5,000 or higher, the bending resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred.
Furthermore, the number-average molecular weight (Mn) of the polyamide-imide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
The degree of molecular weight dispersion of the polyamide-imide is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit for the degree of molecular weight dispersion of the polyamide-imide, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower.
Furthermore, if the resin composition contains multiple types of polyamide-imides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyamide-imides are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyamide-imides are treated as a single resin are, respectively, within the above ranges.

[Method for producing polyimide precursors, etc.]
Polyimide precursors can be obtained by methods such as reacting tetracarboxylic dianhydride with a diamine at low temperature, reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and esterifying it with a condensing agent or alkylating agent, obtaining a diester from tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine in the presence of a condensing agent, or obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine. Of the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferred.
Examples of the condensing agents mentioned above 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.
Examples of the alkylating agents mentioned above include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dialkylformamide dialkylacetal, trimethyl orthoformate, and triethyl orthoformate.
Examples of the halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphorus oxychloride.
In the method for producing polyimide precursors, it is preferable to use an organic solvent during the reaction. One organic solvent may be used, or two or more may be used.
The organic solvent can be appropriately determined depending on the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diglym), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.
In the method for producing polyimide precursors, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.
The basic compound can be appropriately determined depending on the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, and N,N-dimethyl-4-aminopyridine.

- End-capsulation agent -
In the production method of polyimide precursors, etc., it is preferable to encapsulate the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin ends of the polyimide precursor, etc., in order to further improve storage stability. When encapsulating the carboxylic acid anhydride and acid anhydride derivative remaining at the resin ends, examples of end encapsulants include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and from the standpoint of reactivity and film stability, monoalcohols, phenols, and monoamines are more preferable. 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. Preferred phenol compounds include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, and other phenols. 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 include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants.
Furthermore, when sealing the amino groups at the ends of the resin, it is possible to seal them with compounds having functional groups that can react with the amino groups. Preferred sealing agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. Preferred carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic acid anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride. Furthermore, preferred carboxylic acid chloride compounds include acetyl chloride, acrylate chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantane carbonyl chloride, heptafluorobutyryl chloride, stearate chloride, and benzoyl chloride.

-Solid precipitation-
The production of polyimide precursors may include a step for precipitating a solid. Specifically, after filtering out the water-absorbing by-products of the dehydrating condensation agent present in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid. The resulting solid is then dried to obtain the polyimide precursor. To improve the degree of purity, the polyimide precursor may be repeatedly redissolved, reprecipitation, and dried. Furthermore, the process may include a step for removing ionic impurities using an ion exchange resin.

[Content]
The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition.
The resin composition of the present invention may contain only one specific resin or may contain two or more specific resins. When it contains two or more specific resins, it is preferable that the total amount is within the above range.

Furthermore, the resin composition of the present invention preferably contains at least two types of resins.
Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described later, or it may contain two or more specific resins, but it is preferable to contain two or more specific resins.
When the resin composition of the present invention contains two or more specific resins, it is preferable, for example, to include two or more polyimide precursors that have different structures derived from dianhydride (R ¹¹⁵ in formula (2) above).

<Other resins>
The resin composition of the present invention may include the specified resin described above and other resins different from the specified resin (hereinafter also simply referred to as "other resins").
Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, as well as a pattern (cured product) with excellent solvent resistance.
For example, by adding a (meth)acrylic resin with a high polymerizability value (for example, a molar amount of polymerizable groups per 1 g of resin of 1 × ^10⁻³ mol/g or more) with a weight-average molecular weight of 20,000 or less to the resin composition, or in addition to the polymerizable compounds described later, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc., can be improved.

If the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition.
Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition.
Furthermore, in a preferred embodiment of the resin composition of the present invention, the content of other resins may be low. In the above embodiment, the content of other resins 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 above content is not particularly limited and may be 0% by mass or more.
The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

<Silane coupling agent>
The resin composition according to the first aspect of the present invention preferably contains a silane coupling agent.

The silane coupling agent is not particularly limited, but it is preferable to include compound A having at least one group selected from the group consisting of a hydroxyl group, an amino group, and a thiol group, at least one group from an amide group and an ester group, and a group represented by formula (S-1).
Furthermore, from the viewpoint of adhesion to the silicon wafer, it is preferable that compound A contains aromatic groups.
If compound A contains an aromatic group, it is preferable that the aromatic group is located between at least one group selected from the group consisting of a hydroxyl group, an amino group, and a thiol group, and at least one group from the group consisting of an amide group and an ester group.
The above aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred.
The above aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a benzene ring group.
In formula (S-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, x represents an integer between 1 and 3, and * represents a bonding site with another structure.
The amino group contained in the silane coupling agent may have one or both of its two hydrogen atoms substituted by a substituent. Examples of substituents include hydrocarbon groups or heterocyclic groups, with alkyl or aryl groups being preferred. Examples of heteroatoms in the heterocyclic group include oxygen, sulfur, and nitrogen atoms. Furthermore, an embodiment in which the amino group in the silane coupling agent is an unsubstituted amino group is also one of the preferred embodiments of the present invention.
The hydroxyl group contained in the silane coupling agent is preferably directly bonded to an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and more preferably directly bonded to an aliphatic hydrocarbon group.
The thiol group contained in the silane coupling agent is preferably directly bonded to an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and more preferably directly bonded to an aliphatic hydrocarbon group.
The amino group contained in the silane coupling agent is preferably directly bonded to an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and more preferably directly bonded to an aromatic hydrocarbon group.
An amide group is a group represented by -C(=O) ^NRN- . The orientation of the amide group is not particularly limited, but it is preferable that carbon atoms are bonded to both ends of the amide group. The above ^RN represents a hydrogen atom or a monovalent substituent, which is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and particularly preferably a hydrogen atom.
An ester group is a group represented as -C(=O)O-. The orientation of the ester group is not particularly limited, but it is preferable that carbon atoms are bonded to both ends of the ester group.

In formula (S-1), ^R1 is preferably a C1 to C30 hydrocarbon group which may be substituted, more preferably an alkyl group having C1 to C30 or an aromatic hydrocarbon group having C6 to C30, even more preferably an alkyl group having C1 to C4 or a phenyl group, particularly preferably an alkyl group having C1 to C4, even more preferably a methyl group or an ethyl group, and most preferably an ethyl group.
In formula (S-1), ^R2 is independently preferably a C1-C30 hydrocarbon group, more preferably a C1-C30 alkyl group or a C6-C30 aromatic hydrocarbon group, even more preferably a C1-C4 alkyl group or a phenyl group, particularly preferably a C1-C4 alkyl group, even more preferably a methyl group or an ethyl group, and most preferably an ethyl group.
In formula (S-1), x is preferably 2 or 3, and more preferably 3.
The group represented by formula (S-1) is preferably an alkoxysilyl group. The alkoxysilyl group may be a monoalkoxysilyl group, a dialoxysilyl group, or a trialkoxysilyl group, but a dialoxysilyl group or a trialkoxysilyl group is preferred, and a trialkoxysilyl group is more preferred.
The alkoxy group in the alkoxysilyl group is not particularly limited, but an alkoxy group having 1 to 10 carbon atoms is preferred, an alkoxy group having 1 to 4 carbon atoms is more preferred, a methoxy group or an ethoxy group is even more preferred, and an ethoxy group is particularly preferred. Furthermore, the multiple alkoxy groups in the dialkoxysilyl group or trialkoxysilyl group may be the same or different.

Compound A may have multiple or only one of at least one groups selected from the group consisting of hydroxyl groups, amino groups, and thiol groups. If it has multiple groups, it may contain multiple types of groups, such as having both a hydroxyl group and an amino group.
The total number of at least one group selected from the group consisting of hydroxyl groups, amino groups, and thiol groups in compound A is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
Compound A may have multiple or only one of at least one of the groups, an amide group and an ester group. If it has multiple groups, it may contain multiple types of groups, such as having both an amide group and an ester group.
In compound A, the total number of at least one amide group and ester group is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
Compound A may contain two or more groups represented by formula (S-1).
The number of groups represented by formula (S-1) in compound A is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

Compound A is preferably a compound having a hydroxyl group, at least one of an amide group and an ester group, and a group represented by formula (S-1).
Furthermore, it is preferable that compound A is a compound having at least one group selected from the group consisting of a hydroxyl group, an amino group, and a thiol group, an amide group, and a group represented by formula (S-1).
Among these, compound A is more preferably a compound having a hydroxyl group, an amide group, and a group represented by formula (S-1).

A resin composition according to a second aspect of the present invention comprises compound A having at least one group selected from the group consisting of a hydroxyl group, an amino group, and a thiol group, at least one group from an amide group and an ester group, and a group represented by formula (S-1).
Compound A in the resin composition according to the second embodiment is the same as compound A in the resin composition according to the first embodiment, and the same applies to the preferred embodiment.

Compound A is preferably a compound represented by formula (1-1).
In formula (1-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, L represents an m+n valence linking group containing an amide group or an ester group, x represents an integer between 1 and 3, m represents an integer of 1 or more, and n represents an integer of 1 or more.

In formula (1-1), ^R1 , ^R2 , and x are the same as ^R1 , ^R2 , and x in formula (S-1), and the same applies to the preferred embodiment.

In formula (1-1), the orientation of the amide group or ester group in L is not particularly limited.
In formula (1-1), L is preferably an m+n linking group containing an amide group.
Furthermore, L is preferably an m+n linking group containing an amide group or ester group and a hydrocarbon group, and is preferably a group represented by a combination of an amide group or ester group and a hydrocarbon group, or a group represented by a combination of an amide group or ester group, a hydrocarbon group and a heterocyclic group, -O-, -CO-, -S-, ^{-SO2-, or -NRN-} _. ^RN is as described above. A heteroaromatic ring group is preferred as the heterocyclic group. Examples of heteroatoms in the heterocyclic group include oxygen atoms, sulfur atoms, or nitrogen atoms.
The hydrocarbon group described above is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof; more preferably a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof; even more preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof; and particularly preferably a group represented by a combination of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms.
Furthermore, from the viewpoint of adhesion to the silicon wafer, it is preferable that L contains aromatic groups.
If compound A contains an aromatic group, it is preferable that the aromatic group is located between at least one group selected from the group consisting of a hydroxyl group, an amino group, and a thiol group, and at least one group from the group consisting of an amide group and an ester group.
The above aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred.
The above aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a benzene ring group.
Furthermore, the carbon atom in L in formula (1-1) that is directly bonded to the hydroxyl group in formula (1-1) is preferably a carbon atom that constitutes an aliphatic hydrocarbon group.
In other words, the bonding site with the hydroxyl group in formula (1-1) in L is preferably an aliphatic hydrocarbon group.

Specific examples of preferred embodiments of L in formula (1-1) are described below, but the present invention is not limited thereto. In the following examples, * represents the bonding site with the Si atom in formula (1-1), and # represents the bonding site with the hydroxyl group in formula (1-1).

In formula (1-1), x represents an integer between 1 and 3, preferably 2 or 3, and more preferably 3.
In formula (1-1), m is preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 1.
n is preferably an integer from 1 to 4, more preferably 1 or 2, and even more preferably 1.

Compound A is preferably a compound represented by formula (2-1).
In formula (2-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, ^L1 represents a single bond or a divalent linking group, Z represents an amide group, the orientation of the amide group in Z is not particularly limited, ^L2 represents a single bond or a divalent linking group, Ar represents an aromatic group, X represents an alkylene group, and x represents an integer between 1 and 3.

In formula (2-1), ^R1 , ^R2 , and x are synonymous with ^R1 , ^R2 , and x in formula (1-1), respectively, and the same applies to the preferred embodiment.

In formula (2-1), ^L1 is preferably a single bond, a hydrocarbon group, or a group represented by a combination of a hydrocarbon group and -O-, -CO-, -S-, ^{-SO2-, or -NRN-} _, more preferably a hydrocarbon group, or a group represented by a combination of a hydrocarbon group and -O-, and even more preferably a hydrocarbon group.
The hydrocarbon group is preferably an alkylene group, a phenylene group, or a combination thereof, with the alkylene group being more preferred.
The alkylene group described above is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms.

In formula (2-1), Z represents an amide group, which may be a substituted amide group or an unsubstituted amide group, but an unsubstituted amide group is preferred.
The orientation of the amide group is not particularly limited, but for example, one preferred embodiment of the present invention is that the bonding site with ^L2 is the nitrogen atom of the amide group at Z.

In formula (2-1), L ² represents a single bond or a divalent linking group, and is preferably a single bond, or a hydrocarbon group, or a group represented by a combination of a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) _2- , or -NR ^N- , more preferably a hydrocarbon group, or a group represented by a combination of a hydrocarbon group and -C(=O)O- or -C(=O)NR ^N- , and even more preferably a hydrocarbon group.
The hydrocarbon group is preferably an alkylene group, a phenylene group, or a combination thereof, with the alkylene group being more preferred.
The alkylene group described above is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms.

In formula (2-1), Ar is preferably an aromatic hydrocarbon group, and more preferably a phenylene group. Ar may be an aromatic heterocyclic group, or an aromatic hydrocarbon group that forms a heterocyclic ring with a heterocyclic group or a hydrocarbon group. Examples of the aromatic heterocyclic group or the heteroatom in the heterocyclic group include oxygen atoms, sulfur atoms, nitrogen atoms, etc.

In formula (2-1), X is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group.

[Molecular weight]
The molecular weight of compound A is preferably 200 to 1,000, more preferably 300 to 900, and even more preferably 300 to 800.

[Synthesis method]
Compound A can be synthesized, for example, by the method described in the synthesis example in the examples below. Alternatively, it may be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.

Specific examples of compound A are not limited to C-1 to C-23 used in the examples.

[Other silane coupling agents]
The resin composition of the present invention may also contain other silane coupling agents different from compound A described above.
Other silane coupling agents that are known in the art can be used, but are not particularly limited, including the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, the compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, the compounds described in paragraph 0055 of International Publication No. 2014/097594, and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. Furthermore, it is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358. It is also preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group.

Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more.

The content of the silane coupling agent relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 20% by mass. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. The upper limit is more preferably 10% by mass or less, and even more preferably 5% by mass or less.
Silane coupling agents may be used individually or in combination of two or more. When using two or more agents in combination, it is preferable that their total amount be within the above range.
The content of compound A in the resin composition of the present invention, relative to the total solid content, is preferably 0.1 to 20% by mass. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. The upper limit is more preferably 10% by mass or less, and even more preferably 5% by mass or less.
Compound A may be used alone, or two or more compounds may be used in combination. When two or more compounds are used in combination, it is preferable that their total amount be within the above range.
In the present invention, the present invention may also be characterized in that it substantially does not contain any other silane coupling agent other than compound A. Specifically, the content of other silane coupling agents relative to the total solid content of the resin composition of the present invention is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less. The lower limit is not particularly limited and may be 0% by mass.
In the present invention, the present invention may also be substantially free of a silane coupling agent different from the compound represented by formula (2-1). Specifically, the content of a silane coupling agent different from the compound represented by formula (2-1) relative to the total solid content of the resin composition of the present invention is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less. The lower limit is not particularly limited and may be 0% by mass.

<Organometallic complexes>
The resin composition of the present invention may contain organometallic complexes from the viewpoint of chemical resistance.
An organometallic complex can be any organic complex compound containing a metal atom, but it is preferably a complex compound containing both a metal atom and an organic group, more preferably a compound in which an organic group is coordinated to a metal atom, and even more preferably a metallocene compound.
In the present invention, a metallocene compound refers to an organometallic complex having two cyclic pentadienyl anion derivatives, which may have substituents, as η5-ligands.
The above organic group is not particularly limited, but a hydrocarbon group or a group consisting of a hydrocarbon group and a heteroatom is preferred. The heteroatom is preferably an oxygen atom, a sulfur atom, or a nitrogen atom.
In the present invention, it is preferable that at least one of the organic groups is a cyclic group, and more preferably that at least two are cyclic groups.
The above-mentioned cyclic group is preferably selected from a five-membered ring cyclic group and a six-membered ring cyclic group, and more preferably a five-membered ring cyclic group.
The above cyclic group may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferred.
A cyclopentadienyl group is preferred as the cyclic group of the five-membered ring.
Furthermore, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The metal included in the organometallic complex is not particularly limited, but it is preferably a metal belonging to Group 4 elements, more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium, even more preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

Organometallic complexes may contain two or more metal atoms, or only one metal atom, but it is preferable that they contain only one metal atom. When an organometallic complex contains two or more metal atoms, it may contain only one type of metal atom, or it may contain two or more types of metal atoms.

The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound, or a hafnocene compound; more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound; even more preferably a titanocene compound or a zirconocene compound; and particularly preferably a titanocene compound.

An embodiment in which the organometallic complex has the ability to initiate photoradical polymerization is also one of the preferred embodiments of the present invention.
In the present invention, having photo-radical polymerization initiation ability means being able to generate free radicals that can initiate radical polymerization upon irradiation with light. For example, the presence or absence of photo-radical polymerization initiation ability can be confirmed by irradiating a composition containing a radical crosslinking agent and an organometallic complex with light in a wavelength range in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, and checking whether or not the radical crosslinking agent disappears. An appropriate method can be selected depending on the type of radical crosslinking agent to check whether or not it disappears, but for example, it can be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high-performance liquid chromatography).
When the organometallic complex has photoradical polymerization initiation ability, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, even more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.
If the organometallic complex does not have photoradical polymerization initiation ability, the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds and hafnocene compounds, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds and hafnocene compounds, even more preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds, and particularly preferably a titanocene compound.

The molecular weight of the organometallic complex is preferably 50 to 2,000, and more preferably 100 to 1,000.

As organometallic complexes, compounds represented by the following formula (P) are preferred.
In formula (P), M is a metal atom, and R is a substituent, independently of each other.
Preferably, each of the above R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

In formula (P), the metal atom represented by M is preferably an iron atom, a titanium atom, a zirconium atom, or a hafnium atom; more preferably a titanium atom, a zirconium atom, or a hafnium atom; even more preferably a titanium atom or a zirconium atom; and particularly preferably a titanium atom.
Examples of aromatic groups in formula (P) include aromatic groups having 6 to 20 carbon atoms, with aromatic hydrocarbon groups having 6 to 20 carbon atoms being preferred, such as phenyl groups, 1-naphthyl groups, or 2-naphthyl groups.
The alkyl group in R in formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples include methyl group, ethyl group, propyl group, octyl group, isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, etc.
Examples of halogen atoms in R include F, Cl, Br, and I.
The alkyl group constituting the alkylsulfonyloxy group in R above is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples include methyl group, ethyl group, propyl group, octyl group, isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, etc.
The above R may have further substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, and diarylamino groups.

Specific examples of organometallic complexes, though not limited to them, include tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonate)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds.

Other compounds described in paragraphs 0078-0088 of International Publication No. 2018/025738 may also be used, but are not limited thereto.

The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.
One or more organometallic complexes can be used. When using two or more, it is preferable that the total amount is within the above range.

<Polymerizable compound>
The resin composition of the present invention preferably contains a polymerizable compound.
Polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[Radical Crosslinking Agent]
The resin composition of the present invention preferably contains a radical crosslinking agent.
Radical crosslinking agents are compounds having radical polymerizable groups. Preferred radical polymerizable groups are those containing ethylenically unsaturated bonds. Examples of such groups include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, maleimide groups, and (meth)acrylamide groups.
Among these, the (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred as groups containing the ethylenically unsaturated bond, and the (meth)acryloyl group is more preferred from the viewpoint of reactivity.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds.
As for the compounds having two or more ethylenically unsaturated bonds, compounds having 2 to 15 ethylenically unsaturated bonds are preferred, compounds having 2 to 10 ethylenically unsaturated bonds are more preferred, and compounds having 2 to 6 ethylenically unsaturated bonds are even more preferred.
Furthermore, from the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-mentioned 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.

Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides. Preferably, these are esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, or dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

Furthermore, radical crosslinking agents that have a boiling point of 100°C or higher under normal pressure are also preferred. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerin, and trimethylolethane, among others. Examples of polyfunctional acrylates and methacrylates, as well as mixtures thereof, include compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylated; urethane (meth)acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, and Japanese Unexamined Patent Publication No. 51-037193; polyester acrylates as described in Japanese Unexamined Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, and Japanese Patent Publication No. 52-030490; and epoxy acrylates, which are reaction products of epoxy resin and (meth)acrylic acid. Compounds described in paragraphs 0254 to 0257 of Japanese Unexamined Patent Publication No. 2008-292970 are also suitable. Other examples include polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond.

Furthermore, other preferred radical crosslinking agents besides those mentioned above include compounds having a fluorene ring and two or more groups having ethylenically unsaturated bonds, as described in Japanese Patent Publication No. 2010-160418, Japanese Patent Publication No. 2010-129825, Japanese Patent No. 4364216, etc., as well as cardo resins.

Furthermore, other examples include specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, and Japanese Patent Publication No. 01-040336, as well as vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493. Compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. Additionally, those introduced as photopolymerizable monomers and oligomers in the Journal of the Adhesion Society of Japan, Vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents of these are incorporated herein.

Furthermore, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylateing them, as described in Japanese Patent Publication No. 10-062986 with specific examples of formulas (1) and (2), can also be used as radical crosslinking agents.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Publication No. 2015-187211 can also be used as radical crosslinking agents, and these are incorporated herein by reference.

Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

Examples of commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethylene oxy chains, manufactured by Sartomer; SR-209, 231, and 239, difunctional methacrylates with four ethylene oxy chains, also manufactured by Sartomer; DPCA-60, a hexafunctional acrylate with six pentylene oxy chains, manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutylene oxy chains; and urethane. Examples include ligomer UAS-10, UAB-140 (manufactured by Nippon Paper Industries), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and bremmer PME400 (manufactured by NOF Corporation).

Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Furthermore, as radical crosslinking agents, compounds having an amino structure or a sulfide structure in the molecule as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238 can also be used.

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

The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mg KOH/g, and particularly preferably 1 to 100 mg KOH/g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing, as well as excellent developability. Furthermore, it exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition.
Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 Hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other difunctional acrylates and difunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed.
For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the molecular weight of the polyethylene glycol chain is approximately 200.
In the resin composition of the present invention, monofunctional radical crosslinking agents can be preferably used as radical crosslinking agents from the viewpoint of suppressing warping associated with controlling the elastic modulus of the pattern (cured product). Preferred monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate, as well as N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. As monofunctional radical crosslinking agents, compounds with a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure.
Other examples of bifunctional or more radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

If a radical crosslinking agent is included, its content is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount falls within the above-mentioned range.

[Other crosslinking agents]
The resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above.
In the present invention, other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to a photoacid generator or photobase generator, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products through the action of an acid or a base.
The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or photobase generator during the exposure process.
Other preferred crosslinking agents include compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and alkoxymethyl groups, and more preferably compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl groups, methylol groups, and alkoxymethyl groups is directly bonded to a nitrogen atom.
Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluryl, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atoms of the amino group are replaced with acyloxymethyl groups, methylol groups, or alkoxymethyl groups. The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compounds produced by the above method is acceptable. Furthermore, oligomers formed by the self-condensation of methylol groups of these compounds may also be used.
As for the amino group-containing compounds mentioned above, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using glycoluryl, urea, or alkylene urea are called urea-based crosslinking agents, crosslinking agents using alkylene urea are called alkylene urea-based crosslinking agents, and crosslinking agents using benzoguanamine are called benzoguanamine-based crosslinking agents.
Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluryl-based crosslinking agents and melamine-based crosslinking agents, as described later.

Examples of compounds containing at least one alkoxymethyl group and acyloxymethyl group in the present invention include compounds in which the alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic group, the nitrogen atom of the urea structure described below, or on a triazine.
The alkoxymethyl group or acyloxymethyl group in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
The molecular weight of the above compound is preferably 1500 or less, and more preferably 180 to 1200.

R ₁₀₀ represents an alkyl group or acyl group.
R ₁₀₁ and R ₁₀₂ may each independently represent a monovalent organic group and may be bonded to each other to form a ring.

Examples of compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted for an aromatic group include compounds with the following general formula.

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, and R ₁₀₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes upon the action of an acid to produce an alkali-soluble group (for example, a group that is eliminated by the action of an acid, or a group represented as -C(R ⁴ ) ₂ COOR ⁵ (where R ⁴ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents a group that is eliminated by the action of an acid)).
Each R ₁₀₅ independently represents an alkyl group or an alkenyl group, a, b, and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
Groups that decompose under the action of an acid to produce an alkali-soluble group, groups that are eliminated under the action of an acid, ^and groups represented as -C( ^R4 ) _2COOR5 , for example, ^R5 can be -C( _R36 )( _R37 )( _R38 ), -C( _R36 )( _R37 )( _OR39 ), -C( _R01 )( _R02 )( _OR39 ), etc.
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
The alkyl group described above 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 described above may be 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 above cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
The above-mentioned 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-mentioned 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 those described above for preferred embodiments of alkyl and aryl groups.
The above 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.
Furthermore, these groups may have known substituents within the range that the effects of the present invention can be obtained.

_R01 and _R02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

The groups that decompose upon the action of an acid to produce alkali-soluble groups, or the groups that are eliminated upon the action of an acid, are preferably tertiary alkyl ester groups, acetal groups, cumyl ester groups, enol ester groups, etc. More preferably, they are tertiary alkyl ester groups and acetal groups.

The following structures are examples of compounds containing an alkoxymethyl group. Compounds containing an acyloxymethyl group are examples of compounds obtained by changing the alkoxymethyl group in the following compounds to an acyloxymethyl group. Examples of compounds containing an alkoxymethyl group or acyloxymethyl group in the molecule include, but are not limited to, the following compounds.

The compound containing at least one alkoxymethyl group and acyloxymethyl group may be a commercially available product or one synthesized by a known method.
From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or triazine ring are preferred.

Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexasubtoxicbutylmelamine.

Specific examples of urea-based crosslinking agents include glycoluryl crosslinking agents such as monohydroxymethylated glycoluryl, dihydroxymethylated glycoluryl, trihydroxymethylated glycoluryl, tetrahydroxymethylated glycoluryl, monomethoxymethylated glycoluryl, dimethoxymethylated glycoluryl, trimethoxymethylated glycoluryl, tetramethoxymethylated glycoluryl, monoethoxymethylated glycoluryl, diethoxymethylated glycoluryl, triethoxymethylated glycoluryl, tetraethoxymethylated glycoluryl, monopropoxymethylated glycoluryl, dipropoxymethylated glycoluryl, trippropoxymethylated glycoluryl, tetrapropoxymethylated glycoluryl, monobutoxymethylated glycoluryl, dibutoxymethylated glycoluryl, tripbutoxymethylated glycoluryl, or tetrabutoxymethylated glycoluryl;
Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea.
Ethylene urea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea.
Propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea.
Examples include 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

Specific examples of benzoguanamine crosslinking agents include, for example, 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, trippropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tripbutoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

In addition, as compounds having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups, compounds in which at least one group selected from the group consisting of methylol groups and alkoxymethyl groups is directly bonded to an aromatic ring (preferably a benzene ring) are also suitably used.
Specific examples of 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''-ethylidentris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, and the like.

Other crosslinking agents may be commercially available. Suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Industry 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, DDOM-PC, DDOM-PTBP, DDOM-MBPC, TriML-P, and TriML-35XL. Examples include TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac (registered trademark, hereinafter the same) MX-290, Nikarac MX-280, Nikarac MX-270, Nikarac MX-279, Nikarac MW-100LM, Nikarac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.).

Furthermore, the resin composition of the present invention may also preferably contain, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

- Epoxy compounds (compounds containing epoxy groups) -
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at temperatures below 200°C, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is less likely to occur. Therefore, including an epoxy compound is effective in suppressing low-temperature curing and warping of the resin composition of the present invention.

The epoxy compound preferably contains polyethylene oxide groups. This further reduces the elastic modulus and suppresses warping. A polyethylene oxide group refers to a group with two or more repeating units of ethylene oxide, preferably with 2 to 15 repeating units.

Examples of 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, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, Epiclon® 850-S, Epiclon® HP-4032, Epiclon® HP-7200, Epiclon® HP-820, Epiclon® HP-4700, Epiclon® HP-4770, Epiclon® EXA-830LVP, Epiclon® EXA-8183, Epiclon® EXA-8169, Epiclon® N- 660, Epiclon® N-665-EXP-S, Epiclon® N-740 (all product names, manufactured by DIC Corporation), Recaresin® BEO-20E, Recaresin® BEO-60E, Recaresin® HBE-100, Recaresin® DME-100, Recaresin® L-200 (product names, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088 S, EP-3950S (product names, manufactured by ADEKA Corporation), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150, Epolid (registered trademark) GT401, Epolid (registered trademark) PB4700, Epolid (registered trademark) PB3600 (product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-300 Examples include 0-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, and BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also suitably used.

In the formula, n is an integer between 1 and 5, and m is an integer between 1 and 20.

Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7, in order to achieve both heat resistance and improved elongation.

- Oxetane compounds (compounds containing an oxetanyl group) -
Examples of oxetane compounds 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, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples include the Aronoxetane series manufactured by Toagosei Co., Ltd. (e.g., OXT-121, OXT-221), which can be used individually or in combination of two or more.

-Benzoxazine compounds (compounds containing a benzoxazolyl group)-
Benzoxazine compounds are preferred because, due to the crosslinking reaction resulting from a ring-opening addition reaction, degassing does not occur during curing, and furthermore, thermal shrinkage is reduced, suppressing warping.

Preferred examples of benzoxazine compounds include P-d type benzoxazine, F-a type benzoxazine (both trade names, manufactured by Shikoku Chemicals Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resin, and phenol novolac type dihydrobenzoxazine compounds. These may be used individually or in combination of two or more.

The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition of the present invention. The other crosslinking agents may be present as one type or as two or more types. If two or more other crosslinking agents are present, it is preferable that their total content falls within the above range.

[Polymerization initiator]
The resin composition of the present invention preferably contains a polymerization initiator that can initiate polymerization by light and/or heat. It is particularly preferable that it contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that interacts with a photoexcited sensitizer to generate active radicals.

The photoradical polymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 L· ^mol⁻¹ · ^cm⁻¹ in the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g/L.

Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165-0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015/199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in International Publication No. 2018/221177, the photopolymerization initiators described in International Publication No. 2018/110179, the photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are also incorporated herein.

Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As an aminoacetophenone-based initiator, compounds described in Japanese Patent Publication No. 2009-191179, whose maximum absorption wavelength is matched to a light source of wavelength such as 365 nm or 405 nm, can also be used, and this is incorporated herein by reference.

Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Additionally, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins B.V.), IRGACURE-819, and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem).

More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015/152153, compounds described in International Publication No. 2017/051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017/164127, compounds described in International Publication No. 2013/167515, and others, the contents of which are incorporated herein by reference.

Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)(imino))butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photoradical polymerization initiator) as a photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a linking group >C=N-O-C(=O)- in their molecule.

Commercially available options include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), and ADEKA optomer N-1919 (manufactured by ADEKA Corporation, a photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation) can also be used. In addition, DFI-091 (manufactured by Daito Chemix Co., Ltd.) and SpeedCure PDO (manufactured by Sartomer Arkema) can be used. Furthermore, oxime compounds with the following structures can also be used.

As a photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include the compound described in Japanese Patent Application Publication No. 2014-137466 and the compound described in Japanese Patent No. 06636081, the details of which are incorporated herein by reference.

As a photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is replaced by a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in International Publication No. 2013/083505, which are incorporated herein by reference.

Furthermore, it is also possible to use oxime compounds containing a fluorine atom. Specific examples of such oxime compounds include the compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36-40 described in paragraph 0345 of Japanese Patent Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471, the details of which are incorporated herein by reference.

As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably in dimer form. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Publication No. 2014-137466, and the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, the details of which are incorporated herein by reference. Another example of an oxime compound having a nitro group is ADEKA Arclus NCI-831 (manufactured by ADEKA Corporation).

As photoradical polymerization initiators, oxime compounds having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75, described in International Publication No. 2015/036910.

As a photo-radical polymerization initiator, an oxime compound in which a substituent having a hydroxyl group is attached to a carbazole skeleton can also be used. Examples of such photo-polymerization initiators include the compounds described in International Publication No. 2019/088055, which are incorporated herein by reference.

As a photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^OX1 in which an electron-withdrawing group is introduced to the aromatic ring (hereinafter also referred to as oxime compound OX) can be used. Examples of electron-withdrawing groups in the above aromatic ring group Ar ^OX1 include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups. Acyl groups and nitro groups are preferred, acyl groups are more preferred because they easily form films with excellent light resistance, and benzoyl groups are even more preferred. The benzoyl group may have substituents. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group; more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group; and even more preferably an alkoxy group, an alkylsulfanyl group, or an amino group.

The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2).
In the formula, R ^X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group.
R ^X2 represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, or amino group.
R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent;
However, at least one of R ^X10 to R ^X14 is an electron-withdrawing group.

In the above formula, it is preferable that R ^X12 is an electron-withdrawing group, and R ^X10 , R ^X11 , R ^X13 , and R ^X14 are hydrogen atoms.

Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the details of which are incorporated herein by reference.

The most preferred oxime compounds include oxime compounds having specific substituents as shown in Japanese Patent Publication No. 2007-269779 and oxime compounds having a thioaryl group as shown in Japanese Patent Publication No. 2009-191061, the details of which are incorporated herein by reference.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

Further preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is even more preferred, and the use of a metallocene compound or an oxime compound is even more preferred.

Furthermore, photoradical polymerization initiators can also be benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones fused with aromatic rings such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethylketal. Compounds represented by the following formula (I) can also be used.

In formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a phenyl group substituted with at least one alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms, or a biphenyl group; R ^I01 is a group represented by formula (II) or the same group as R ^I00 ; and R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in formula (I) above.

Furthermore, the photoradical polymerization initiator may also be a compound described in paragraphs 0048-0055 of International Publication No. 2015/125469, which is incorporated herein by reference.

As the photoradical polymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases and solubility in solvents, etc., improves, making precipitation less likely over time and improving the long-term stability of the resin composition. Specific examples of bifunctional or trifunctional or more photoradical polymerization initiators include dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015/004565, paragraphs 0407-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017/033680, as well as compounds (E) and (G) described in JP 2013-522445, and International Publication No. 2016/0 Examples include Cmpd1 to 7 described in Patent No. 34963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

If a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition of the present invention. Only one type of photopolymerization initiator may be included, or two or more types may be included. If two or more types of photopolymerization initiators are included, it is preferable that the total amount is within the above range.
Furthermore, since photopolymerization initiators can also function as thermal polymerization initiators, heating with an oven or hot plate may further accelerate the crosslinking process by the photopolymerization initiator.

[Sensitizer]
The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases.
Suitable sensitizers include compounds such as benzophenones, Michlaz ketones, coumarins, pyrazole azos, anilino azos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, pyrazolotriazole azos, pyridone azos, cyanines, phenothiazines, pyrrolopyrazole azomethine, xanthenes, phthalocyanines, benzopyrans, and indigos.
Examples of sensitizers include Michla'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-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzoate Examples include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide.
Other sensitizing dyes may also be used.
Details of the sensitizing dye can be found in paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, which are incorporated herein by reference.

When the resin composition contains a sensitizer, the sensitizer content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[Chain transport agent]
The resin composition of the present invention may contain a chain transfer agent. A chain transfer agent is defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include compounds having -S-S-, _-SO₂ -S-, -N-O-, SH, PH, SiH, and GeH in their molecules, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015/199219, which is incorporated herein by reference.

When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total is within the above range.

<Base Generator>
The resin composition of the present invention may contain a base-generating agent. Here, a base-generating agent is a compound that can generate a base by physical or chemical action. Preferred base-generating agents for the resin composition of the present invention include thermal base-generating agents and photobase-generating agents.
In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition also contains a base generator. By including a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example by heating, resulting in a cured product with good mechanical properties and chemical resistance, and thus good performance as an interlayer insulating film for redistribution layers included in semiconductor packages.
The base generator can be either an ionic or nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines.
There are no particular restrictions on the base generating agent according to the present invention, and known base generating agents can be used. Examples of known base generating agents include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like.
Specific examples of nonionic base-generating compounds include those represented by formulas (B1), (B2), or (B3).

In formulas (B1) and (B2), Rb ¹ , Rb ² , and Rb ³ are each independently an organic group that does not have a tertiary amine structure, a halogen atom, or a hydrogen atom. However, Rb ¹ and Rb ² cannot be hydrogen atoms at the same time. Also, Rb ¹ , Rb ² , and Rb ³ cannot have a carboxyl group. In this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbonyl group, that is, when it forms an amide group together with the nitrogen atom.

In formulas (B1) and (B2), ^Rb1 , ^Rb2 , and ^Rb3 preferably contain at least one cyclic structure, and more preferably at least two cyclic structures. The cyclic structure may be a monoring or a fused ring, with a monoring or a fused ring formed by the fusion of two monorings being preferred. The monoring is preferably a five-membered ring or a six-membered ring, with a six-membered ring being more preferred. The monoring is preferably a cyclohexane ring or a benzene ring, with a cyclohexane ring being more preferred.

More specifically, Rb ¹ and Rb ² are preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12 carbon atoms). These groups may have substituents within a range that provides the effects of the present invention. Rb ¹ and Rb ² may be bonded to each other to form a ring. The formed ring is preferably a 4 to 7-membered nitrogen-containing heterocycle. Rb ¹ and Rb ² are particularly preferably substituted linear, branched, or cyclic alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), more preferably substituted cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12 carbon atoms), and even more preferably substituted cyclohexyl groups.

Examples of ^Rb3 include alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6), arylalkyl groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), arylalkenyl groups (preferably with 8 to 24 carbon atoms, more preferably 8 to 20, and even more preferably 8 to 16), alkoxy groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryloxy groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or arylalkyloxy groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). Among these, cycloalkyl groups (preferably with 3 to 24 carbon atoms, more preferably with 3 to 18 carbon atoms, and even more preferably with 3 to 12 carbon atoms), arylalkenyl groups, and arylalkyloxy groups are preferred. Rb ³ may further have substituents within a range that provides the effects of the present invention.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or formula (B1-2).

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as Rb ¹ and Rb ² in formula (B1), respectively.
Rb ¹³ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12 carbon atoms), and may have substituents within a range that provides the effects of the present invention. Among these, an aryl alkyl group is preferred for Rb ¹³ .

Rb ³³ and Rb ³⁴ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8, and even more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11 carbon atoms), with the hydrogen atom being preferred.

Rb ³⁵ is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and even more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and even more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and even more preferably with 6 to 12 carbon atoms), and an aryl alkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and even more preferably with 7 to 12 carbon atoms), with the aryl group being preferred.

Compounds represented by formula (B1-1) are preferred, as are compounds represented by formula (B1-1a).

Rb ¹¹ and Rb ¹² are equivalent to Rb ¹¹ and Rb ¹² in equation (B1-1).
Rb ¹⁵ and Rb ¹⁶ are a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably with 1 to 6 carbon atoms, and even more preferably with 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 6 carbon atoms, and even more preferably with 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18 carbon atoms, and even more preferably with 6 to 10 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19 carbon atoms, and even more preferably with 7 to 11 carbon atoms), with a hydrogen atom or a methyl group being preferred.
Rb ¹⁷ is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and even more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and even more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and even more preferably with 6 to 12 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and even more preferably with 7 to 12 carbon atoms), with the aryl group being the most preferred.

In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the linking chain pathway connecting adjacent oxygen and carbon atoms, and having three or more atoms on the linking chain pathway. Also, R ^N1 and R ^N2 each independently represent a monovalent organic group.

In this specification, "linking chain" refers to the atomic chain on the path connecting two atoms or groups of atoms to be linked, specifically the one that links these linked objects in the shortest possible distance (minimum number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "length of the linking chain") is 4.

The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018/038002.

Furthermore, the base generator may also preferably contain a compound represented by the following formula (N1).

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, R ^C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms in the shortest path between the two carbonyl groups in the formula.

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), and are preferably hydrocarbon groups (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10 carbon atoms). Specifically, examples include aliphatic hydrocarbon groups (preferably having 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10 carbon atoms) or aromatic hydrocarbon groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), with aliphatic hydrocarbon groups being preferred. When aliphatic hydrocarbon groups are used as R ^N1 and R ^N2 , the resulting base is preferably highly basic. The aliphatic hydrocarbon group and aromatic hydrocarbon group may have substituents, and the aliphatic hydrocarbon group and aromatic hydrocarbon group may have oxygen atoms in the aliphatic hydrocarbon chain, aromatic ring, or substituent. In particular, embodiments in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain are exemplified.

Examples of aliphatic hydrocarbon groups constituting R ^N1 and R ^N2 include linear or branched linear alkyl groups, cyclic alkyl groups, groups relating to a combination of linear and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. Linear or branched linear alkyl groups are preferably those having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12. Examples of linear or branched linear alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group, and the like.
The cyclic alkyl group is preferably one having 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Examples of cyclic alkyl groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group.
The group comprising the combination of a linear alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Examples of the group comprising the combination of a linear alkyl group and a cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, and ethylcyclohexylethyl group.
The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched.
In particular, from the viewpoint of increasing the boiling point of the decomposition-derived bases described later, R ^N1 and R ^N2 are preferably alkyl groups having 5 to 12 carbon atoms. However, in formulations where adhesion when laminating with a metal (e.g., copper) layer is important, groups having a cyclic alkyl group or alkyl groups having 1 to 8 carbon atoms are preferred.

R ^N1 and R ^N2 may be linked to each other to form a cyclic structure. When forming a cyclic structure, oxygen atoms or the like may be present in the chain. The cyclic structure formed by R ^N1 and R ^N2 may be a monoring or a fused ring, but a monoring is preferred. The cyclic structure formed is preferably a five-membered or six-membered ring containing the nitrogen atom in formula (N1), and examples include pyrrole rings, imidazole rings, pyrazole rings, pyrroline rings, pyrrolidine rings, imidazolidine rings, pyrazolidine rings, piperidine rings, and morpholine rings, with pyrroline rings, pyrrolidine rings, piperidine rings, and morpholine rings being preferred.

R ^C1 represents a hydrogen atom or a protecting group, with a hydrogen atom being preferred.

As a protecting group, one that decomposes upon the action of an acid or base is preferred, and a protecting group that decomposes with an acid is particularly preferred.

Specific examples of protecting groups include linear or cyclic alkyl groups or linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl groups. Specific examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methyloxymethyl (MOM) and ethyloxyethyl (EE) groups. Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, glycidyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

There are no specific requirements for the divalent linking group constituting L, but hydrocarbon groups are preferred, and aliphatic hydrocarbon groups are more preferred. The hydrocarbon group may have substituents, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, it is preferable to have a divalent hydrocarbon linking group which may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group which may have an oxygen atom in the chain, or a group which is a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group which may have an oxygen atom in the chain, and even more preferably a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain. It is preferable that these groups do not have an oxygen atom.
The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group relating to the combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

The preferred linking group L is specifically a linear or branched linear alkylene group, a cyclic alkylene group, a group relating to a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched linear alkenylene group, a cyclic alkenylene group, an arylene group, or an arylenealkylene group.
The linear or branched alkylene group is preferably composed of 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms.
The cyclic alkylene group is preferably one with 3 to 12 carbon atoms, and more preferably one with 3 to 6 carbon atoms.
The combination of a linear alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6 carbon atoms.
The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms.

The linear or branched alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched alkenylene group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3.
The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2.
The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms.
The arylenealkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11.
Among these, linear alkylene groups, cyclic alkylene groups, alkylene groups having oxygen atoms in the chain, linear alkenylene groups, arylene groups, and arylenealkylene groups are preferred, and 1,2-ethylene groups, propanediyl groups (especially 1,3-propanediyl groups), cyclohexanediyl groups (especially 1,2-cyclohexanediyl groups), vinylene groups (especially cisvinylene groups), phenylene groups (1,2-phenylene groups), phenylenemethylene groups (especially 1,2-phenylenemethylene groups), and ethyleneoxyethylene groups (especially 1,2-ethyleneoxy-1,2-ethylene groups) are more preferred.

Examples of base-generating agents are listed below, but the present invention is not intended to be limited thereto.

The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018/038002.

Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these.

Specific examples of iminium salts include the following compounds, but the present invention is not limited to these.

If the resin composition of the present invention contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or 4 parts by mass or less.
One or more types of base-generating agents may be used. When using two or more types, it is preferable that the total amount is within the above range.

<Solvent>
The resin composition of the present invention preferably contains a solvent.
Any known solvent can be used as the solvent. Organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, alkyloxyethyl acetate, alkyloxybutyl acetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and 2-alkyloxy Suitable examples include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

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

As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

From the viewpoint of improving the properties of the coated surface, a mixture of two or more solvents is also preferable.

In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate, is particularly preferred.

From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method.

The resin composition of the present invention may contain only one solvent or two or more solvents. If two or more solvents are included, it is preferable that their total concentration falls within the above-mentioned range.

<Metal Adhesion Improver>
The resin composition of the present invention preferably contains a metal adhesion modifier to improve adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion modifiers include aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[Aluminum-based adhesive aid]
Examples of aluminum-based adhesives include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

Furthermore, other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935, the details 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. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. 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 their total value is within the above range.

<Migration inhibitors>
The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, it is possible to effectively suppress the movement of metal ions originating from the metal layer (metal wiring) into the film.

There are no particular restrictions on the migration inhibitors, but examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

Alternatively, an ion trapping agent that captures anions such as halogen ions can be used.

Other migration inhibitors that can be used include the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.

Specific examples of migration inhibitors include the following compounds.

When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition of the present invention.

The migration inhibitor may be one type or two or more types. If there are two or more migration inhibitors, it is preferable that their total number falls within the above range.

<Potromylation inhibitors>
The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

Specific polymerization inhibitor compounds include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine monocerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso 1-Naphthol, 2-Nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-Nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-Tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenothiazine, phenoxazine, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbanate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. are preferably used. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Publication No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 may also be used, and this is incorporated herein by reference.

If the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition of the present invention.

The polymerization inhibitor may be one type or two or more types. If there are two or more polymerization inhibitors, it is preferable that their total number falls within the above range.

<Other additives>
The resin composition of the present invention may optionally contain various additives, such as photoacid generators, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anti-aggregating agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013/0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and the contents of these publications are incorporated herein. When these additives are incorporated, it is preferable that their total amount be 3% by mass or less of the solid content of the resin composition of the present invention.

[Surfactants]
Various surfactants can be used, including fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid properties (especially fluidity) when prepared as a coating solution are further improved, and the uniformity of the coating thickness and the efficiency of the liquid can be further improved. Specifically, when forming a film using a coating solution to which a composition containing a surfactant has been applied, the interfacial tension between the surface to be coated and the coating solution decreases, improving wettability to the surface to be coated and improving coatability to the surface to be coated. Therefore, it is possible to more favorably form a film of uniform thickness with less thickness variation.

Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (all manufactured by DIC Corporation), Florard FC430, FC431, FC171, Novec FC4430, FC4432 (all manufactured by 3M Corporation). Examples include Asahi Glass Co., Ltd.'s Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, and KH-40, as well as PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA). Fluorine-based surfactants may also be compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503, and these contents are incorporated herein by reference. Block polymers can also be used as fluorine-based surfactants. Specific examples include the compounds described in Japanese Patent Publication No. 2011-89090, the details of which are incorporated herein by reference.
Fluorine-based surfactants can also preferably be fluorine-containing polymer compounds that include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). The following compounds are also examples of fluorine-based surfactants used in the present invention.

The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.
Fluorine-based surfactants can also be fluorine-containing polymers having ethylenically unsaturated groups in their side chains. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Commercially available examples include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Toray Dow Corning Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials, Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BIC Chemie Co., Ltd.).

Examples of hydrocarbon-based surfactants include Pionin A-76, Newcalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T, etc. (all manufactured by Takemoto Oil & Fat Co., Ltd.).

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available products include Pluronic® L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000 (manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Paionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

Examples of cationic surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 77, No. 90, and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

Examples of anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.).

One type of surfactant may be used, or two or more types may be used in combination.
The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[Higher fatty acid derivative]
In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention may contain a higher fatty acid derivative such as behenic acid or behenic acid amide, which may be unevenly distributed on the surface of the resin composition during the drying process after application.

Furthermore, higher fatty acid derivatives may also be compounds described in paragraph 0155 of International Publication No. 2015/199219, which are incorporated herein by reference.

When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. There may be only one type of higher fatty acid derivative, or there may be two or more types. If there are two or more types of higher fatty acid derivatives, it is preferable that their total is within the above range.

[Thermal polymerization initiator]
The resin composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals in response to thermal energy, thereby initiating or promoting the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, thereby further improving solvent resistance. In addition, the photopolymerization initiators mentioned above may also have the function of initiating polymerization in response to heat, and may be added as thermal polymerization initiators.

Specifically, examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the details of which are incorporated herein by reference.

If a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition of the present invention. Only one thermal polymerization initiator may be included, or two or more may be included. If two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[Inorganic particles]
The resin composition of the present invention may contain inorganic fine particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm.
The above-mentioned average particle diameter of the fine particles is both the primary particle diameter and the volume-average particle diameter. The volume-average particle diameter can be measured by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.).
If the above measurement methods are difficult, measurements can also be performed using centrifugal sedimentation light transmission, X-ray transmission, or laser diffraction/scattering methods.

[UV absorber]
The composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers that can be used include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers.
Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-t-butylphenyl salicylate, while examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, and 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole.

Examples of substituted acrylonitrile-based UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triazine-based UV absorbers include mono(hydroxyphenyl)triazine compounds such as 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis(2-hydroxy(hydroxy) Examples include bis(hydroxyphenyl)triazine compounds such as c-3-methyl-4-propyloxyphenyl)-6-(4-methylphenyl)-1,3,5-triazine and 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine; and tris(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]-1,3,5-triazine.

In the present invention, the above-mentioned ultraviolet absorbers may be used individually or in combination of two or more types.
The composition of the present invention may or may not contain an ultraviolet absorber, but if it does, the amount of ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less, based on the total solid content mass of the composition of the present invention.

[Organotitanium compounds]
The resin composition of this embodiment may contain an organotitanium compound. By including an organotitanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

Examples of usable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds.
Specific examples of organotitanium compounds are shown in I) to VII) below:
I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and yield a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), and titanium diisopropoxidebis(ethylacetoacetate).
II) Tetraalkoxy titanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], etc.
III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc.
IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.
V) Titanium oxide compounds: For example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, etc.
VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate, etc.
VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

In particular, from the viewpoint of achieving better chemical resistance, the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds, and III) titanocene compounds. Titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are especially preferred.

When incorporating an organic titanium compound, the amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are more effectively expressed in the resulting cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is superior.

[Antioxidant]
The composition of the present invention may contain an antioxidant. Including an antioxidant as an additive can improve the elongation properties of the cured film and its adhesion to metal materials. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. Any phenol compound known as a phenolic antioxidant can be used. A preferred phenol compound is a hindered phenol compound. Compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group are preferred. Preferred substituents are substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Furthermore, compounds having both a phenol group and a phosphite ester group within the same molecule are also preferred as antioxidants. Phosphorus-based antioxidants can also be suitably used. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphate. Examples of commercially available antioxidants include ADEKA STUB AO-20, ADEKA STUB AO-30, ADEKA STUB AO-40, ADEKA STUB AO-50, ADEKA STUB AO-50F, ADEKA STUB AO-60, ADEKA STUB AO-60G, ADEKA STUB AO-80, and ADEKA STUB AO-330 (all manufactured by ADEKA Corporation). Furthermore, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 may also be used as antioxidants, and this information is incorporated herein. Additionally, the compositions of the present invention may optionally contain latent antioxidants. Examples of latent antioxidants include compounds in which the antioxidant portion is protected by a protecting group, and which function as antioxidants when heated at 100 to 250°C or when heated at 80 to 200°C in the presence of an acid/base catalyst, thereby removing the protecting group. Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Publication No. 2017-008219, the contents of which are incorporated herein by reference. Examples of commercially available latent antioxidants include ADEKA Arclus GPA-5001 (manufactured by ADEKA Corporation).
Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and the compound represented by formula (3).

In general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R ⁶ represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R ⁷ represents a 1-4 valent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer from 1 to 4.

The compound represented by formula (3) suppresses the oxidative degradation of aliphatic groups and phenolic hydroxyl groups present in resins. Furthermore, it can suppress metal oxidation by providing rust prevention to metal materials.

Since it can act on both the resin and the metal material simultaneously, k is more preferably an integer between 2 and 4. Examples of R7 include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof, and may also have substituents. Among these, alkyl ether groups and -NH- are preferred from the viewpoint of solubility in the developer and metal adhesion, and -NH- is more preferred from the viewpoint of interaction with the resin and metal adhesion due to metal complex formation.

Examples of compounds represented by general formula (3) include the following, but are not limited to the structures shown below.

The amount of antioxidant added 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. Adding 0.1 parts by mass or more makes it easier to obtain improved elongation properties and adhesion to metal materials even in high-temperature and high-humidity environments. Adding 10 parts by mass or less improves the sensitivity of the resin composition, for example, through interaction with the photosensitive agent. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.

[Anti-coagulation agent]
The resin composition of this embodiment may optionally contain an anti-flocculation agent. Examples of anti-flocculation agents include sodium polyacrylate.

In the present invention, one type of anticoagulant may be used alone, or two or more types may be used in combination.
The composition of the present invention may or may not contain an anti-coagulant. If it does contain an anti-coagulant, the amount of the anti-coagulant is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less, based on the total solid content mass of the composition of the present invention.

[Phenol compounds]
The resin composition of this embodiment may optionally contain a phenolic compound. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

In this invention, a single phenolic compound may be used alone, or two or more compounds may be used in combination.
The composition of the present invention may or may not contain a phenolic compound. If it does contain a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content of the composition of the present invention.

[Other polymer compounds]
Other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified forms into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

In this invention, the other polymer compounds may be used individually or in combination of two or more.
The composition of the present invention may or may not contain other polymer compounds, but if it does, the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less, based on the total solid content mass of the composition of the present invention.

<Properties of resin composition>
The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, a viscosity of 1,000 ^mm² /s to 12,000 ^mm² /s is preferred, 2,000 ^mm² /s to 10,000 ^mm² /s is more preferred, and 2,500 ^mm² /s to 8,000 ^mm² /s is even more preferred. Within the above range, it becomes easy to obtain a coating film with high uniformity. If the viscosity is 1,000 ^mm² /s or higher, it is easy to coat the film with the thickness required for, for example, a rewiring insulating film, and if the viscosity is 12,000 ^mm² /s or lower, a coating film with excellent surface properties can be obtained.

<Restrictions on substances contained in resin compositions>
The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved.
Methods for maintaining moisture content include adjusting humidity during storage and reducing the porosity of the storage container.

From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

Furthermore, methods for reducing metal impurities unintentionally present in the resin composition of the present invention include selecting raw materials with low metal content as constituent materials of the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and performing distillation under conditions that suppress contamination as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

When considering the application of the resin composition of the present invention as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. In particular, the amount of halogen atoms present in the form of halogen ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above ranges.
Methods for adjusting the halogen atom content include ion exchange treatment.

Conventional containers can be used as containers for the resin composition of the present invention. Furthermore, to suppress the incorporation of impurities into the raw materials and the resin composition of the present invention, it is also preferable to use multilayer bottles with an inner wall constructed of six types of resin in six layers, or bottles with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

<Cured product of resin composition>
A cured product of the resin composition of the present invention can be obtained by curing the resin composition.
The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
The curing of the resin composition is preferably by heating, more preferably within the range of 120°C to 400°C, even more preferably within the range of 140°C to 380°C, and particularly preferably within the range of 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited and can be selected according to the application, such as in the form of a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. Furthermore, the shape of the cured product can be selected according to the application by pattern processing of the resin composition, such as forming a protective film on the wall surface, forming via holes for conductivity, adjusting impedance, capacitance or internal stress, or providing heat dissipation functions. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage rate of the resin composition of the present invention upon curing is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated using the following formula.
Shrinkage rate [%] = 100 - (Volume after hardening ÷ Volume before hardening) × 100

<Properties of cured resin compositions>
The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

<Preparation of resin composition>
The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods.
Mixing can be achieved using methods such as mixing with agitators, mixing with a ball mill, or mixing by rotating the tank itself.
The mixing temperature is preferably 10 to 30°C, and more preferably 15 to 25°C.

Furthermore, it is preferable to perform filtration using a filter to remove foreign matter such as dirt and fine particles from the resin composition of the present invention. The filter pore size can be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. If the filter material is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter may be one that has been pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. As an example of a connection configuration, an HDPE filter with a pore size of 1 μm is connected in series as the first stage, and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Furthermore, various materials may be filtered multiple times. When filtering multiple times, circulating filtration may be used. Furthermore, filtration may be performed under pressure. When filtration is performed under pressure, the pressure applied may be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. A combination of filter filtration and impurity removal using an adsorbent may also be used. As the adsorbent, any known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
Furthermore, after filtration using a filter, the resin composition filled into the bottle may be subjected to a degassing process by placing it under reduced pressure.

(Method for manufacturing hardened product)
The method for producing the cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film.
Furthermore, the method for producing a cured product of the present invention more preferably includes the above-mentioned film formation step, an exposure step for selectively exposing the film formed in the film formation step, and a developing step for developing the film exposed in the exposure step using a developer to form a pattern.
The method for producing a cured product of the present invention is particularly preferably to include at least one of the above-mentioned film formation step, exposure step, development step, and a heating step for heating the pattern obtained in the development step and a post-development exposure step for exposing the pattern obtained in the development step.
Furthermore, the manufacturing method of the present invention may also preferably include the above-mentioned film formation step and the step of heating the above-mentioned film.
The details of each step are explained below.

<Film formation process>
The resin composition of the present invention can be used in a film-forming process, where it is applied to a substrate to form a film.
The method for producing the cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film.

[Base material]
The type of substrate can be appropriately determined according to the application, but examples include semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal, and substrates in which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass); TFT (thin film transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). In the present invention, semiconductor fabrication substrates are particularly preferred, and silicon substrates, Cu substrates, and mold substrates are more preferred.
Furthermore, these substrates may have layers on their surface, such as an adhesion layer or an oxidation layer, provided with hexamethyldisilazane (HMDS) or the like.
Furthermore, the shape of the base material is not particularly limited and may be circular or rectangular.
For the base material, if it is circular, for example, the diameter is 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, for example, the length of the shorter side is 100 to 1000 mm, preferably 200 to 700 mm.
Furthermore, as the base material, for example, a plate-shaped, preferably panel-shaped, base material (substrate) is used.

Furthermore, when a resin composition is applied to the surface of a resin layer (for example, a layer made of cured material) or a metal layer to form a film, the resin layer or metal layer serves as the substrate.

As a means of applying the resin composition of the present invention onto a substrate, coating is preferred.

Specific examples of application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating are more preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate; for circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
Alternatively, a method can be applied in which a coating film, which has been previously applied and formed on a temporary support using the above application method, is transferred onto a substrate.
Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Publication No. 2006-047592 can be suitably used in the present invention as well.
Furthermore, a process to remove excess film from the edges of the substrate may be performed. Examples of such processes include edge bead rinsing (EBR) and back rinsing.
Alternatively, a pre-wetting process may be employed in which the substrate is coated with various solvents to improve its wettability before applying the resin composition to the substrate.

<Drying process>
The above film may be subjected to a drying step (a process in which the formed film (layer) is dried in order to remove the solvent after the film formation step (layer formation step).
In other words, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film formation step.
Furthermore, it is preferable that the above drying step be performed after the film formation step and before the exposure step.
The drying temperature of the film in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

<Exposure Process>
The above film may be subjected to an exposure process in which the film is selectively exposed.
In other words, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film formation step.
Selective exposure means exposing only a portion of a film. Selective exposure creates areas on the film that are exposed (exposed regions) and areas that are not exposed (unexposed regions).
The exposure amount is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is preferably 50 to 10,000 mJ/ ^cm² and more preferably 200 to 8,000 mJ/ ^cm² in terms of exposure energy at a wavelength of 365 nm.

The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

In relation to the light source, the exposure wavelengths include: (1) semiconductor lasers (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths: g, h, and i), (4) excimer lasers, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), _F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beams, and (7) the second harmonic 532 nm and third harmonic 355 nm of YAG lasers. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and among these, exposure with the i-line is preferred. This can result in particularly high exposure sensitivity.
Furthermore, the exposure method is not particularly limited, and any method in which at least a portion of the film made of the resin composition of the present invention is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

<Post-exposure heating process>
The above film may be subjected to a heating step after exposure (post-exposure heating step).
In other words, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed by the exposure step is heated.
The post-exposure heating step can be performed after the exposure step and before the development step.
The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C.
The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes.
The heating rate in the post-exposure heating process is preferably 1 to 12°C/min from the initial heating temperature to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min.
Furthermore, the heating rate may be changed as needed during the heating process.
The heating means in the post-exposure heating process is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used.
Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, or argon through the system.

<Developing process>
The film after exposure may be subjected to a developing process in which it is developed using a developing solution to form a pattern.
In other words, the method for producing a cured product of the present invention may include a developing step in which the film exposed in the exposure step is developed using a developer to form a pattern. By developing, one of the exposed and unexposed parts of the film is removed, and a pattern is formed.
Here, development in which the unexposed parts of the film are removed by the development process is called negative development, and development in which the exposed parts of the film are removed by the development process is called positive development.

[Developer]
Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

When the developing solution is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and TMAH is more preferred. The content of basic compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, when TMAH is used, based on the total mass of the developer.

When the developer contains an organic solvent, the organic solvent is an ester, such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, alkyloxyethyl acetate, alkyloxybutyl acetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyethyl acetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxypropionate) Methyl methyl phosphate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl esters of 2-alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvic acid Methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl Suitable examples include propyl ether acetates, ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone, cyclic hydrocarbons such as toluene, xylene, anisole, and other aromatic hydrocarbons, cyclic terpenes such as limonene, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the developer contains an organic solvent, one or more organic solvents can be used in mixture form. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.

When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The above content may also be 100% by mass.

The developing solution may contain other components as well.
Other components include, for example, known surfactants and known defoaming agents.

[Method of supplying developing solution]
There are no particular restrictions on the method of supplying the developer, as long as the desired pattern can be formed. These methods include immersing the substrate on which the film has been formed in the developer, paddle development where the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, and spray nozzles.
From the viewpoint of developer penetration, removal of non-image areas, and manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying it with a spray nozzle is preferred, and from the viewpoint of developer penetration into the image area, the method of supplying with a spray nozzle is more preferred.
Alternatively, the process may involve continuously supplying the developer solution through a straight nozzle, spinning the substrate to remove the developer solution from the substrate, spin-drying, and then continuously supplying the developer solution again through a straight nozzle, spinning the substrate to remove the developer solution from the substrate. This process may be repeated multiple times.
Furthermore, possible methods for supplying the developer during the developing process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept in a nearly stationary state on the substrate, a process in which the developer is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer solution during development is not particularly specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.

In the development process, after processing with the developer solution, the pattern may be further washed (rinsed) with a rinsing solution. Alternatively, methods such as supplying the rinsing solution before the developer solution in contact with the pattern completely dries may be employed.

[Rinsing solution]
If the developer is an alkaline aqueous solution, water can be used as the rinsing solution. If the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

When the rinse solution contains an organic solvent, the organic solvent can be an ester such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, alkyloxyethyl acetate, alkyloxybutyl acetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyethyl acetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxypropyl Methyl propyl 2-alkyloxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), propyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), Methyl phosphate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono Suitable examples include propyl ether acetate, ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone, cyclic hydrocarbons such as toluene, xylene, anisole, and other aromatic hydrocarbons, cyclic terpenes such as limonene, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. In this invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are even more preferred.

When the rinsing solution contains an organic solvent, it is preferable that the rinsing solution contains 50% or more by mass of the organic solvent, more preferably 70% or more by mass, and even more preferably 90% or more by mass. Alternatively, the rinsing solution may contain 100% by mass of the organic solvent.

The rinse solution may contain other ingredients as well.
Other components include, for example, known surfactants and known defoaming agents.

[Method of supplying rinse solution]
There are no particular restrictions on the method of supplying the rinse solution, as long as a desired pattern can be formed. These methods include immersing the substrate in the rinse solution, supplying the solution by pouring it onto the substrate, supplying the rinse solution to the substrate with a shower, and continuously supplying the rinse solution to the substrate using means such as a straight nozzle.
From the viewpoint of the penetration of the rinse solution, the removal of non-image areas, and manufacturing efficiency, there are methods for supplying the rinse solution using shower nozzles, straight nozzles, spray nozzles, etc. A method of continuous supply using a spray nozzle is preferred, and from the viewpoint of the penetration of the rinse solution into the image area, the method of supplying with a spray nozzle is more preferred. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc.
In other words, the rinsing step is preferably a step of supplying the rinsing solution to the exposed film using a straight nozzle or a continuous supply step, and more preferably a step of supplying the rinsing solution using a spray nozzle.
Furthermore, possible methods for supplying the rinsing solution in the rinsing process include a process in which the rinsing solution is continuously supplied to the substrate, a process in which the rinsing solution is kept in a nearly stationary state on the substrate, a process in which the rinsing solution is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

<Heating process>
The pattern obtained by the developing process (or the pattern after rinsing, if a rinsing process is performed) may be subjected to a heating process in which the pattern obtained by the developing process is heated.
In other words, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the developing step.
Furthermore, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing a developing step, or a film obtained by a film formation step.
During the heating process, resins such as polyimide precursors undergo cyclization to become resins such as polyimide.
Furthermore, crosslinking of unreacted crosslinkable groups in specific resins or other crosslinking agents also proceeds.
The heating temperature (maximum heating temperature) in the heating process is preferably 50 to 450°C, more preferably 150 to 350°C, even more 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 heating promotes the cyclization reaction of the polyimide precursor within the pattern by the action of bases generated from the base generating agent.

In the heating process, heating is preferably carried out at a heating rate of 1 to 12°C/min from the initial heating temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the heating rate to 1°C/min or more, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the heating rate to 12°C/min or less, it is possible to alleviate residual stress in the cured product.
In addition, in the case of an oven capable of rapid heating, it is preferable to raise the temperature from the initial temperature to the maximum heating temperature at a rate of 1 to 8°C/second, more preferably 2 to 7°C/second, and even more preferably 3 to 6°C/second.

The starting temperature for 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 starting temperature for heating refers to the temperature at which the process of heating to the maximum heating temperature is initiated. For example, when the resin composition of the present invention is applied to a substrate and then dried, this is the temperature of the film (layer) after drying. For example, it is preferable to start the heating process from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

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.

In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, 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 carried out in stages. For example, the process may involve raising the temperature from 25°C to 120°C at a rate of 3°C/min, holding at 120°C for 60 minutes, raising the temperature from 120°C to 180°C at a rate of 2°C/min, and holding at 180°C for 120 minutes. It is also preferable to treat while irradiating with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such pretreatment steps can improve the properties of the film. The pretreatment step is best carried out for a short time, from about 10 seconds to 2 hours, with 15 seconds to 30 minutes being more preferable. The pretreatment may consist of two or more steps; for example, the first pretreatment step may be performed in the range of 100 to 150°C, followed by the second pretreatment step in the range of 150 to 200°C.
Furthermore, the mixture may be cooled after heating, and in this case, the cooling rate is preferably 1 to 5°C/minute.

The heating process is preferably carried out in a low-oxygen atmosphere by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, in order to prevent the decomposition of specific resins. The oxygen concentration is preferably 50 ppm (by volume) or less, and more preferably 20 ppm (by volume) or less.
The heating means in the heating process are not particularly limited, but examples include hot plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

<Post-development exposure process>
The pattern obtained by the development process (or the pattern after rinsing, if a rinsing process is performed) may be subjected to a post-development exposure process in which the pattern after the development process is exposed, either in place of the heating process or in addition to the heating process.
In other words, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or it may include only one of the heating step and the post-development exposure step.
In the post-development exposure process, for example, reactions such as the cyclization of polyimide precursors, etc., by exposure to a photobase generator, and the elimination of acid-degradable groups by exposure to a photoacid generator can be accelerated.
In the post-development exposure step, it is sufficient for at least a portion of the pattern obtained in the development step to be exposed, but it is preferable for the entire pattern to be exposed.
The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/ ^cm² , and more preferably 100 to 15,000 mJ/ ^cm² , in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive.
The post-development exposure step can be performed, for example, using the light source from the exposure step described above, and it is preferable to use broadband light.

<Metal layer formation process>
The pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process) may be subjected to a metal layer formation process in which a metal layer is formed on the pattern.
In other words, the method for producing a cured product of the present invention preferably includes a metal layer formation step in which a metal layer is formed on a pattern obtained by a developing step (preferably one that has been subjected to a heating step and at least one of a post-development exposure step).

The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography and etching, and patterning methods combining photolithography and electroplating can be mentioned. Preferred embodiments of plating include electroplating using copper sulfate or copper cyanide plating solutions.

The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

<Application>
Examples of applications for the cured product of the present invention include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. Other applications include etching patterns onto sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), or insulating films for the above-mentioned mounting applications. For more information on these applications, please refer to, for example, Science & Technology Co., Ltd., "High-Performance Polyimide Materials and Application Technologies," April 2008, supervised by Masaaki Kakimoto; CMC Technical Library, "Fundamentals and Development of Polyimide Materials," November 2011; and the Japan Polyimide and Aromatic Polymer Research Association, ed., "Latest Polyimides: Fundamentals and Applications," NTS, August 2010.

Furthermore, the method for manufacturing the cured product of the present invention, or the cured product of the present invention, can also be used in the manufacture of printing plates such as offset plates or screen printing plates, for etching molded parts, and for the manufacture of protective lacquers and dielectric layers in electronics, particularly microelectronics.

(Laminate and method for manufacturing the laminate)
The laminate of the present invention refers to a structure having multiple layers made of the cured product of the present invention.
The laminate of the present invention is a laminate comprising two or more layers made of a cured material, and may be a laminate comprising three or more layers.
Of the two or more layers of the cured material contained in the laminate, at least one is made of the cured material of the present invention. From the viewpoint of suppressing shrinkage of the cured material or deformation of the cured material due to such shrinkage, it is also preferable that all layers of the cured material contained in the laminate are made of the cured material of the present invention.

In other words, the method for manufacturing the laminate of the present invention preferably includes a method for manufacturing the cured product of the present invention, and more preferably includes repeating the method for manufacturing the cured product of the present invention multiple times.

The laminate of the present invention preferably comprises two or more layers made of a cured material, with a metal layer included between any of the layers made of the cured material. The metal layer is preferably formed by the metal layer formation process described above.
In other words, the method for manufacturing a laminate of the present invention preferably further includes a metal layer formation step in which a metal layer is formed on a layer made of a cured product during multiple processes for manufacturing a cured product. Preferred embodiments of the metal layer formation step are as described above.
As an example of the above-mentioned laminate, a preferred laminate is one that includes at least three layers in which a layer made of a first cured material, a metal layer, and a layer made of a second cured material are laminated in this order.
Preferably, both the layer made of the first cured product and the layer made of the second cured product are layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may be compositions with the same composition or compositions with different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a redistribution layer.

<Lamination process>
The method for manufacturing the laminate of the present invention preferably includes a lamination step.
The lamination process is a series of steps that include performing, in this order, at least one of the following on the surface of a pattern (resin layer) or metal layer: (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step, and post-development exposure step. However, the film formation step in (a) and at least one of the heating step and post-development exposure step in (d) may be repeated. Furthermore, a metal layer formation step in (e) may be included after at least one of the heating step and post-development exposure step. Needless to say, the lamination process may also include the above-mentioned drying step, etc., as appropriate.

If further lamination is performed after the lamination process, a surface activation treatment step may be performed after the exposure process, the heating process, or the metal layer formation process. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be described later.

The above lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times.
For example, a configuration with two to twenty layers of resin, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a configuration with two to nine layers is even more preferred.
Each of the above layers may or may not have the same composition, shape, film thickness, etc.

In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer. Specifically, examples include repeating the following steps in order: (a) film formation step, (b) exposure step, (c) development step, (d) heating step and at least one of the post-development exposure step, and (e) metal layer formation step, or repeating the following steps in order: (a) film formation step, (d) heating step and at least one of the post-development exposure step, and (e) metal layer formation step. By alternately performing the lamination step of stacking the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately stacked.

(Surface activation treatment process)
The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step of surface activating at least a portion of the above-mentioned metal layer and resin composition layer.
The surface activation treatment step is usually performed after the metal layer formation step, but the surface activation treatment step may be performed on the resin composition layer after the development step (preferably after at least one of the heating step and the post-development exposure step) before the metal layer formation step is performed.
The surface activation treatment may be performed on at least a portion of the metal layer, on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion with the resin composition layer (film) provided on that surface can be improved.
Furthermore, it is preferable to perform the surface activation treatment on part or all of the resin composition layer (resin layer) after exposure. By performing the surface activation treatment on the surface of the resin composition layer in this way, the adhesion between the surface-activated surface and the metal layer or resin layer can be improved. In particular, when the resin composition layer has hardened, such as when negative type development is performed, it is less susceptible to damage from the surface treatment and adhesion is easily improved.
Specifically, surface activation treatments can be selected from plasma treatment with various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment with _CF₄ / _O₂ , _NF₃ / _O₂ , _SF₆ , _NF₃ , _NF₃ / _O₂ , surface treatment using ultraviolet (UV) ozone method, immersion in an aqueous hydrochloric acid solution to remove the oxide film followed by immersion in an organic surface treatment agent containing at least one amino group and a thiol group, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500 to 200,000 J/ ^m² , more preferably 1,000 to 100,000 J/ ^m² , and most preferably 10,000 to 50,000 J/ ^m² .

(Method of manufacturing semiconductor devices)
The present invention also discloses semiconductor devices comprising a cured product of the present invention or a laminate of the present invention.
The present invention also discloses a method for manufacturing a cured product of the present invention, or a method for manufacturing a semiconductor device including a method for manufacturing a laminate of the present invention. Specific examples of semiconductor devices in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 and Figure 1 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

(compound)
The compound of the present invention is a compound represented by the following formula (2-1).
In formula (2-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, ^L1 represents a single bond or a divalent linking group, Z represents an amide group, the orientation of the amide group in Z is not particularly limited, ^L2 represents a single bond or a divalent linking group, Ar represents an aromatic group, X represents an alkylene group, and x represents an integer between 1 and 3.
The compound of the present invention is synonymous with the compound represented by formula (2-1) described in the resin composition of the present invention above, and the preferred embodiments are also the same.

The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

<Method for producing precursors of cyclized resins>
[Synthesis Example 1: Synthesis of a precursor (resin 2) of a cyclized resin]
23.48 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and 22.27 g of bisphthalic acid dianhydride (BPDA) were placed in a separable flask, 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of tetrahydrofuran were added, and the mixture was stirred at room temperature (25°C). While stirring, 24.66 g of pyridine was added to obtain the reaction mixture. After the exothermic reaction was complete, the mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes with stirring. Subsequently, 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.73 g of tetrahydrofuran was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethyl alcohol was added and stirred for 1 hour, and then 136.83 g of tetrahydrofuran was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.
The resulting reaction solution was added to 716.21 g of ethyl alcohol to produce a precipitate consisting of crude polymer. The crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the resulting precipitate was filtered off and then vacuum dried to obtain 80.3 g of powdered resin 2. The molecular weight of resin 2 was measured by gel permeation chromatography (on a standard polystyrene basis), and the weight-average molecular weight (Mw) was found to be 20,000. The structure of resin 2 is presumed to be represented by the following formula (P-1).

[Synthesis Example 2: Synthesis of a Precursor for Cyclic Resin (Resin 1)]
21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyclyme (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and while maintaining the temperature at -10±5°C, 17.0 g of thionyl chloride was added over 60 minutes. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 60 minutes at -10±5°C, and the mixture was stirred at room temperature for 2 hours. Then, 10.0 g of ethanol was added and the mixture was stirred at room temperature for 1 hour.
Next, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was filtered and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) was added to the resulting solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was filtered again and dried under reduced pressure at 45°C for 3 days.
46.6 g of the dried powder was dissolved in 419.6 g of tetrahydrofuran, and then 2.3 g of triethylamine was added and the mixture was stirred at room temperature for 35 minutes. After that, 3000 g of ethanol was added and the precipitate was filtered off. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) were added and the mixture was stirred for 4 hours. The ion exchange resin was then removed by filtration, and the resulting polymer solution was added to a mixed solution of 4500 g of heptane and 500 g of ethyl acetate to obtain a precipitate. The precipitate was filtered off and dried under reduced pressure at 45°C for 24 hours to obtain 45.1 g of resin 1.
The structure of resin 1 is presumed to be represented by the following formula (P-2). When the molecular weight of resin 1 was measured by gel permeation chromatography (on a standard polystyrene basis), the weight-average molecular weight (Mw) was found to be 20,000. Furthermore, by appropriately adjusting the equivalent amount of 4,4'-diaminodiphenyl ether, resin 1 with an Mw of 10,000 and resin 1 with an Mw of 30,000 were also synthesized.

[Synthesis Examples 3-8: Synthesis of Precursors of Cyclic Resins (Resins 3-8)]
Resins 3 to 8, each having a structure represented by one of the following formulas (P-3) to (P-8), were synthesized in the same manner as in Synthesis Example 2, except that the compounds used were changed as appropriate.
The Mw values for resin 3 were 20,000, resin 4 were 20,000, resin 5 were 20,000, resin 6 were 20,000, resin 7 were 20,000, and resin 8 were 20,000.

[Synthesis Example 9: Synthesis of Resin 9]
In a flask equipped with a condenser and stirrer, 18.0 g (40.5 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP) while removing water. Next, 7.95 g (39.7 mmol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 3 hours, followed by stirring at 45°C for another 3 hours. Then, 12.8 g (160 mmol) of pyridine, 10.3 g (101 mmol) of acetic anhydride, and 40.0 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80°C for 3 hours. Finally, 50 g of N-methylpyrrolidone (NMP) was added to dilute the mixture.
This reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. The obtained resin was dried under reduced pressure at 40°C for 1 day to obtain resin 9. The molecular weight of resin 9 was measured by gel permeation chromatography (in terms of standard polystyrene), and the weight-average molecular weight (Mw) was 20,000. The structure of resin 9 is presumed to be represented by the following formula (P-9).

[Synthesis Example 10: Synthesis of Resin 10]
Resin 10 was obtained by the same method as in Synthesis Example 9, except that 4,4'-(hexafluoroisopropylidene)diphthalic anhydride was replaced with an equimolar amount of 4,4'-oxydiphthalic dianhydride (ODPA), and 4,4'-diaminodiphenyl ether was replaced with an equimolar amount of 2,2'-bis(trifluoromethyl)benzidine. The molecular weight of resin 10 was measured by gel permeation chromatography (on a standard polystyrene basis), and the weight-average molecular weight (Mw) was 20,000. The structure of resin 10 is presumed to be represented by the following formula (P-10).

<Examples and Comparative Examples>
In each example, the components listed in the table below were mixed to obtain each resin composition. Similarly, in each comparative example, the components listed in the table below were mixed to obtain each comparative composition.
Specifically, the content (amount blended) of each component listed in the table other than the solvent was the amount (parts by mass) indicated in the "parts by mass" column for each column in the table.
The solvent content (amount blended) was determined so that the solid content concentration of the composition matched the value (mass %) in the "Solid Content Concentration" column of the table, and the ratio of the content of each solvent to the total mass of the solvent (mass ratio) matched the ratio indicated in the "Ratio" column of the table.
The obtained resin composition and comparative composition were subjected to pressure filtration using a polytetrafluoroethylene filter with a pore width of 0.8 μm.
In addition, in the table, a "-" indicates that the composition does not contain the corresponding ingredient.

Details of each component listed in the table are as follows:

〔resin〕
• Resins 1 to 10: Resins 1 to 10 obtained by the above synthesis example.

[Monomers (polymerizable compounds)]
• M-1: Compound with the structure shown below; the subscript in parentheses indicates the number of repetitions.

[Polymerization initiator or photoacid generator]
• I-1 to I-5: Compounds with the following structures

[Thermal base generator]
A-1: Compound with the following structure

[Polymerization inhibitors]
• B-1 to B-2: Compounds with the following structure

[Compound A or silane coupling agent]
• C-1 to C-21: Compounds with the following structure. All of C-1 to C-21 are compounds corresponding to compound A mentioned above.
CX-1: A compound with the structure shown below. CX-1 is a compound that corresponds to the other silane coupling agents mentioned above.
RC-1: A compound with the structure shown below. RC-1 is a compound that corresponds to the other silane coupling agents mentioned above.
Furthermore, in the following structure, Me represents a methyl group and Et represents an ethyl group.

[Synthesis Example C-1: Synthesis of Compound C-1]
5.0 g of 3-isochromanone was dissolved in 33.7 g of tetrahydrofuran in a flask. The solution was cooled to -5°C to 0°C in an ice bath with NaCl. 7.1 g of 3-aminopropyltriethoxysilane was added dropwise, and the reaction solution was then heated to 50°C. After confirming that the starting materials had disappeared, 12.4 g of the target product C-1 in oil form was obtained by heating and reducing the pressure of the solution. ^1H -NMR data is shown below.
¹ H-NMR, 400 MHz, δ ((CDCl ₃ ) ppm: 0.54 (2H, t, J = 8), 1.20 (9H, t, J = 6), 1.51-1.60 (2H, m), 3.18 (2H, q, J = 7.3), 3.73-3.80 (8H, m), 4.66 (2H, s), 6.80 (1H, bs), 7.24-7.38 (4H, m).

[Migration inhibitors]
• D-1: Compound with the following structure

[Additives]
• E-1 to E-3: Compounds with the following structure

〔solvent〕
NMP: N-methyl-2-pyrrolidone, EL: ethyl lactate, DMSO: dimethyl sulfoxide, GBL: γ-butyrolactone

<Evaluation>
[Evaluation of storage stability]
The viscosity (day 0) of the resin compositions and comparative compositions prepared in each example and comparative example was measured using an E-type viscometer. After the compositions were left to stand for 14 days at 25°C in a light-shielded, sealed container, the viscosity (day 14) was measured again using an E-type viscometer. The viscosity fluctuation rate (%) was calculated using the following formula. The obtained viscosity fluctuation rate (%) was evaluated according to the evaluation criteria below, and the evaluation results are recorded in the "Resist Storage Stability Evaluation" column of the table below. The lower the viscosity fluctuation rate, the higher the storage stability of the composition.
Viscosity fluctuation rate (%) = |100 × {1 - (viscosity (14 days) / viscosity (0 days))}|
Viscosity measurements were to be performed at 25°C, and all other specifications were to conform to JIS Z 8803:2011.
—Evaluation Criteria—
A: The viscosity fluctuation rate was 5% or less.
B: The viscosity fluctuation rate was greater than 5% but less than or equal to 10%.
C: The viscosity fluctuation rate was greater than 10% but less than or equal to 15%.
D: The viscosity fluctuation rate was greater than 15% but less than or equal to 20%.

[Evaluation of adhesion to copper substrate]
The resin composition or comparative composition prepared in each example and comparative example was applied in layers to a copper substrate by spin coating to form a resin composition layer or comparative composition layer. The copper substrate on which the obtained resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes to obtain a resin composition layer or comparative composition layer on the copper substrate with a uniform thickness and the film thickness indicated in the "Film Thickness (μm)" column of the table. The resin composition layer or comparative composition layer on the copper substrate was exposed to light at the exposure wavelength (nm) indicated in the "Exposure Wavelength nm" column of the table, using an exposure energy of 500 mJ/ ^cm² , with a photomask having a 100 μm square non-mask area formed in the example where "Negative" was indicated in the "Development Conditions" column of the table, and a photomask having a 100 μm square mask area formed in the example where "Positive" was indicated in the "Development Conditions" column of the table.
In the example where "M" is written in the exposure conditions column, exposure was performed using a stepper as the light source.
In the example where "D" is written in the exposure conditions column, a direct exposure system (Adtec DE-6UH III) was used as the light source, and laser direct imaging exposure was performed on a 100 μm square area without using a photomask.
The material was then developed for 60 seconds using the developer listed in the table to obtain a 100 μm square resin layer. The entry for "TMAH aqueous solution" in the table refers to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.
In the examples where a numerical value is listed in the "Cure Temperature" column, the resin composition layer after exposure was heated using a hot plate under a nitrogen atmosphere at a heating rate of 10°C/min until it reached the temperature indicated in the "Cure Temperature (°C)" column of the table, and then maintained at that temperature for the time indicated in the "Cure Time (min)" column of the table.
In the cases where "IR" is written in the "Cure Temperature (°C)" column, an infrared lamp heating device (Advance Riko Co., Ltd., RTP-6) was used to heat the resin film obtained in each example in a nitrogen atmosphere at a heating rate of 10°C/min until it reached 230°C, and then the above temperature was maintained for the time indicated in "Cure Time (min)" in the table.
For a 100 μm square resin layer on a copper substrate, the shear force was measured using a bond tester (CondorSigma, XYZTEC) under conditions of 25°C and 65% relative humidity (RH), and evaluated according to the evaluation criteria below. The evaluation results are shown in the "Adhesion to Copper Substrate Evaluation" column of the table. The greater the shear force, the better the metal adhesion (copper adhesion) of the cured film.
—Evaluation Criteria—
A: The shear force exceeded 30 gf.
B: The shear force was greater than 25 gf and less than or equal to 30 gf.
C: The shear force was greater than 20 gf and less than or equal to 25 gf.
D: The shear force was 20 gf or less.
Also, 1 gf is equal to 0.00980665 N.

[Evaluation of adhesion to silicon wafers]
The adhesion to the silicon wafer was evaluated using the same method as the adhesion evaluation to the copper substrate, except that the copper substrate used in the evaluation to the copper substrate was replaced with a silicon wafer. The evaluation results are listed in the "Adhesion Evaluation to Silicon Wafer" column of the table.

[Measurement of carboxylic acid anhydride content]
The content of carboxylic acid anhydride relative to the total mass of the resin composition was quantified by mixing 0.20 g of the resin composition with 0.80 g of heavy DMSO and measuring ^1H -NMR. The detection limit was set at 0.01% by mass, and values below the detection limit were indicated as "<0.01". The quantitative results are shown in the "Carboxylic Acid Anhydride Amount (mass%)" column of the table.

From the above results, it can be seen that using the resin composition of the present invention improves the storage stability of the resulting cured product.
The comparative composition in Comparative Example 1 contains more than 0.5% by mass of carboxylic acid anhydride relative to the total mass of the resin composition, and does not contain the compound represented by formula (2-1). It can be seen that such a composition has poor storage stability. The reason why the carboxylic acid anhydride content in Comparative Example 1 exceeded 0.5% by mass is presumed to be that compound RC-1 decomposed over time and changed into carboxylic acid anhydride.

<Example 101>
The resin composition used in Example 1 was applied in layers to the surface of a copper thin layer formed on a resin substrate by spin coating, and dried at 100°C for 5 minutes to form a photosensitive film with a thickness of 20 μm. The film was then exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After the exposure, the film was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain the layer pattern.
Next, under a nitrogen atmosphere, the temperature was increased at a rate of 10°C/min until it reached 230°C, and then maintained at 230°C for 180 minutes to form an interlayer insulating film for the redistribution layer. This interlayer insulating film for the redistribution layer exhibited excellent insulating properties.
Furthermore, we confirmed that semiconductor devices manufactured using these interlayer insulating films for redistribution layers function without any problems.

Claims (16)

At least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor,
Silane coupling agents, and
Contains a photopolymerization initiator ,
The content of carboxylic acid anhydride relative to the total mass of the resin composition is 0.5% by mass or less.
The silane coupling agent includes compound A having at least one group selected from the group consisting of a hydroxyl group, an amino group, and a thiol group, at least one group consisting of an amide group and an ester group, and a group represented by the following formula (S-1).
Compound A contains an aromatic group
Resin composition.
In formula (S-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, x represents an integer between 1 and 3, and * represents a bonding site with another structure. At least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor,
Compound A having at least one group selected from the group consisting of a hydroxyl group, an amino group, and a thiol group, at least one group consisting of an amide group and an ester group, and a group represented by the following formula (S-1),
Contains a photopolymerization initiator ,
A resin composition in which compound A contains an aromatic group.
In formula (S-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, x represents an integer between 1 and 3, and * represents a bonding site with another structure. The resin composition according to claim 1 or 2 , wherein compound A is a compound represented by formula (1-1).
In formula (1-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, L represents an m+n valence linking group containing an amide group or an ester group, x represents an integer between 1 and 3, m represents an integer of 1 or more, and n represents an integer of 1 or more. The resin composition according to claim 3 , wherein the carbon atom contained in L in formula (1-1) that is directly bonded to the hydroxyl group in formula (1-1) is a carbon atom that constitutes an aliphatic hydrocarbon group. The resin composition according to any one of claims 1 to 4 , wherein compound A is a compound represented by formula (2-1).
In formula (2-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, ^L1 represents a single bond or a divalent linking group, Z represents an amide group, the orientation of the amide group in Z is not particularly limited, ^L2 represents a single bond or a divalent linking group, Ar represents an aromatic group, X represents an alkylene group, and x represents an integer between 1 and 3. The resin composition according to any one of claims 1 to 5 , wherein the molecular weight of compound A is 300 to 1,000. A resin composition according to any one of claims 1 to 6 , comprising a polymerizable compound. A resin composition according to any one of claims 1 to 7, comprising a base-generating agent. A resin composition according to any one of claims 1 to 8 , used for forming an interlayer insulating film for redistribution layers. A cured product obtained by curing the resin composition according to any one of claims 1 to 9 . A laminate comprising two or more layers made of the cured material described in claim 10 , wherein a metal layer is included between any of the layers made of the cured material. A method for producing a cured product, comprising a film-forming step of applying a resin composition according to any one of claims 1 to 9 onto a substrate to form a film. A method for producing a cured product according to claim 12 , comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern. A method for producing a cured product according to claim 12 or 13 , comprising a heating step of heating the film to 50 to 450°C. A semiconductor device comprising a cured product according to claim 10 or a laminate according to claim 11 . A compound represented by formula (2-1).
In formula (2-1), each ^R1 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, each ^R2 independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, ^L1 represents a single bond or a hydrocarbon group , Z represents an amide group, the orientation of the amide group in Z is not particularly limited, ^L2 represents a single bond or a divalent linking group, Ar represents an aromatic group, X represents an alkylene group, and x represents an integer between 1 and 3.