JP7780274B2 - Resin composition, cured product, laminate, method for manufacturing cured product, method for manufacturing laminate, method for manufacturing semiconductor device, semiconductor device, and compound - Google Patents

Description

The present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, a semiconductor device, and a compound.

Cyclated resins such as polyimides have excellent heat resistance and insulating properties, making them suitable for a variety of applications. While not limited to these applications, examples include insulating films, encapsulants, and protective films for semiconductor devices. They are also used as base films and coverlays for flexible substrates.

For example, in the above-mentioned applications, the cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of the cyclized resin such as a polyimide precursor.
Such a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are carried out to form a cured product on the substrate.
The precursor of the cyclized resin, such as a polyimide precursor, is cyclized, for example, by heating, and becomes a cyclized resin, such as a polyimide, in the cured product.
The resin composition can be applied by known coating methods, etc., and therefore can be said to have excellent adaptability in manufacturing, for example, a high degree of freedom in designing the shape, size, application position, etc. of the resin composition when applied. In addition to the high performance of cyclized resins such as polyimides, from the viewpoint of such excellent adaptability in manufacturing, there are increasing expectations for the industrial application and development of the above-mentioned resin composition.

For example, Patent Document 1 describes a photosensitive resin composition that contains a polymer precursor whose reaction to form a final product is accelerated by a basic substance or by heating in the presence of a basic substance, and a base generator that has a specific structure and generates a base when irradiated with electromagnetic waves and heated.

JP 2011-121962 A

Resin compositions used to obtain cured products are required to produce cured films that have excellent adhesion between the metal and the cured film even after a long period of time has passed (i.e., cured films with excellent reliability).

The present invention aims to provide a resin composition that produces a cured product with excellent reliability, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the laminate, and a semiconductor device including the cured product or the laminate.

Examples of typical embodiments of the present invention are given below.
<1> At least one resin selected from the group consisting of cyclized resins and precursors thereof;
A resin composition comprising a compound represented by the following formula (1-1):
In formula (1-1), each R ¹ independently represents a hydrogen atom or a monovalent organic group, each R ² independently represents an aromatic heterocycle, each R ³ independently represents a hydrogen atom or a monovalent organic group, each L ¹ independently represents a divalent linking group, n represents an integer of 1 or more, and L ² represents an n-valent linking group.
<2> The resin composition according to <1>, wherein R ² in formula (1-1) contains an azole structure.
<3> The resin composition according to <1> or <2>, wherein R ² in formula (1-1) contains a purine structure.
<4> The resin composition according to any one of <1> to <3>, wherein n in formula (1-1) is 1 and L ² is a group represented by the following formula (L2-1):
In formula (L2-1), Ar represents an aromatic group, ^L represents a single bond or a divalent linking group, ^R represents a hydrogen atom, a hydroxy group or a monovalent organic group, and * represents a bonding site with the carbonyl group in formula (1-1).
<5> The resin composition according to any one of <1> to <4>, wherein R ³ in formula (1-1) is a hydrogen atom.
<6> The resin composition according to any one of <1> to <5>, wherein L ¹ in formula (1-1) is a structure represented by the following formula (L1-1):
In formula (L1-1), L ^L1 represents a divalent linking group, # represents the bonding site to the nitrogen atom to which R ³ in formula (1-1) is bonded, and * represents the bonding site to the nitrogen atom to which R ¹ in formula (1-1) is bonded.
<7> The resin composition according to any one of <1> to <6>, wherein the compound represented by formula (1-1) is a compound that generates a base when exposed to light or heat.
<8> The resin composition according to any one of <1> to <7>, wherein the resin is at least one resin selected from polyimides and polyimide precursors.
<9> The resin composition according to any one of <1> to <8>, which is used for forming an interlayer insulating film for a rewiring layer.
<10> A cured product obtained by curing the resin composition according to any one of <1> to <9>.
<11> A laminate comprising two or more layers made of the cured product according to <10>, and a metal layer between any two of the layers made of the cured product.
<12> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of <1> to <9> onto a substrate to form a film.
<13> The method for producing a cured product according to <12>, comprising: an exposure step of selectively exposing the film to light; and a development step of developing the film with a developer to form a pattern.
<14> A method for producing a cured product according to <12> or <13>, comprising a heating step of heating the film at 50 to 450°C.
<15> A method for producing a laminate, comprising the method for producing a cured product according to any one of <12> to <14>.
<16> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <12> to <14> or the method for producing a laminate according to <15>.
<17> A semiconductor device comprising the cured product according to <10> or the laminate according to <11>.
<18> A compound represented by the following formula (1-1):
In formula (1-1), each R ¹ independently represents a hydrogen atom or a monovalent organic group, each R ² independently represents an aromatic heterocycle, each R ³ independently represents a hydrogen atom or a monovalent organic group, each L ¹ independently represents a divalent linking group, n represents an integer of 1 or more, and L ² represents an n-valent linking group.

The present invention provides a resin composition that produces a cured product with excellent reliability, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the laminate, and a semiconductor device including the cured product or the laminate.

The main embodiments of the present invention will be described below, but the present invention is not limited to the embodiments explicitly described.
In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values before and after "to" as the lower and upper limits, respectively.
In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps, so long as the intended effect of the step can be achieved.
In the description of groups (atomic groups) in this specification, when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents. For example, the term "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
In this specification, unless otherwise specified, the term "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic" means both or either of "acrylic" and "methacrylic", and "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl".
In this specification, in the structural formulae, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, the term "total solids content" refers to the total mass of all components of the composition excluding the solvent, and the term "solids concentration" refers to the mass percentage of the components excluding 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-8220GPC (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, if THF is not suitable as an eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is performed using a UV (ultraviolet) ray (ultraviolet) detector with a wavelength of 254 nm.
In this specification, when the positional relationship of each layer constituting a laminate is described as "upper" or "lower," it is sufficient that there is another layer above or below the reference layer among the multiple layers being considered. In other words, 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. Furthermore, unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "upper." Alternatively, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "upper" direction in this specification may differ from the vertically upward direction.
In this specification, unless otherwise specified, a composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
In this specification, unless otherwise specified, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH.
As used herein, combinations of preferred embodiments are more preferred embodiments.

(Resin composition)
The resin composition of the present invention contains at least one resin selected from the group consisting of cyclized resins and precursors thereof, and a compound represented by the following formula (1-1) (hereinafter also referred to as the “specific compound”).
In formula (1-1), each R ¹ independently represents a hydrogen atom or a monovalent organic group, each R ² independently represents an aromatic heterocycle, each R ³ independently represents a hydrogen atom or a monovalent organic group, each L ¹ independently represents a divalent linking group, n represents an integer of 1 or more, and L ² represents an n-valent linking group.

The resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and more preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent.
The resin composition of the present invention can be used to form, for example, an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a rewiring layer.
The resin composition of the present invention may be used to form a photosensitive film to be subjected to positive development, or may be used to form a photosensitive film to be subjected to negative development.
In the present invention, negative development refers to development in which the unexposed areas are removed by development, and positive development refers to development in which the exposed areas are removed by development.
As the exposure method, the developer, and the development method, for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the method for producing a cured product described below can be used.

According to the resin composition of the present invention, a cured film with excellent reliability can be obtained.
Conventionally, adhesion to metals has been improved by adding a nitrogen-containing compound (e.g., a compound having a triazole structure or a tetrazole structure) to a resin composition containing a cyclized resin or a precursor thereof. However, there is still room for improvement in terms of adhesion between the metal and the cured film after a long period of time has elapsed.
Therefore, the present inventors conducted extensive research and found that by using a resin composition containing a specific compound, it is possible to obtain a cured film that has excellent adhesion between the metal and the cured film even after a long period of time has passed (i.e., a cured film that has excellent reliability).
The mechanism by which the above effects are obtained is unknown, but is speculated as follows.
It is believed that the compound represented by formula (1-1) decomposes upon heating or the like to generate a compound having an amino group and an aromatic heterocycle.
The aromatic heterocyclic structure in this compound has high adsorption to metals, and the amino group in the generated compound forms a strong bond such as an imide bond with the cyclized resin or its precursor resin, which is thought to introduce the aromatic heterocyclic ring into the resin. As a result, it is thought that the adhesion between the resin and metal is improved, and a cured film with excellent reliability can be obtained.
Furthermore, as described above, heating during the formation of the cured film decomposes the specific compound to produce a compound that has high adsorption to metal and forms a strong bond with the resin, such as an imide bond. Therefore, it is presumed that voids are less likely to form at the boundary between the cured film and the metal layer after curing, even after a long period of time has passed.
Furthermore, since the specific compound before decomposition has low basicity, it is believed that the composition also has excellent storage stability during storage.
Furthermore, as described above, compounds having amino groups are generated from the decomposed specific compounds. These amino groups promote cyclization of the precursor of the cyclized resin and the unclosed portion of the cyclized resin, and therefore the resulting cured product is thought to have excellent elongation at break.

However, Patent Document 1 does not disclose any resin compositions containing specific compounds.

The components contained in the resin composition of the present invention are described in detail below.

<Specific resin>
The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.
The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.
In the present invention, the main chain refers to the relatively longest connecting chain in the resin molecule.
Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamideimide.
The precursor of a cyclized resin refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a cyclized resin. A resin that undergoes a change in chemical structure due to heat to become a cyclized resin is preferred, and a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a cyclized resin is more preferred.
Examples of the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor.
That is, the resin composition of the present invention preferably contains, as the 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, as the specific resin, at least one resin selected from the group consisting of polyimides and polyimide precursors.
The specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
When the specific resin has a radical polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator described below, and more preferably contains both the radical polymerization initiator described below and a radical crosslinking agent described below. Furthermore, if necessary, the resin composition of the present invention may contain a sensitizer described below. For example, a negative-tone photosensitive film can be formed from such a resin composition of the present invention.
The specific resin may also have a polarity conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the resin composition of the present invention preferably contains a photoacid generator described later. From such a resin composition of the present invention, for example, a chemically amplified positive-working photosensitive film or negative-working photosensitive film is formed.

[Polyimide precursor]
The polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2).
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), A ¹ and A ² each independently represent an oxygen atom or —NH—, and preferably an oxygen atom.
R ¹¹¹ in formula (2) represents a divalent organic group. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. A linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Preferred embodiments of the present invention include groups represented by -Ar- and -Ar-L-Ar-, and particularly preferred is a group represented by -Ar-L-Ar-. wherein each Ar is independently an aromatic group, and L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO ₂ — or —NHCO—, or a group consisting of a combination of two or more of the above. The preferred ranges for these are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of diamines used in producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
Specifically, diamines containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof are preferred, and diamines containing an aromatic group having 6 to 20 carbon atoms are more preferred. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom. Examples of groups containing an aromatic group include the following.

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

Specific examples of diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl nyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 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-aminophenyl) 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'-diaminodiphenyl sulfone, 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]hexafluoropropane propane, 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'-diaminodiphenyl sulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, methyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis( 4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3- At least one diamine selected from the group consisting of 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfone, 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'-hexafluorotolidine, and 4,4'-diaminoquaterphenyl.

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

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

From the viewpoint of flexibility of the obtained organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. However, each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO ₂ -. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

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

In formula (2), R ¹¹⁵ represents a tetravalent organic group. The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6).
In formula (5) or formula (6), * each independently represents a bonding site to another structure.
In formula (5), R ¹¹² represents a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, or a group selected from combinations thereof; more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO ₂ -; and still more preferably a divalent group selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S-, and -SO ₂ -.

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

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, 2,2 ',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and alkyl and alkoxy derivatives thereof having 1 to 6 carbon atoms.

Further preferred examples include the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598.

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 contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. It is also preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and more preferably that 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 capable of undergoing a crosslinking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group contained in the polyimide precursor is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
In formula (III), * represents a bonding site to another structure.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH(OH)CH ₂ —, a cycloalkylene group, or a polyalkyleneoxy group.
Suitable examples of R ²⁰¹ include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, —CH ₂ CH(OH)CH ₂ —, and polyalkyleneoxy groups, of which alkylene groups such as ethylene and propylene, —CH ₂ CH(OH)CH ₂ —, cyclohexyl, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups are even more preferred.
In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating.
The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.
The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is preferred, a polyethyleneoxy group or a polypropyleneoxy group is more preferred, and a polyethyleneoxy group is even more preferred. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiments of the number of repetitions of the ethyleneoxy groups etc. in these groups are as described above.

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

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

It is also preferable that the polyimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and 20% by mass or less.

In addition, to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as diamines.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), it becomes possible to further widen the range of exposure latitude.
Formula (2-A)
In formula (2-A), A ¹ and A ² represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ is a group containing a polymerizable group, and it is preferred that both are groups containing a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same meaning as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and the preferred ranges are also the same.
R ¹¹² has the same meaning as R ¹¹² in formula (5), and the preferred range is also the same.

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

One embodiment of the polyimide precursor of the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably greater than 90 mol%. There is no particular upper limit to the total content, and all repeating units in the polyimide precursor, excluding the terminal units, 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 polyimide precursor preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
In this specification, the molecular weight dispersity is a value calculated by dividing the weight average molecular weight by the number average molecular weight.
When the resin composition contains multiple polyimide precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide precursor are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as a single resin are within the above-mentioned ranges.

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

- Fluorine atom -
From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains fluorine atoms.
The fluorine atom is preferably contained in, for example, R132 in the repeating unit represented by formula (4) described later or R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably contained as a fluorinated alkyl group in R132 in the repeating unit represented by formula (4) described later or R131 in the repeating unit represented by formula (4) described later.
The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.

-Silicon atom-
From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains a silicon atom.
The silicon atom is preferably contained in R131 in the repeating unit represented by formula (4) described later, and more preferably contained in R131 in the repeating unit represented by formula (4) described later as an organically modified (poly)siloxane structure described later.
The silicon atom or the organically modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

- Ethylenically unsaturated bond -
From the viewpoint of the film strength of the resulting organic film, the polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in a side chain.
The ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably contained in R ¹³² in the repeating unit represented by formula (4) described later or in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably contained as a group having an ethylenically unsaturated bond in R ¹³² in the repeating unit represented by formula (4) described later or in R ¹³¹ in the repeating unit represented by formula (4) described later.
Among these, the ethylenically unsaturated bond is preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably contained as a group having an ethylenically unsaturated bond in R ¹³¹ in the repeating unit represented by formula (4) described later.
Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring, such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group 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, and is preferably a hydrogen atom or a methyl group.

In formula (IV), R ²¹ represents an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(═O)O-, -O(C═O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group consisting of a combination of two or more of these.
The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, and alkylene groups represented by a combination thereof.
The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

Among these, R ²¹ is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).
In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together; X represents an oxygen atom or a sulfur atom; * represents a bonding site to another structure; and ● represents a bonding site to the oxygen atom to which ^R21 in formula (IV) is bonded.
In formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms for L are the same as the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms for ^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 preferred embodiments are also the same.
The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).
The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate).
The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).

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

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

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

- Polarity conversion group -
The polyimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R ¹¹³ and R ¹¹⁴ in the above formula (2), and preferred embodiments are also the same.
The polarity conversion group is contained, for example, in R ¹³¹ and R ¹³² in the repeating unit represented by formula (4) described below, or at the terminal of the polyimide.

- Acid value -
When the polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
The acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
Furthermore, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably from 1 to 35 mgKOH/g, more preferably from 2 to 30 mgKOH/g, and even more preferably from 5 to 20 mgKOH/g.
The acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
The acid group contained in the polyimide preferably has a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability.
pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa. In this specification, pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified. Alternatively, values listed in "Revised 5th Edition Chemistry Handbook, Basics" edited by the Chemical Society of Japan may be referenced.
Furthermore, when the acid group is a polyvalent acid such as phosphoric acid, the pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

-Phenolic hydroxy group-
From the viewpoint of ensuring an appropriate development rate with an alkaline developer, the polyimide preferably has a phenolic hydroxy group.
The polyimide may have a phenolic hydroxy group at the end of the main chain or on a side chain.
The phenolic hydroxy group is preferably contained in, for example, R ¹³² in the repeating unit represented by formula (4) described below, or R ¹³¹ in the repeating unit represented by formula (4) described below.
The amount of phenolic hydroxy groups relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains a repeating unit represented by the following formula (4).
In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group.
When a polymerizable group is contained, the polymerizable group may be located at at least one of R ¹³¹ and R ¹³² , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2).
Formula (4-1)
In formula (4-1), R ¹³³ is a polymerizable group, and the other groups have the same meanings as 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 groups have the same meanings as in formula (4).

Examples of the polymerizable group include the above-mentioned group containing an ethylenically unsaturated bond, and crosslinkable groups other than the above-mentioned group having an ethylenically unsaturated bond.
R ¹³¹ represents a divalent organic group. Examples of the divalent organic group include the same as those of R ¹¹¹ in formula (2), and the preferred ranges are also the same.
Furthermore, R ¹³¹ may be a diamine residue remaining after removal of the amino group of the diamine. Examples of the diamine include aliphatic, alicyclic, or aromatic diamines. Specific examples include the examples of R ¹¹¹ in formula (2) of the polyimide precursor.

R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain, from the viewpoint of more effectively suppressing the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.

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

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group include the same as those of R ¹¹⁵ in formula (2), and the preferred ranges are also the same.
For example, the four bonds of the tetravalent organic group exemplified as R ¹¹⁵ bond to the four —C(═O)— moieties in the above formula (4) to form a condensed ring.

Furthermore, R ¹³² may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride. Specific examples include 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 preferred that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, preferred examples of R ¹³¹ include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above-mentioned (DA-1) to (DA-18), and more preferred examples of R ¹³² include the above-mentioned (DAA-1) to (DAA-5).

It is also preferable that the polyimide has fluorine atoms in its structure. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and 20% by mass or less.

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

In addition, to improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are blocked with a terminal blocking agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. Of these, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy Examples include 2-5-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-capping agents may be reacted to introduce multiple end groups.

-Imidization rate (ring closure rate)-
The imidization rate (also referred to as "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 viewpoints of the film strength, insulating properties, etc. of the resulting organic film.
There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less.
The imidization rate is measured, for example, by the following method.
The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ⁻¹ , which is an absorption peak derived from the imide structure, is determined. Next, the polyimide is heat-treated at 350°C for 1 hour, and the infrared absorption spectrum is measured again, and the peak intensity P2 near 1377 cm ⁻¹ is determined. The obtained peak intensities P1 and P2 can be used to calculate the imidization ratio of the polyimide based on the following formula:
Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

The polyimide may contain repeating units represented by the above formula (4) all containing one type of R ¹³¹ or R ¹³² , or may contain repeating units represented by the above formula (4) containing two or more different types of R ¹³¹ or R ^132. Furthermore, the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Examples of other types of repeating units include the repeating units represented by the above formula (2).

Polyimides can be synthesized by, for example, reacting tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-capping agent) at low temperatures; reacting tetracarboxylic dianhydride with a diamine (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-capping agent) at low temperatures; obtaining a diester from tetracarboxylic dianhydride with an alcohol, followed by reaction with a diamine (partially substituted with a monoamine end-capping agent) in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol, then converting the remaining dicarboxylic acid to an acid chloride and reacting it with a diamine (partially substituted with a monoamine end-capping agent). These polyimides can then be fully imidized using known imidization reaction methods. Alternatively, the imidization reaction can be terminated midway to introduce a partial imide structure. Furthermore, a partial imide structure can be introduced by blending a fully imidized polymer with the polyimide precursor. Other known polyimide synthesis methods can also be used.

The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By making the weight-average molecular weight 5,000 or more, the fold resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., breaking elongation), a weight-average molecular weight of 15,000 or more is particularly preferred.
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 polyimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the polyimide molecular weight dispersity is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
When the resin composition contains multiple polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyimide are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyimides as a single resin are within the above-mentioned ranges.

[Polybenzoxazole precursor]
The polybenzoxazole precursor used in the present invention is not particularly limited with respect to its structure, but preferably contains a repeating unit 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 each have the same definition as R ¹¹³ in formula (2), and the preferred range is 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 type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferred, and a dicarboxylic acid residue containing an aromatic group is more preferred.
The dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid consisting of a linear or branched (preferably linear) aliphatic group and two -COOH groups. 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, still 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, succinic 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. , suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioctic acid, heneicosanedioctic acid, docosanedioctic acid, tricosanedioctic acid, tetracosanedioctic acid, pentacosanedioctic acid, hexacosanedioctic acid, heptacosanedioctic acid, octacosanedioctic acid, nonacosanedioctic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and further dicarboxylic acids represented by the following formula:

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

As dicarboxylic acids containing an aromatic group, the following dicarboxylic acids containing an aromatic group are preferred, and the following dicarboxylic acids consisting of only a group containing an aromatic group and two -COOH groups are more preferred.

In the formula, A represents a divalent group selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C(CF ₃ ) ₂ —, and —C(CH ₃ ) ₂ —, and * each independently represents a bonding site to another structure.

Specific examples of dicarboxylic acids containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as 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 the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, 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-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4 ... Examples of bisaminophenols include 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 alone or in combination.

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

In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , or -NHCO-, and * and # each represent a bonding site to another structure. 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. It is also preferable that ^R122 is a structure represented by the above formula. When R ¹²² has a structure represented by the above formula, it is preferable that of the total of four * and #, any two 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; it is more preferable that the two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded and the two # are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded; or it is more preferable that the two * are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded and the two # are bonding sites to the oxygen atom to which R ¹²² in formula (3) ^is bonded; it is even more preferable that the two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded and the two # 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 (As).

In formula (A-s), R ₁ is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, a single bond, or an organic group selected from the group represented by the following formula (A-sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and 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 bisaminophenol derivative represented by formula (A-s) above.)

In the above formula (As), having a substituent at the ortho position of the phenolic hydroxy group, i.e., at _R3 , is particularly preferred in that it is thought to bring the distance between the carbonyl carbon of the amide bond and the hydroxy group closer, further enhancing the effect of achieving a high cyclization rate when cured at low temperatures.

In addition, in the above formula (As), it is preferable that R ₂ is an alkyl group and R ₃ is an alkyl group, since this can maintain the effects of high transparency to i-line and a high cyclization rate when cured at a low temperature.

In the formula (A-s), it is more preferable that R ₁ is alkylene or substituted alkylene. Specific examples of the alkylene and substituted alkylene for R ₁ include linear or branched alkyl groups having 1 to 8 carbon atoms, of which -CH ₂ -, -CH(CH ₃ )-, and -C(CH ₃ ) ₂ - are more preferable in that they can provide a well-balanced polybenzoxazole precursor that has sufficient solubility in solvents while maintaining the effects of high transparency to i-line and a high cyclization rate when cured at low temperature.

For a method for producing the bisaminophenol derivative represented by the above formula (A-s), see, for example, paragraphs [0085] to [0094] and Example 1 (paragraphs [0189] to [0190]) of JP 2013-256506 A, the contents of which are incorporated herein by reference.

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 JP 2013-256506 A, the contents of which are incorporated herein by reference. Needless to say, the present invention is not limited to these examples.

The polybenzoxazole precursor may contain 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 warping due to ring closure can be suppressed.

In formula (SL), Z has an a-structure and a b-structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ^2s is a hydrocarbon group having 1 to 10 carbon atoms, at least one of R ^3s , R ^4s , R ^5s , and R ^6s 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. The 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 a+b is 100 mol %.

In formula (SL), preferred examples of Z include those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, 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 of the polybenzoxazole precursor after dehydration ring closure, thereby achieving both the effect of suppressing warpage and the effect of improving solvent solubility.

When the diamine residue represented by formula (SL) is contained as another type of repeating unit, it is also preferable to further contain, as a repeating unit, a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic acid dianhydride. Examples of such a tetracarboxylic acid residue include the examples of R ¹¹⁵ in formula (2).

The weight-average molecular weight (Mw) of the polybenzoxazole precursor is, for example, 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 polybenzoxazole precursor preferably has a molecular weight dispersity of 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly limited, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, still more preferably 2.3 or less, and even more preferably 2.2 or less.
When the resin composition contains multiple polybenzoxazole precursors as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polybenzoxazole precursor be within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polybenzoxazole precursors as a single resin be within the above-mentioned ranges.

[Polybenzoxazole]
The polybenzoxazole is not particularly limited as long as it is a polymeric compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) having a polymerizable group. The polymerizable group is preferably a radically polymerizable group. Alternatively, it may be a compound represented by the following formula (X) having a polarity conversion group such as an acid-decomposable group.
In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group.
When a polarity conversion group such as a polymerizable group or an acid-decomposable group is contained, the polarity conversion group such as a polymerizable group or an acid-decomposable group may be located at at least one of R ¹³³ and R ¹³⁴ , or may be located at an end of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2).
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-decomposable group, and when it is not a polarity conversion group such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other groups are as defined in formula (X).
Formula (X-2)
In formula (X-2), R ¹³⁷ is a polarity conversion group such as a polymerizable group or an acid-decomposable group, and the other groups are substituents, and the other groups have the same meanings as in formula (X).

The polarity conversion group, such as a polymerizable group or an acid-decomposable group, has the same meaning as the polymerizable group described above for the polymerizable group possessed by the polyimide precursor.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic group or an aromatic group. Specific examples include the examples of R ¹²¹ in formula (3) of the polybenzoxazole precursor. Preferred examples are the same as those of R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. Examples of the tetravalent organic group include the examples of R ¹²² in formula (3) of the polybenzoxazole precursor. Preferred examples thereof are the same as those of R ¹²² .
For example, the four bonds of the tetravalent organic group exemplified as R ¹²² bond to the nitrogen atom and oxygen atom in the above formula (X) to form a fused ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. In the following structure, * represents the bonding site with the nitrogen atom or oxygen atom in formula (X), respectively.

The polybenzoxazole preferably has an oxazolization rate of 85% or more, more preferably 90% or more. The upper limit is not particularly limited and may be 100%. When the oxazolization rate is 85% or more, film shrinkage due to ring closure that occurs when oxazolized by heating is reduced, and warpage can be more effectively suppressed.
The oxazole ratio is measured, for example, by the following method.
The infrared absorption spectrum of the polybenzoxazole is measured, and the peak intensity Q1 near 1650 cm ⁻¹ , which is an absorption peak derived from the amide structure of the precursor, is determined. This is then normalized by the absorption intensity of the aromatic ring observed near 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 near 1650 cm ⁻¹ is determined and normalized by the absorption intensity of the aromatic ring observed near 1490 cm ⁻¹ . The normalized values of the peak intensities Q1 and Q2 obtained can be used to calculate the oxazolization rate of the polybenzoxazole based on the following formula:
Oxazolization rate (%) = (normalized value of peak intensity Q1/normalized value of peak intensity Q2) × 100

The polybenzoxazole may contain repeating units of the above formula (X) all containing one type of R ¹³¹ or R ¹³² , or may contain repeating units of the above formula (X) containing two or more different types of R ¹³¹ or R ^132. Furthermore, the polybenzoxazole may contain other types of repeating units in addition to the repeating units of the above formula (X).

Polybenzoxazole 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 dicarboxylic acid to obtain a polybenzoxazole precursor, which is then oxazolized using a known oxazolization reaction method.
In the case of dicarboxylic acids, in order to increase the reaction yield, etc., it is also possible to use an active ester type dicarboxylic acid derivative which has been previously reacted with 1-hydroxy-1,2,3-benzotriazole or the like.

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 more, the fold resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more. Furthermore, when two or more types of polybenzoxazoles are contained, it is preferable that the weight-average molecular weight of at least one type of polybenzoxazole be within the above range.
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 polybenzoxazole preferably has a molecular weight dispersity of 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole is not particularly specified, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less.
When the resin composition contains multiple polybenzoxazoles as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polybenzoxazole are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polybenzoxazoles as a single resin are within the above-mentioned ranges.

[Polyamide-imide precursor]
The polyamideimide precursor preferably contains a repeating unit 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 a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked together via a single bond or a linking group; a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined together via a single bond or a linking group is preferred; and an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined together via a single bond or a linking group is more preferred.
The linking group is preferably -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and 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 carboxy group may be halogenated, and the halogenation is preferably chlorination.
In the present invention, a compound having three carboxy groups is called a tricarboxylic acid compound.
Two of the three carboxy groups of the tricarboxylic acid compound may be converted into acid anhydrides.
Examples of the tricarboxylic acid compound which may be halogenated and is used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic, and aromatic tricarboxylic acid compounds.
These tricarboxylic acid compounds may be used alone or in combination of two or more.

Specifically, tricarboxylic acid compounds containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group combining two or more of these groups via a single bond or a linking group are preferred, and tricarboxylic acid compounds containing an aromatic group having 6 to 20 carbon atoms, or a group combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group are more preferred.

Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, —O—, —CH ₂ —, —C(CH ₃ ) ₂ —, —C(CF ₃ ) ₂ —, —SO ₂ —, or a phenylene group.
These compounds may be compounds in which two carboxy groups are anhydrides (e.g., trimellitic anhydride), or may be compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).

In formula (PAI-2), R ¹¹¹ , A ² and R ¹¹³ have the same meanings as R ¹¹¹ , A ² and R ¹¹³ in formula (2) above, respectively, and preferred embodiments are also the same.

The polyamideimide precursor may further comprise other repeating units.
Examples of other repeating units include the repeating unit represented by the above formula (2) and the repeating unit represented by the following formula (PAI-1).

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 a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked together via a single bond or a linking group, and is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined together via a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined together via a single bond or a linking group.
The linking group is preferably -O-, -S-, -C(=O)-, -S(=O) ₂ -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these.
The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group.
The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and 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 carboxy groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound.
The carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example, i.e., the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
Examples of the optionally halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic dicarboxylic acid compound or dicarboxylic acid dihalide compound.
These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group combining two or more of these groups via a single bond or a linking group, and more preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms, or a group combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

Specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic 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, sebacic acid, and hexadecafluoroadipic acid. Examples of the carboxylic acid include fluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedicarboxylic acid, heneicosanedicarboxylic acid, docosanedicarboxylic acid, tricosanedicarboxylic acid, tetracosanedicarboxylic acid, pentacosanedicarboxylic acid, hexacosanedicarboxylic acid, heptacosanedicarboxylic acid, octacosanedicarboxylic acid, nonacosanedicarboxylic 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, and benzophenone-4,4'-dicarboxylic acid.
Specific examples of the dicarboxylic acid dihalide compound include compounds in which two carboxy groups in the specific examples of the dicarboxylic acid compounds mentioned above are halogenated.

In formula (PAI-1), R ¹¹¹ has the same meaning as R ¹¹¹ in formula (2) above, and preferred embodiments are also the same.

It is also preferable that the polyamideimide precursor has fluorine atoms in its structure. The fluorine atom content in the polyamideimide precursor is preferably 10% by mass or more and 20% by mass or less.

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

In one embodiment of the polyamideimide precursor of the present invention, the total content of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2) is 50 mol% or more of all repeating units. This total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular upper limit to the total content, and all repeating units in the polyamideimide precursor excluding the terminal repeating units may be any of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2).
Another embodiment of the polyamideimide precursor of the present invention is one in which the total content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or more of all repeating units. This total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular upper limit to the total content, and all repeating units in the polyamideimide precursor excluding the terminal repeating units may be either the repeating units represented by formula (PAI-2) or the repeating units represented by formula (PAI-1).

The weight average molecular weight (Mw) of the polyamideimide 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 molecular weight dispersity of the polyamideimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Furthermore, when the resin composition contains multiple types of polyamideimide precursors as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of polyamideimide precursor are within the above-mentioned ranges. Furthermore, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of polyamideimide precursors as a single resin are each within the above-mentioned ranges.

[Polyamide-imide]
The polyamideimide used in the present invention may be an alkali-soluble polyamideimide, or may be a polyamideimide that is soluble in a developer containing an organic solvent as a main component.
In this specification, alkali-soluble polyamideimide refers to a polyamideimide that dissolves at least 0.1 g in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C. From the viewpoint of pattern formability, a polyamideimide that dissolves at least 0.5 g is preferred, and a polyamideimide that dissolves at least 1.0 g is more preferred. The upper limit of the 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 polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain.

- Fluorine atom -
From the viewpoint of the film strength of the resulting organic film, the polyamideimide preferably contains a fluorine atom.
The fluorine atom is preferably contained in, for example, R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described below, and more preferably contained as a fluorinated alkyl group in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described below.
The amount of fluorine atoms relative to the total mass of the polyamideimide is preferably 5% by mass or more and 20% by mass or less.

- Ethylenically unsaturated bond -
From the viewpoint of the film strength of the resulting organic film, the polyamideimide may have an ethylenically unsaturated bond.
The polyamideimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in a side chain.
The ethylenically unsaturated bond preferably has radical polymerizability.
The ethylenically unsaturated bond is preferably contained in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described below, and more preferably contained as a group having an ethylenically unsaturated bond in R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described below.
Preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments 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 the polyamideimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

-Polymerizable group other than ethylenically unsaturated bond-
The polyamideimide may have a polymerizable group other than an ethylenically unsaturated bond.
Examples of the polymerizable group other than the ethylenically unsaturated bond in the polyamideimide include the same groups as the polymerizable group other than the ethylenically unsaturated bond in the polyimide described above.
The polymerizable group other than the ethylenically unsaturated bond is preferably contained in, for example, R ¹¹¹ in the repeating unit represented by formula (PAI-3) described below.
The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of the polyamideimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g.

- Polarity conversion group -
The polyamideimide may have a polarity conversion group such as an acid-decomposable group. The acid-decomposable group in the polyamideimide is the same as the acid-decomposable group described for R ¹¹³ and R ¹¹⁴ in the above formula (2), and preferred embodiments are also the same.

- Acid value -
When the polyamideimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyamideimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
The acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
Furthermore, when the polyamideimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyamideimide is preferably 2 to 35 mgKOH/g, more preferably 3 to 30 mgKOH/g, and even more preferably 5 to 20 mgKOH/g.
The acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
The acid group contained in the polyamideimide may be the same as the acid group in the polyimide described above, and the preferred embodiments are also the same.

-Phenol hydroxy group-
From the viewpoint of ensuring an appropriate development rate with an alkaline developer, the polyamideimide preferably has a phenolic hydroxy group.
The polyamideimide may have a phenolic hydroxy group at the end of the main chain or on a side chain.
The phenolic hydroxy group is preferably contained in, for example, R ¹¹⁷ or R ¹¹¹ in the repeating unit represented by formula (PAI-3) described below.
The amount of phenolic hydroxy groups relative to the total mass of the polyamideimide is preferably 0.1 to 30 mol/g, 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 have the same meanings as R ¹¹¹ and R ¹¹⁷ in formula (PAI-2), respectively, and preferred embodiments are also the same.
When the polyamideimide has a polymerizable group, the polymerizable group may be located at at least one of R ¹¹¹ and R ¹¹⁷ , or may be located at the end of the polyamideimide.

In addition, to improve the storage stability of the resin composition, it is preferable to cap the main chain ends of the polyamideimide with a terminal capping agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. Preferred aspects of the terminal capping agent are the same as those for the polyimide described above.

-Imidization rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of the polyamideimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film.
There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less.
The imidization rate is measured in the same manner as the ring closure rate of the polyimide.

The polyamideimide may contain repeating units represented by the above formula (PAI-3) that all contain one type of R111 or R117, or may contain repeating units represented by the above formula (PAI-3) that contain two or more different types of R131 or R132. Furthermore, the polyamideimide may contain other types of repeating units in addition to the repeating units represented by the above formula (PAI-3). Examples of other types of repeating units include the repeating units represented by the above formula (PAI-1) or formula (PAI-2).

Polyamideimide can be synthesized, for example, by obtaining a polyamideimide precursor by a known method and then completely imidizing it using a known imidization reaction method, or by terminating the imidization reaction midway and introducing a partial imide structure, or by blending a fully imidized polymer with the polyamideimide precursor to introduce a partial imide structure.

The weight-average molecular weight (Mw) of the polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By making the weight-average molecular weight 5,000 or more, the fold resistance of the film after curing can be improved. In order to obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more.
The number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
The polyamideimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the polyamideimide molecular weight dispersity is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
When the resin composition contains multiple polyamideimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamideimide are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple polyamideimides as a single resin are each within the above-mentioned ranges.

[Method for producing polyimide precursors, etc.]
The polyimide precursor or the like can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and then esterifying the polyamic acid using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting the diester with a diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine, etc. Among the above production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the diamine is more preferred.
Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.
Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.
Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride.
In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent during the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.
In the method for producing a polyimide precursor, etc., it is preferable to add a basic compound during the reaction. The basic compound may be one kind or two or more kinds.
The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

-End-capping agent-
In the production method of a polyimide precursor or the like, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like to further improve storage stability. When capping the carboxylic acid anhydride or acid anhydride derivative remaining at the resin terminal, examples of end-capping agents include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and from the perspective of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, 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 phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, and hydroxystyrene. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples 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, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end-capping agents.
Furthermore, when capping the amino groups at the resin terminals, they can be capped with a compound having a functional group capable of reacting with the amino group. Preferred capping agents for the amino group 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 anhydride compounds include acetic anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, benzoic acid anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride. Preferred examples of carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

-Solid precipitation-
The production of polyimide precursors and the like may include a step of precipitating a solid. Specifically, after filtering out water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution as needed, the resulting polymer component is added to a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain polyimide precursors and the like. To improve the degree of purification, the polyimide precursors and the like may be repeatedly subjected to operations such as redissolution, reprecipitation, and drying. Furthermore, the process may include a step of 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. Also, 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 two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.

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

<Other resins>
The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as "another resin").
Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.
For example, instead of or in addition to the polymerizable compound described below, by adding a (meth)acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, the molar amount of polymerizable groups contained in 1 g of resin is 1 × 10 ^-3 mol/g or more) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product), etc.

When 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, still more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to 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.
In addition, a preferred embodiment of the resin composition of the present invention may be an embodiment in which the content of the other resin is low. In this embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

<Specific compound>
The resin composition of the present invention contains a compound (specific compound) represented by the following formula (1-1).
In formula (1-1), each R ¹ independently represents a hydrogen atom or a monovalent organic group, each R ² independently represents an aromatic heterocycle, each R ³ independently represents a hydrogen atom or a monovalent organic group, each L ¹ independently represents a divalent linking group, n represents an integer of 1 or more, and L ² represents an n-valent linking group.

[R ¹ ]
In formula (1-1), each R ¹ is preferably a hydrogen atom.
The organic group in ^R1 includes hydrocarbon groups such as alkyl groups, alkenyl groups, and aryl groups, and alkyl groups and aryl groups are preferred.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 4 carbon atoms.
The aryl group is preferably an aromatic hydrocarbon group, more preferably a phenyl group.
The hydrocarbon group may further have a known substituent.

[R ² ]
Examples of heteroatoms that are ring members in the aromatic heterocycle of ^R2 include a nitrogen atom, an oxygen atom, and a sulfur atom, and it is preferable that at least a nitrogen atom is contained as a ring member.
In addition, it is also one of the preferred embodiments that all heteroatoms that are ring members in the aromatic heterocycle in ^R2 are nitrogen atoms.
The number of heteroatoms in the aromatic heterocycle is preferably 1 to 4, and more preferably 2 to 4.

Furthermore, when the heteroatom is a nitrogen atom, the nitrogen atom may be directly bonded to a hydrogen atom, or may be directly bonded to a carbonyl group, a sulfonyl group, or a thiocarbonyl group in a substituent having a carbonyl group, a sulfonyl group, or a thiocarbonyl group.
The group bonded to the side opposite to the nitrogen atom that is a member of the nitrogen-containing heterocycle in the carbonyl group, sulfonyl group, or thiocarbonyl group is not particularly limited, but includes hydrocarbon groups and groups represented by a combination of a hydrocarbon group and at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N -, with hydrocarbon groups being preferred.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group, preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. These hydrocarbon groups may further have a substituent.
Specific examples of the hydrocarbon group include linear alkyl groups such as a methyl group, an ethyl group, and a propyl group; branched alkyl groups such as an isopropyl group, a t-butyl group, and a 2-ethylhexyl group; cyclic alkyl groups such as a cyclopentanyl group, a bornyl group, an isobornyl group, and an adamantyl group; alkenyl groups such as a methylvinyl group; and aromatic hydrocarbon groups such as a phenyl group, a naphthyl group, a 4-methylphenyl group, and a 2,6-methylphenyl group.
The above R ^N represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.

Preferably, ^R2 contains an azole structure.
The azole structure refers to a five-membered heterocyclic ring structure containing one or more nitrogen atoms as ring members. The azole structure in ^R2 is preferably a five-membered heterocyclic ring structure containing two or more nitrogen atoms as ring members. Preferred examples thereof include an imidazole structure, a triazole structure, and a tetrazole structure.
^R2 preferably contains an imidazole structure, a triazole structure, a tetrazole structure, or a fused ring structure of any of these rings with another ring, and more preferably contains a purine structure.
Furthermore, ^R2 is also preferably an imidazole structure, a triazole structure, a tetrazole structure, or a fused ring structure of these rings with another ring (for example, a benzene ring, a pyrimidine ring, etc.), and is more preferably a purine structure.
When ^R2 is a purine structure, the bonding site of the purine structure with the nitrogen atom to which ^R1 in formula (1-1) is bonded is not particularly limited, but is preferably, for example, the carbon atom at position 6 of the purine structure.

Preferred embodiments of ^R2 include, but are not limited to, the following structures: In the following formula, * represents the bonding site with the nitrogen atom to which ^R1 in formula (1-1) is bonded.

[L ¹ ]
In formula (1-1), L ¹ may be a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least one structure selected from the group consisting of —O—, —C(═O)—, —S—, —S(═O) ₂ —, and —NR ^N —, and is preferably a hydrocarbon group.
The hydrocarbon group may be any of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, but an aliphatic hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group is more preferred.

From the viewpoint of reliability, ^L1 is preferably a structure represented by the following formula (L1-1): According to such an embodiment, it is believed that the phthalimide structure in the cured product described below will be a stable structure.
In formula (L1-1), L ^L1 represents a divalent linking group, # represents the bonding site to the nitrogen atom to which R ³ in formula (1-1) is bonded, and * represents the bonding site to the nitrogen atom to which R ¹ in formula (1-1) is bonded.

In formula (L1-1), L ^L1 is preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N -, more preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and at least one structure selected from the group consisting of -O- and -S-, and more preferably a hydrocarbon group.
The hydrocarbon group may be any of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, but an alkylene group is preferred.
The alkylene group is preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and even more preferably an alkylene group having 2 to 4 carbon atoms.

Preferred embodiments of ^L1 in formula (1-1) include, but are not limited to, the following structures: In the following formula, # represents the bonding site to the nitrogen atom to which ^R3 in formula (1-1) is bonded, and * represents the bonding site to the nitrogen atom to which ^R1 in formula (1-1) is bonded.

[R ³ ]
In formula (1-1), R ³ is preferably a hydrogen atom.
In particular, from the viewpoint of reliability, it is preferable that ^L1 is a structure represented by the above formula (L1-1) and ^R3 is a hydrogen atom. According to such an embodiment, it is believed that a phthalimide structure in the cured product described below is easily formed and that the structure is stable.
The organic group in ^R3 includes hydrocarbon groups such as alkyl groups, alkenyl groups, and aryl groups, and alkyl groups and aryl groups are preferred.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 4 carbon atoms.
The aryl group is preferably an aromatic hydrocarbon group, more preferably a phenyl group.
The hydrocarbon group may further have a known substituent.

[ ^L2 ]
In formula (1-1), L ² is preferably a hydrocarbon group or a group represented by a combination of one or more hydrocarbon groups with at least one structure selected from the group consisting of heterocyclic groups, -O-, -C(═O)-, -S-, -S(═O) ₂ -, and -NR ^N -, and more preferably a hydrocarbon group or a group represented by a combination of one or more hydrocarbon groups with at least one structure selected from the group consisting of -O-, -S-, and -NR ^N -. The heterocyclic group is preferably a heteroaromatic ring group. Examples of heteroatoms contained in the heterocyclic group include an oxygen atom, a sulfur atom, and a nitrogen atom. The R ^N represents a hydrogen atom or a monovalent substituent, and is preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.
The hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof, but preferably contains at least an aromatic hydrocarbon group, and more preferably is a group represented by a combination of an aromatic hydrocarbon group and an aliphatic hydrocarbon group.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a group in which multiple hydrogen atoms have been removed from a benzene ring. The aromatic hydrocarbon group may have a substituent, or may form a condensed ring with another ring structure.
The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, still more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.

From the viewpoint of the efficiency of generating a base, ^L2 preferably contains an aromatic ring structure.
Examples of the aromatic ring structure in ^L2 include the above-mentioned aromatic hydrocarbon groups and the above-mentioned heteroaromatic ring groups, with aromatic hydrocarbon groups being preferred.

^L2 also preferably contains a hydroxy group, a carboxy group or an alkoxycarbonyl group. The alkoxy group in the alkoxycarbonyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
When ^L2 contains a hydroxy group, the number of atoms on the shortest path of the linking chain between the hydroxy group in ^L2 and the —C(═O)— to which ^L2 is bonded in formula (1-1) (linking chain length) is preferably 3 to 6, and more preferably 3 or 4.
When ^L2 contains a carboxy group or an alkoxycarbonyl group, the number of atoms on the shortest path of the linking chain between the carboxy group or alkoxycarbonyl group in ^L2 and the —C(═O)— to which ^L2 is bonded in formula (1-1) (linking chain length) is preferably 2 to 5, and more preferably 2 or 3.
In any of the above cases, ^L2 preferably contains an aromatic ring structure (preferably a phenylene group which may have a substituent or a fused ring, more preferably a 1,2-phenylene group which may have a substituent or a fused ring), and it is preferable that the aromatic ring structure be included on the shortest path.
It is also preferable that ^L2 contains an oxygen atom or a sulfur atom on the shortest path.

From the viewpoint of chemical resistance, ^L2 preferably has a polymerizable group, more preferably a radically polymerizable group.
Examples of the radically polymerizable group include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyloxy group, a maleimide group, and a (meth)acrylamide group. Of these, a (meth)acryloxy group, a (meth)acrylamide group, or a vinylphenyl group is preferred, and from the viewpoint of reactivity, a (meth)acryloxy group is more preferred.
When ^L2 has a radical polymerizable group, it is preferable that at least one of the following conditions is satisfied: the cyclized resin or a precursor thereof has a radical polymerizable group, or the resin composition contains a radical crosslinking agent described below.
According to such an embodiment, the base generator is incorporated into the polymer formed by polymerization, and therefore, for example, the distribution of the base generator in the composition becomes nearly uniform, which is thought to result in further improvements in the breaking elongation, pattern rectangularity, etc. of the cured product.

Among these, it is preferable that in formula (1-1), n is 1 and ^L2 is a group represented by the following formula (L2-1).
In formula (L2-1), Ar represents an aromatic group, ^L represents a single bond or a divalent linking group, ^R represents a hydrogen atom, a hydroxy group or a monovalent organic group, and * represents a bonding site with the carbonyl group in formula (1-1).

In formula (L2-1), Ar may be an aromatic hydrocarbon group or a heteroaromatic ring group, but is preferably an aromatic hydrocarbon group.
The aromatic hydrocarbon group or heteroaromatic ring group for Ar includes the above-mentioned aromatic hydrocarbon groups and heteroaromatic ring groups, with aromatic hydrocarbon groups being preferred.

In formula (L2-1), L ^L2 and R ^L2 are preferably located at adjacent positions in the aromatic group represented by Ar.
Here, A and B being located at adjacent positions in the aromatic group means that the atom that is a ring member of the aromatic group to which A is bonded and the atom that is a ring member of the aromatic group to which B is bonded are adjacent ring members in the aromatic group, and if the aromatic group is a benzene ring, this means that they are located at meta positions.

In formula (L2-1), the divalent linking group for L ^L2 is preferably an alkylene group or a group represented by a combination of one or more alkylene groups and at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N -, and more preferably an alkylene group or a group represented by a combination of one or more alkylene groups and at least one structure selected from the group consisting of -O-, -S-, and -NR ^N -.
^RN is as described above.
The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms.

In formula (L2-1), examples of the monovalent organic group for R ^L2 include a hydroxyalkyl group, an alkoxy group, a carboxy group, and an alkoxycarbonyl group.

Preferred embodiments of ^L2 in formula (1-1) include, but are not limited to, the following structures: In the following formula, * represents the bonding site with the carbonyl group in formula (1-1).
In the above structure, one ^R1 is a hydrogen atom and the other is the following structure, and one ^R2 is a hydrogen atom and the other is the following structure. In the below structure, # represents the bonding site with the oxygen atom in the above structure. In the below structure, * represents the bonding site with the carbonyl group in formula (1-1).

[n]
In formula (1-1), n represents an integer of 1 or more, preferably an integer of 1 to 4, and more preferably 1 or 2. An embodiment in which n is 1 is also one of the preferred embodiments of the present invention.

The compound represented by formula (1-1) is preferably a compound that generates a base when exposed to light or heat, and preferably generates a base when exposed to light or heat via cleavage between the nitrogen atom bonded to ^R3 in formula (1-1) and the carbonyl group in formula (1-1).
The compound represented by formula (1-1) is preferably a compound that generates a base under the action of heat, and the compound represented by formula (1-1) preferably generates a base by cleavage between the nitrogen atom bonded to ^R3 in formula (1-1) and the carbonyl group in formula (1-1) under the action of heat.

Specifically, the specific compound preferably generates a base when heated at 250° C., more preferably when heated at 230° C., even more preferably when heated at 220° C., still more preferably when heated at 200° C., particularly preferably when heated at 190° C., and most preferably when heated at 180° C. There are no particular restrictions on the lower limit of the temperature at which the base is generated, but from the viewpoint of the storage stability of the composition, for example, it is preferably 100° C. or higher.
Whether or not a certain compound A exhibits the property of generating a base at a certain temperature X° C. can be determined by the following method.
One mole of compound A is heated in a sealed container at 1 atmosphere at the above-mentioned X° C. for 3 hours, and then the amount of decomposition is quantified by a method such as HPLC (high performance liquid chromatography), and if 0.01 mole or more of a base is generated, it is determined that compound A generates a base upon heating at X° C. Whether or not the generated compound is a base can be confirmed, for example, by using ¹ H-NMR.
The amount of the base generated is preferably 0.1 mol or more, more preferably 0.5 mol or more. There is no particular upper limit to the amount of the base generated, but it can be, for example, 1000 mol or less.

Furthermore, when the specific compound generates a base upon exposure to light, a composition A is prepared by dissolving the specific compound in a solvent, and the composition A is irradiated with broadband light having a wavelength of 190 to 800 nm at an exposure illuminance of 25 W/cm2 for 30 seconds under conditions of ¹ atmosphere and 25°C. The amount of decomposition is then quantified by a method such as HPLC (high performance liquid chromatography), and if 0.01 mole or more of base is generated relative to the total molar amount of the specific compound, it is determined that compound A generates a base upon exposure to light. The amount of base generated is preferably 0.1 mole or more, and more preferably 0.5 mole or more. The upper limit of the amount of base generated is not particularly limited, but can be, for example, 1000 moles or less.
When the resin composition contains a solvent, the concentration of the specific compound in composition A can be the same as the concentration in the resin composition, and the type of solvent in the composition can be the same as the solvent contained in the resin composition. When the resin composition does not contain a solvent, the concentration of the specific compound in composition A can be about 1.0 mass% relative to the total mass of composition A, and the type of solvent that can be used can be N-methyl-2-pyrrolidone or the like.

The base generated from the specific compound is preferably a compound represented by the following formula (2-1).
In formula (2-1), R ¹ , R ² , R ³ and L ¹ have the same meanings as R ¹ , R ² , R ³ and L ¹ in formula (1-1), respectively, and the preferred embodiments are also the same.

The molecular weight of the base generated from the specific compound is preferably 70 to 500, more preferably 80 to 300, and even more preferably 90 to 220.
The base generated from the specific compound is preferably a base having a conjugate acid with a pKa of 0 or more, more preferably 3 or more, and still more preferably 6 or more. The upper limit of the pKa of the conjugate acid is not particularly limited, but is preferably 30 or less.
pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm, pKa. In this specification, pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified.
When the conjugate acid has a plurality of pKa values, it is preferable that at least one of them is within the above range.
Furthermore, from the viewpoint of storage stability of the composition, the pKa of the conjugate acid of the specific compound (the pKa of the conjugate acid of the specific compound before decomposition) is preferably 1.0 or less, more preferably 0.0 or less, and even more preferably -0.5 or less. The lower limit is not particularly limited, but may be, for example, -20 or more.
When the conjugate acid has a plurality of pKa values, it is more preferable that the maximum value is within the above range.

Specific examples of the generated base include, but are not limited to, bases having the following structures: In addition, in the composition, these bases may undergo further structural changes, such as elimination of a substituent bonded to a nitrogen atom in an azole structure (including an azole structure contained in a fused ring such as a purine ring structure).

[Molecular weight]
The molecular weight of the specific compound is preferably 150 to 1,000, more preferably 180 to 800, and even more preferably 200 to 700.

[Synthesis method]
The specific compound can be synthesized, for example, by the synthesis method described in the Examples below. Alternatively, other known synthesis methods may be used for synthesis, and the synthesis method is not particularly limited. For example, the structure corresponding to ^R2 in formula (1-1) may be bonded to the structure corresponding to ^L1 , and then further bonded to the structure corresponding to ^L2 , or the structure corresponding to ^L1 may be bonded to the structure corresponding to ^L2 , and then the structure corresponding to ^R2 may be further bonded to the structure corresponding to ^L1 .

Specific examples of specific compounds include, but are not limited to, F-1 to F-24, which were used in the examples.

The content of the specific compound relative to the total solid content of the resin composition of the present invention is preferably 0.05 to 10% by mass. The lower limit is more preferably 0.1% by mass or more. The upper limit is more preferably 5% by mass or less, and even more preferably 2% by mass or less.
The specific compound may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.
In the resin composition of the present invention, the content of the specific compound relative to 100 parts by mass of the specific resin is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.

<Primary amine>
The resin composition of the present invention preferably has a primary amine content of 1% by mass or less.
In the present invention, a primary amine refers to a compound in which one of the hydrogen atoms of ammonia has been substituted with an organic group.
The content of the primary amine is more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less. The lower limit of the content is not particularly limited, and may be 0% by mass.
In addition, the content of the primary amine in the resin composition of the present invention is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, relative to the total mass of the specific compound. The lower limit of the content is not particularly limited, and may be 0% by mass.

<Polymerizable compound>
The resin composition of the present invention preferably contains a polymerizable compound.
The polymerizable compound may be a radical crosslinking agent or other crosslinking agent.

[Radical crosslinking agent]
The resin composition of the present invention preferably contains a radical crosslinking agent.
The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
Among these, the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds, and may also have three or more ethylenically unsaturated bonds.
The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds.
In addition, 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 the compound having three or more ethylenically unsaturated bonds.

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

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.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohols, and amides of unsaturated carboxylic acids and polyamines. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl, amino, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, compounds in which the above unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. can also be used. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

Furthermore, compounds having a boiling point of 100°C or higher under normal pressure are also preferred as radical crosslinking agents. 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, trimethylolethane, and many other compounds. Examples of suitable compounds include polyfunctional acrylates and methacrylates, such as compounds obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth)acrylating the resulting compound, urethane (meth)acrylates as described in JP-B Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates as described in JP-A Nos. 48-064183, 49-043191, and 52-030490, and epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of JP-A 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 and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate.

Other preferred radical crosslinking agents that can be used include compounds having a fluorene ring and two or more groups with ethylenically unsaturated bonds, as described in JP-A Nos. 2010-160418, 2010-129825, and Japanese Patent No. 4364216, and cardo resins.

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

In addition to the above, the compounds described in paragraphs [0048] to [0051] of JP 2015-034964 A and the compounds described in paragraphs [0087] to [0131] of WO 2015/199219 A can also be preferably used, the contents of which are incorporated herein by reference.

In addition, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resulting compound, which are described in JP-A-10-062986 as formula (1) and formula (2) along with specific examples thereof, can also be used as radical crosslinking agents.

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP 2015-187211 A can also be used as radical crosslinking agents, the contents of which are incorporated herein by reference.

Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd., and A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.), as well as those in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these compounds can also be used.

Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains manufactured by Sartomer Corporation; SR-209, 231, and 239, difunctional methacrylates with four ethyleneoxy chains manufactured by Sartomer Corporation; DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.; and urethane Examples include oligomer UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).

Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, as well as urethane compounds with an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Furthermore, compounds with an amino structure or sulfide structure in the molecule, as described in JP-A No. 63-277653, JP-A No. 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.

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

The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, and particularly preferably 1 to 100 mgKOH/g. When the acid value of the radical crosslinking agent is within this range, it provides excellent handling during manufacturing and developability. It also provides good polymerizability. The acid value is measured in accordance with JIS K 0070:1992.

From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate for 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, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other bifunctional acrylates having a urethane bond and bifunctional methacrylates having a urethane bond can be used. Two or more of these can be mixed and used as needed.
For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain.
In the resin composition of the present invention, from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. Examples of the monofunctional radical crosslinking agent 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; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds having a boiling point of 100°C or higher under normal pressure are also preferred as the monofunctional radical crosslinking agent.
Other examples of the bifunctional or higher functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

When a radical crosslinking agent is contained, its content is preferably more than 0% by mass and not more than 60% by mass, based on the total solids 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, or two or more may be used in combination. When two or more types are used in combination, it is preferable that the total amount be within the above range.

[Other crosslinking agents]
The resin composition of the present invention preferably contains a crosslinking agent other than the above-mentioned radical crosslinking agent.
In the present invention, the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photoacid generator or photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
As the other crosslinking agent, a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is preferred, and a compound having a structure in which at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an alkoxymethyl group is directly bonded to a nitrogen atom is more preferred.
Other crosslinking agents include, for example, compounds having a structure in which an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and an alcohol, and the hydrogen atom of the amino group is substituted with an acyloxymethyl group, a methylol group, or an alkoxymethyl group.The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compound produced by the above method may be used.In addition, oligomers formed by self-condensation of the methylol groups of these compounds may also be used.
As the amino group-containing compound, a crosslinking agent using melamine is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent.
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 glycoluril-based crosslinking agents and melamine-based crosslinking agents, which will be described later.

Examples of the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group or a nitrogen atom of the following urea structure, or on a triazine.
The alkoxymethyl group or acyloxymethyl group contained in the above compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and even more preferably 2 carbon atoms.
The total number of alkoxymethyl groups and acyloxymethyl groups contained in the compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
The molecular weight of the compound is preferably 1,500 or less, and more preferably 180 to 1,200.

R ₁₀₀ represents an alkyl group or an acyl group.
R ₁₀₁ and R ₁₀₂ 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 an acyloxymethyl group is directly substituted on an aromatic group include compounds represented by the following general formula:

In the formula, X represents a single bond or a divalent organic group, each of the individual 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 under the action of an acid to produce an alkali-soluble group (for example, a group that is eliminated by the action of an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (each 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)).
R ₁₀₅ each independently represents an alkyl group or an alkenyl group; a, b, and c each independently represent 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.
Examples of R ⁵ in a group that decomposes under the action of an acid to generate an alkali-soluble group, a group that leaves under the action of an acid, and a group represented by —C(R ⁴ ) ₂ COOR ⁵ include —C(R ₃₆ )(R ₃₇ )(R ₃₈ ), —C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and —C(R ₀₁ )(R ₀₂ )(OR ₃₉ ).
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, and R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.
The alkyl group may be either linear or branched.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms.
The cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms.
The above aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms.
These groups may further have known substituents within the range in which the effects of the present invention can be obtained.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

Preferably, the group that decomposes under the action of an acid to generate an alkali-soluble group, or the group that is eliminated under the action of an acid, is a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably, it is a tertiary alkyl ester group or an acetal group.

Specific examples of compounds having an alkoxymethyl group include the structures below. Examples of compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the compounds below has been replaced with an acyloxymethyl group. Examples of compounds having an alkoxymethyl group or acyloxymethyl group in the molecule include, but are not limited to, the following compounds.

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

Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

Specific examples of the urea-based crosslinking agent include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, and tetrabutoxymethylated glycoluril;
urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea;
ethyleneurea-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, monoethoxymethylated 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-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

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

Other commercially available crosslinking agents may be used. Suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, and TriML-35XL. , 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.), Nikalac (registered trademark, the same applies hereinafter) MX-290, Nikalac MX-280, Nikalac MX-270, Nikalac MX-279, Nikalac MW-100LM, Nikalac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), and others.

It is also preferable that the resin composition of the present invention contains, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

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

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

Examples of epoxy compounds include, but are not limited to, bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol epoxy resins or polyhydric alcohol hydrocarbon 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 epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane. Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-830LVP, Epicron (registered trademark) EXA-8183, Epicron (registered trademark) EXA-8169, Epicron (registered trademark) N- 660, Epicron (registered trademark) N-665-EXP-S, Epicron (registered trademark) N-740 (all trade names, manufactured by DIC Corporation), Rikaresin (registered trademark) BEO-20E, Rikaresin (registered trademark) BEO-60E, Rikaresin (registered trademark) HBE-100, Rikaresin (registered trademark) DME-100, Rikaresin (registered trademark) L-200 (trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088 S, EP-3950S (all trade names, manufactured by ADEKA Corporation), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (all trade names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-300 Examples of suitable compounds 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 suitable for use:

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

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

-Oxetane compound (compound having an oxetanyl group)-
Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, such as 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 that can be suitably used include the Aron Oxetane series (e.g., OXT-121, OXT-221) manufactured by Toagosei Co., Ltd., and these may be used alone or in combination of two or more.

-Benzoxazine compound (compound having a benzoxazolyl group)-
Benzoxazine compounds are preferred because they undergo a crosslinking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and further, they reduce thermal shrinkage and suppress warping.

Preferred examples of benzoxazine compounds include P-d-type benzoxazine, Fa-type benzoxazine (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazine compounds. These may be used alone or in combination of two or more.

The content of the other crosslinking agent 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 solids content of the resin composition of the present invention. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total amount is preferably within the above range.

[Polymerization initiator]
The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat, and particularly preferably contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations 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 range is preferred. Alternatively, it may be an activator that reacts in some way with a photoexcited sensitizer to generate active radicals.

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

Any known photoradical polymerization initiator can be used. 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, hexaarylbiimidazoles, oxime compounds such as 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, organic boron compounds, and iron arene complexes. For details, please refer to paragraphs [0165] to [0182] of JP 2016-027357 A and paragraphs [0138] to [0151] of WO 2015/199219 A, the contents of which are incorporated herein by reference. Other examples include the compounds described in paragraphs [0065] to [0111] of JP 2014-130173 A and Japanese Patent No. 6,301,489 A, the peroxide-based photopolymerization initiators described in MATERIAL STAGE, pp. 37-60, Vol. 19, No. 3, 2019, the photopolymerization initiators described in WO 2018/221177 A, the photopolymerization initiators described in WO 2018/110179 A, the photopolymerization initiators described in JP 2019-043864 A, the photopolymerization initiators described in JP 2019-044030 A, and the peroxide-based initiators described in JP 2019-167313 A, the contents of which are also incorporated herein by reference.

Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitable.

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, the aminoacetophenone initiators described in JP-A-10-291969 and the acylphosphine oxide initiators described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and 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).

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

As an aminoacetophenone initiator, compounds described in JP 2009-191179 A, which have a maximum absorption wavelength matching a wavelength light source such as 365 nm or 405 nm, can also be used, the contents of which are incorporated herein by reference.

Examples of acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Other examples include Omnirad 819 and Omnirad TPO (manufactured by IGM Resins B.V.), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF).

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

Oxime compounds are more preferred as photoradical polymerization initiators. By using oxime compounds, it is possible to more effectively improve exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.

Specific examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Examples of such compounds include those described in J.Non-Oxidative Stress Technology (1995, pp. 202-232), those described in JP-A-2000-066385, those described in JP-T-2004-534797, those described in JP-A-2017-019766, those described in JP-A-6065596, those described in WO-A-2015/152153, those described in WO-A-2017/051680, those described in JP-A-2017-198865, those described in paragraphs 0025 to 0038 of WO-A-2017/164127, and those described in WO-A-2013/167515, the contents of which are incorporated herein by reference.

Preferred oxime compounds include, for example, compounds having the following structure: 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-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 the photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a linking group of >C=N-O-C(=O)- within the molecule.

Commercially available products such as IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A) are also suitable for use. In addition, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation) can also be used. Also usable are DFI-091 (manufactured by Daito ChemiX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Also usable are oxime compounds having the following structure:

Oxime compounds having a fluorene ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a fluorene ring include the compounds described in JP 2014-137466 A and Japanese Patent No. 06636081, the contents 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 a carbazole ring is replaced with a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in WO 2013/083505, the contents of which are incorporated herein by reference.

It is also possible to use oxime compounds containing fluorine atoms. Specific examples of such oxime compounds include the compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and compound (C-3) described in paragraph 0101 of JP 2013-164471 A, the contents of which are incorporated herein by reference.

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

Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75, which are described in WO 2015/036910.

As a photoradical polymerization initiator, an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include the compounds described in WO 2019/088055, the contents of which are incorporated herein by reference.

As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can also be used. Examples of the electron-withdrawing group in the aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl groups and nitro groups are preferred, and acyl groups are more preferred because they are more likely to form a film with excellent light resistance, and benzoyl groups are even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group, and 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 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group;
R ^X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group;
R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent.
However, at least one of R ^X10 to R ^X14 is an electron-withdrawing group.

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 contents of which are incorporated herein by reference.

The most preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP-A-2007-269779 and oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, the contents 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, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

More 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 a metallocene compound or an oxime compound is even more preferred.

In addition, photoradical polymerization initiators that can be used include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenones such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's 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 an aromatic ring such as alkylanthraquinones, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkylbenzoins, and benzyl derivatives such as benzil dimethyl ketal. Compounds represented by the following formula (I) can also be used.

In formula (I), R ^I00 represents 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 a phenyl group substituted with at least one of 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, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, or a biphenyl group; R ^I01 represents a group represented by formula (II) or the same group as R ^I00 ; and R ^I02 to R ^I04 each independently represent 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 the above formula (I).

In addition, the photoradical polymerization initiator may be the compound described in paragraphs 0048 to 0055 of WO 2015/125469, the contents of which are incorporated herein by reference.

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

When a photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, it is preferable that the total amount is in the above range.
In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[Sensitizer]
The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator or the photoradical polymerization initiator undergoes a chemical change and decomposes, generating a radical, an acid, or a base.
Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds.
Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, and 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 (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Examples of such an alkyl acrylate copolymer include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide.
Other sensitizing dyes may also be used.
For details about the sensitizing dye, please refer to the description in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

When the resin composition contains a sensitizer, the content of the sensitizer 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 solids content of the resin composition. One type of sensitizer may be used alone, or two or more types may be used in combination.

[Chain transfer agent]
The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include compounds having -S-S-, -SO ₂ -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These donate hydrogen to low-activity radicals to generate radicals, or can generate radicals by being oxidized and then deprotonated. Thiol compounds are particularly preferred.

The chain transfer agent may also be the compound described in paragraphs 0152-0153 of WO 2015/199219, the contents of which are 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, per 100 parts by mass of the total solids content of the resin composition of the present invention. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total amount is preferably within the above range.

<Base Generator>
The resin composition of the present invention may contain a base generator. Here, the base generator is a compound that can generate a base by physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
However, the base generators corresponding to the above-mentioned specific compounds are not considered to be the base generators referred to here.
In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in good performance as an interlayer insulating film for a rewiring layer included in, for example, a semiconductor package.
The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
The base generator according to the present invention is not particularly limited, and known base generators can be used, such as carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds.
Specific examples of the non-ionic base generator include compounds represented by formula (B1), formula (B2), and formula (B3).

In formula (B1) and formula (B2), ^Rb1 , ^Rb2 , and ^Rb3 are each independently an organic group not having a tertiary amine structure, a halogen atom, or a hydrogen atom. However, ^Rb1 and ^Rb2 are not simultaneously hydrogen atoms. Furthermore, none of ^Rb1 , ^Rb2 , and ^Rb3 has a carboxy group. In this specification, the term "tertiary amine structure" refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, this does not apply to cases where the bonded carbon atom is a carbon atom that forms a carbonyl group, that is, when the bonded carbon atom forms an amide group together with the nitrogen atom.

In formulas (B1) and (B2), it is preferable that at least one of ^Rb1 , ^Rb2 , and ^Rb3 contains a cyclic structure, and more preferably at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a fused ring, and a monocyclic ring or a fused ring formed by condensing two monocyclic rings is preferable. The monocyclic ring is preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

More specifically, ^Rb1 and ^Rb2 are preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent within the range in which the effects of the present invention are exhibited. ^Rb1 and ^Rb2 may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocycle. ^Rb1 and ^Rb2 are particularly preferably a linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

Examples of ^Rb3 include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and even more preferably having 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably having 8 to 20 carbon atoms, and even more preferably having 8 to 16 carbon atoms), an alkoxyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), and an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferred. ^Rb3 may further have a substituent within the range in which the effects of the present invention are exhibited.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (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 having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), which may have a substituent within the range in which the effects of the present invention are exhibited. Among these, Rb ¹³ is preferably an arylalkyl group.

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

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

The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a).

Rb ¹¹ and Rb ¹² have the same meanings as Rb ¹¹ and Rb ¹² in formula (B1-1).
^Rb15 and ^Rb16 are each a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and a hydrogen atom or a methyl group is preferred.
Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferred.

In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the linking chain is 3 or more. Furthermore, ^R and ^R each independently represent a monovalent organic group.

In this specification, the term "linking chain" refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked, which links these atoms to be linked in the shortest possible manner (with the smallest 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 the 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 the "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 progressing the 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 WO 2020/066416 and the compounds described in paragraphs [0143] to [0177] of WO 2018/038002.

The base generator also preferably contains 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 present in the atomic sequence that forms 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 carbon atoms, and even more preferably 3 to 12 carbon atoms), preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 10 carbon atoms). Specific examples include aliphatic hydrocarbon groups (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 10 carbon atoms) and aromatic hydrocarbon groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), with aliphatic hydrocarbon groups being preferred. Using aliphatic hydrocarbon groups as R ^N1 and R ^N2 is preferred because the basicity of the generated base is high. The aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, aromatic ring, or substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

Examples of the aliphatic hydrocarbon group constituting R ^N1 and R ^N2 include a linear or branched chain alkyl group, a cyclic alkyl group, a group relating to a combination of a linear alkyl group and a cyclic alkyl group, and an alkyl group having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, an isopentyl group, a neopentyl group, a tertiary pentyl group, and an isohexyl group.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
The group representing the combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12. Examples of the group representing the combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an 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. The alkyl group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched.
Among these, from the viewpoint of increasing the boiling point of the decomposition product base described below, R ^N1 and R ^N2 are preferably alkyl groups having 5 to 12 carbon atoms. However, in a formulation in which importance is placed on adhesion when laminating with a metal (e.g., copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

R ^N1 and R ^N2 may be linked to each other to form a cyclic structure. When forming the cyclic structure, an oxygen atom or the like may be contained in the chain. Furthermore, the cyclic structure formed by R ^N1 and R ^N2 may be a monocyclic ring or a fused ring, but a monocyclic ring is preferable. The cyclic structure formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc., and preferred examples include a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.

R ^C1 represents a hydrogen atom or a protecting group, and is preferably a hydrogen atom.

Preferred protecting groups are those that are decomposed by the action of an acid or a base, and preferred examples of such protecting groups are those that are decomposed by an acid.

Specific examples of protecting groups include linear or cyclic alkyl groups, and 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 specific examples include 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.

The divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent and may have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linking group which may have an oxygen atom in the chain is preferred, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group relating to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group is more preferred, and a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is even more preferred. It is more preferred 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 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. Groups representing a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably have 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 10 carbon atoms.

Specific examples of the linking group L include linear or branched chain alkylene groups, cyclic alkylene groups, groups relating to a combination of a linear alkylene group and a cyclic alkylene group, alkylene groups having an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylene groups, and arylene alkylene groups.
The linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
The cyclic alkylene group preferably has 3 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms.
The group relating to the combination of the chain alkylene group and the cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, 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 carbon atoms, and even more preferably 1 to 3 carbon atoms.

The linear or branched chain 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 chain 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 or 2.
The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
Among these, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferred, and a 1,2-ethylene group, a propanediyl group (particularly a 1,3-propanediyl group), a cyclohexanediyl group (particularly a 1,2-cyclohexanediyl group), a vinylene group (particularly a cis-vinylene group), a phenylene group (1,2-phenylene group), a phenylenemethylene group (particularly a 1,2-phenylenemethylene group), and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.

Examples of base generators include the following, but the present invention should not be construed as being 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 the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 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.

When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition 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, and even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
The base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.
The resin composition of the present invention may also be in an embodiment that is substantially free of any base generator other than the specific compound.
Specifically, the content of the base generator other than the specific compound 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, relative to the total mass of the resin composition. The lower limit is not particularly limited, and may be 0% by mass.

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

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, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxy Suitable examples include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (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), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

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

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

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

A suitable example of a sulfoxide is dimethyl sulfoxide.

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

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

Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

From the perspective of improving the properties of the coated surface, it is also preferable to mix two or more solvents.

In the present invention, a solvent selected from the group consisting of 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, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more of these solvents, is preferred. A combination of dimethyl sulfoxide and γ-butyrolactone, or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

From the standpoint of coatability, the solvent content is preferably an amount that results in a total solids concentration of the resin composition of the present invention of 5 to 80% by mass, more preferably an amount that results in a total solids concentration of 5 to 75% by mass, even more preferably an amount that results in a total solids concentration of 10 to 70% by mass, and even more preferably an amount that results in a total solids concentration of 20 to 70% by mass. The solvent content may be adjusted depending on 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. When two or more solvents are contained, it is preferable that the total amount thereof is within the above range.

<Metal adhesion improver>
The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[Silane coupling agent]
Examples of silane coupling agents include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002 A, compounds described in paragraphs 0063 to 0071 of WO 2011/080992 A, compounds described in paragraphs 0060 to 0061 of JP 2014-191252 A, compounds described in paragraphs 0045 to 0052 of JP 2014-041264 A, compounds described in paragraph 0055 of WO 2014/097594 A, compounds described in paragraphs 0067 to 0078 of JP 2018-173573 A, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compound as the silane coupling agent: In the following formula, Me represents a methyl group, and Et represents an ethyl group.

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

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

Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.

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. Setting it at or above the lower limit above will improve adhesion between the pattern and the metal layer, while setting it at or below the upper limit above will improve the 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 the total be within the above range.

<Migration inhibitor>
The resin composition of the present invention preferably further contains a migration inhibitor, which makes it possible to effectively inhibit metal ions derived from the metal layer (metal wiring) from migrating into the film.

Migration inhibitors are not particularly limited, but examples include compounds having a heterocycle (such as a 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, 6H-pyran ring, triazine ring, or a fused ring such as a purine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferred.

Alternatively, ion trapping agents that capture anions such as halogen ions can also be used.

Other migration inhibitors that can be used include the rust inhibitors described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compounds described in paragraph 0052 of JP 2011-059656 A, the compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520 A, and the compounds described in paragraph 0166 of WO 2015/199219, 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 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the resin composition of the present invention.
In addition, an embodiment in which the resin composition of the present invention does not substantially contain a migration inhibitor is also one of the preferred embodiments of the present invention.
"Substantially free of migration inhibitor" means that the content of migration inhibitor is less than 0.01% by mass relative to 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 two or more types of migration inhibitors are used, it is preferable that the total amount is within the above range.

<Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.

Specific compounds used as polymerization inhibitors 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 cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic 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, dibutyldithiocarbonate copper(II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like are preferably used. Additionally, the polymerization inhibitors described in paragraph 0060 of JP 2015-127817 A and the compounds described in paragraphs 0031 to 0046 of WO 2015/125469 A can also be used, the contents of which are incorporated herein by reference.

When 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 solids content of the resin composition of the present invention.

The polymerization inhibitor may be one type, or two or more types. If two or more types of polymerization inhibitors are used, it is preferable that the total amount is within the above range.

<Other additives>
The resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, within the scope of achieving the effects of the present invention. By appropriately incorporating these components, film properties and other properties can be adjusted. For details of these components, please refer to, for example, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013/0034812 ), and paragraphs 0101-0104, 0107-0109, etc. of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are incorporated, the total amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[Surfactant]
As the surfactant, various surfactants can be used, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid properties (particularly fluidity) of the composition when prepared as a coating liquid are further improved, resulting in improved uniformity of the coating thickness and liquid saving. In other words, when a film is formed using a coating liquid containing a surfactant-containing composition, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving wettability to the surface to be coated and improving coatability to the surface to be coated. This makes it possible to more effectively form a film of uniform thickness with minimal 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, and RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, FC431, FC171, Novec FC4430, and FC4432 (all manufactured by 3M). Examples of suitable surfactants include Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, and Surflon KH-40 (all manufactured by Asahi Glass Co., Ltd.), and PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). Fluorine-based surfactants may also be used, such as compounds described in paragraphs 0015 to 0158 of JP-A 2015-117327 and compounds described in paragraphs 0117 to 0132 of JP-A 2011-132503, the contents of which are incorporated herein by reference. A block polymer can also be used as the fluorine-based surfactant, and specific examples include compounds described in JP-A-2011-89090, the contents of which are incorporated herein by reference.
As the fluorosurfactant, a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups) can also be preferably used, and the following compounds are also exemplified as the fluorosurfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.
The fluorosurfactant may also be a fluorine-containing polymer having an ethylenically unsaturated group in the side chain. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. Commercially available products include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

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

Examples of silicone 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 Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF6001, and KF6002 (all manufactured by Shin-Etsu Silicone Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK-Chemie Co., Ltd.).

Examples of hydrocarbon surfactants include Paionin A-76, Newkalgen FS-3PG, Paionin B-709, Paionin B-811-N, Paionin D-1004, Paionin D-3104, Paionin D-3605, Paionin D-6112, Paionin D-2104-D, Paionin D-212, Paionin D-931, Paionin D-941, Paionin D-951, Paionin E-5310, Paionin P-1050-B, Paionin P-1028-P, and Paionin P-4050-T (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 (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Co., Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), Paionin D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), and Olfine E1010 and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

Specific examples of cationic surfactants include organosiloxane polymer KP-341 (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.).

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

The surfactant may be used alone or in combination of two or more.
The content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 1.0% by mass, based on the total solid content of the composition.

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

In addition, the higher fatty acid derivative may be a compound described in paragraph 0155 of WO 2015/199219, the contents of 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 mass% based on the total solids content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When two or more types of higher fatty acid derivatives are used, the total content is preferably 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 by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. Adding a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance. In addition, the above-mentioned photopolymerization initiator may also have the function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.

Specific examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A, the contents of which are incorporated herein by reference.

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

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

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

[Ultraviolet absorber]
The composition of the present invention may contain an ultraviolet absorber, such as a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based ultraviolet absorber.
Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-t-butylphenyl salicylate. Examples of benzophenone-based ultraviolet 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 ultraviolet 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 ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Further, examples of the triazine-based ultraviolet absorber 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; Examples include bis(hydroxyphenyl)triazine compounds such as 2,4-bis(2-hydroxy-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 various ultraviolet absorbents may be used singly or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber. When the composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably from 0.001% by mass to 1% by mass, and more preferably from 0.01% by mass to 0.1% by mass, relative to the total solid content mass of the composition of the present invention.

[Organotitanium Compounds]
The resin composition of the present embodiment may contain an organotitanium compound. When the resin composition contains an organotitanium compound, a resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organotitanium compound are shown below as I) to VII):
I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability to the resin composition and a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate).
II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc.
III) 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-pyrrol-1-yl)phenyl)titanium, and the like.
IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.
V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.
VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate.
VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

Among these, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds is preferred as the organic titanium compound, as it provides better chemical resistance. Titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.

When an organotitanium compound is added, the amount added 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 added is 0.05 parts by mass or more, the resulting cured pattern more effectively exhibits good heat resistance and chemical resistance, while when the amount added is 10 parts by mass or less, the composition has better storage stability.

[Antioxidants]
The composition of the present invention may contain an antioxidant. The inclusion of an antioxidant as an additive can improve the elongation properties of the cured film and its adhesion to metal materials. Examples of antioxidants include phenolic compounds, phosphite ester compounds, and thioether compounds. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at the site adjacent to the phenolic hydroxy group (ortho position) are preferred. The aforementioned substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Furthermore, compounds having a phenolic group and a phosphite ester group in the same molecule are also preferred. Furthermore, phosphorus-based antioxidants can also be suitably used as the antioxidant. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Commercially available antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (all manufactured by ADEKA Corporation). Furthermore, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as the antioxidant, the contents of which are incorporated herein by reference. Furthermore, the composition of the present invention may contain a latent antioxidant, if necessary. Examples of latent antioxidants include compounds in which the moiety functioning as an antioxidant is protected with a protecting group, and which function as an antioxidant when heated at 100 to 250°C or at 80 to 200°C in the presence of an acid/base catalyst, resulting in the elimination of the protecting group. Examples of latent antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219 A, the contents of which are incorporated herein by reference. Commercially available latent antioxidants include ADEKA ARCLES 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), ^R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ^R6 represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ^R7 represents a monovalent to tetravalent 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, and k represents an integer of 1 to 4.

The compound represented by formula (3) inhibits oxidative degradation of the aliphatic groups and phenolic hydroxyl groups contained in resins. It also has a rust-preventing effect on metal materials, thereby inhibiting metal oxidation.

Since it can act simultaneously on resins and metal materials, k is more preferably an integer of 2 to 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 further have a substituent. Among these, from the viewpoints of solubility in a developer and metal adhesion, it is preferable to have an alkyl ether group or -NH-, and from the viewpoints of interaction with resins and metal adhesion due to metal complex formation, -NH- is more preferable.

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

The amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By adding an amount of 0.1 part by mass or more, it is easier to obtain improved elongation properties and adhesion to metal materials, even in high-temperature, high-humidity environments. By adding an amount of 10 parts by mass or less, the sensitivity of the resin composition is improved, for example, through interaction with the photosensitizer. 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 the total amount be within the above range.

[Anti-aggregating agent]
The resin composition of the present embodiment may contain an anti-aggregation agent, if necessary. Examples of the anti-aggregation agent include sodium polyacrylate.

In the present invention, the anti-aggregating agent may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an anti-aggregating agent. When the composition of the present invention contains an anti-aggregating agent, the content of the anti-aggregating agent 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, relative to the total mass of the solid content of the composition of the present invention.

[Phenol compounds]
The resin composition of this embodiment may contain a phenolic compound as needed. Examples of the phenolic compound 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, Methylenetrith-FR-CR, and BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

In the present invention, the phenolic compounds may be used singly or in combination of two or more.
The composition of the present invention may or may not contain a phenolic compound. When the composition of the present invention contains a phenolic compound, the content of the phenolic compound is preferably from 0.01% by mass to 30% by mass, and more preferably from 0.02% by mass to 20% by mass, relative to the total solid mass of the composition of the present invention.

[Other polymer compounds]
Examples of other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolak resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. The other polymer compounds may be modified by introducing a crosslinking group such as a methylol group, an alkoxymethyl group, or an epoxy group.

In the present invention, the other polymer compounds may be used singly or in combination of two or more.
The composition of the present invention may or may not contain other polymer compounds. When the composition of the present invention contains other polymer compounds, 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, relative to the total solid content by mass of the composition of the present invention.

<Characteristics of Resin Composition>
The viscosity of the resin composition of the present invention can be adjusted by the solids concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm ² /s to 12,000 mm ² /s, more preferably 2,000 mm ² /s to 10,000 mm ² /s, and even more preferably 2,500 mm ² /s to 8,000 mm ² /s. Within the above range, it is easy to obtain a highly uniform coating film. If it is 1,000 mm ² /s or more, it is easy to apply the film to a thickness required for, for example, an insulating film for rewiring, and if it is 12,000 mm ² /s or less, a coating film with excellent coating surface condition can be obtained.

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

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 this does not include metals contained as complexes of organic compounds with metals. When multiple metals are contained, the total amount of these metals is preferably within the above range.

In addition, methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

Considering the use of the resin composition of the present invention as a semiconductor material, the content of halogen atoms is preferably less than 500 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. Among them, those present in the form of halogen ions are 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 of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range.
A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

Any conventional container known in the art can be used as a container for storing the resin composition of the present invention. Furthermore, in order to prevent impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made up of six layers of six types of resin, or a bottle with a seven-layer structure made up of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

<Cured product of resin composition>
By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
The resin composition is preferably cured by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, even more preferably in the range of 140°C to 380°C, and particularly preferably in the range of 170°C to 350°C.

The form of the cured product of the present invention is not particularly limited, and can be selected according to the application, such as a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. Furthermore, by patterning the resin composition, the shape of the cured product can be selected according to the application, such as forming a protective film on a wall surface, forming via holes for electrical conduction, adjusting impedance, capacitance, or internal stress, or imparting a heat dissipation function. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less.
The shrinkage percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage percentage refers to the percentage of volume change before and after curing of the resin composition, and can be calculated using the following formula.
Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

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

The cured product preferably has a phthalimide structure.
The phthalimide structure in the cured product is preferably a phthalimide structure represented by the following formula (PH-1).
In formula (PH-1), ^R1 represents a hydrogen atom or a monovalent organic group, ^R2 represents an aromatic heterocycle, ^L1 represents a divalent linking group, and each R independently represents a hydrogen atom or a bonding site to another structure.

In formula (PH-1), the preferred embodiments of R ¹ , R ² and L ¹ are the same as the preferred embodiments of R ¹ , R ² and L ¹ in formula (1-1).

In formula (PH-1), it is preferable that at least one of the Rs represents a bonding site with another structure.

The phthalimide structure represented by formula (PH-1) is preferably contained in the resin in the cured product.
For example, when the resin composition of the present invention contains a polyimide precursor or a polyimide, it is preferable that a phthalic acid structure or a phthalate ester structure present at the terminal of the polyimide precursor or the polyimide reacts with a base generated from the specific compound to form a phthalimide structure.

Specific examples of phthalimide structures contained in the cured product are shown below, but the present invention is not limited to these. In the structures below, * represents the bonding site with other structures, and n represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1. Furthermore, in this specification, a bond crossing a side of a ring structure indicates that any of the hydrogen atoms in the ring structure may be substituted. Furthermore, for example, in the composition, these bases may undergo further structural changes, such as elimination of a substituent bonded to a nitrogen atom in an azole structure (including an azole structure contained in a fused ring such as a purine ring structure).

The molar amount of the phthalimide structure (particularly the molar amount of the phthalimide structure represented by formula (PH-1)) per 1 g of the cured product is preferably 0.0001 to 5 mmol/g, more preferably 0.0002 to 2 mmol/g, and even more preferably 0.001 to 1 mmol/g.

<Preparation of Resin Composition>
The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method.
The mixing can be performed by using a stirring blade, a ball mill, or by rotating the tank itself.
The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

Furthermore, filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the resin composition of the present invention. The filter pore size may 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. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferable. The filter may be pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. An example of a connection configuration is a series connection of an HDPE filter with a pore size of 1 μm in the first stage and an HDPE filter with a pore size of 0.2 μm in the second stage. Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtration is performed under pressure, the pressure to be 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. Filter filtration and impurity removal using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples of the adsorbent 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 in the bottle may be subjected to a degassing step by placing it under reduced pressure.

(Method for producing cured product)
The method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto 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 of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern.
It is particularly preferable that the method for producing a cured product of the present invention includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained in the development step and a post-development exposure step of exposing the pattern obtained in the development step.
The production method of the present invention also preferably includes the film forming step and the step of heating the film.
Each step will be described in detail below.

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

[Base material]
The type of substrate can be appropriately determined depending on the application, but includes semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, 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, plasma display panel (PDP) electrode plates, etc., and are not particularly limited. In the present invention, semiconductor production substrates are particularly preferred, and silicon substrates, Cu substrates and mold substrates are more preferred.
Furthermore, these substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface.
The shape of the substrate is not particularly limited, and may be circular or rectangular.
The size of the substrate is, for example, 100 to 450 mm, preferably 200 to 450 mm, in diameter if circular, and 100 to 1000 mm, preferably 200 to 700 mm, in length of the short side if rectangular.
The substrate may be, for example, a plate-shaped substrate, preferably a panel-shaped substrate (substrate).

Furthermore, when a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer made of a cured product) or the surface of a metal layer, the resin layer or metal layer serves as the substrate.

The preferred method for applying the resin composition of the present invention to a substrate is coating.

Specific examples of the application method 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 application conditions depending on the method, a film of the desired thickness can be obtained. In addition, the application method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc. are preferred, and for rectangular substrates, slit coating, spray coating, inkjet coating, etc. 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 coating film may be formed by applying the coating to a temporary support in advance using the above-mentioned application method, and then transferred onto the substrate.
Regarding the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used in the present invention.
In addition, a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinsing (EBR) or back rinsing.
Furthermore, a pre-wetting step may be employed in which the substrate is coated with various solvents before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

<Drying process>
After the film-forming step (layer-forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent.
That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
The drying step is preferably carried out after the film-forming step and before the exposure step.
The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

<Exposure process>
The film may be subjected to an exposure step to selectively expose the film to light.
That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film formation step to light.
Selective exposure means that only a portion of the film is exposed, and selective exposure results in exposed and unexposed areas of the film.
The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but is preferably 50 to 10,000 mJ/cm ² , more preferably 200 to 8,000 mJ/cm ² , converted into exposure energy at a wavelength of 365 nm.

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

In terms of the exposure wavelength, in relation to the light source, (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), _F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc. For the resin composition of the present invention, exposure by a high-pressure mercury lamp is particularly preferred, and among these, exposure by i-line is preferred. This allows for particularly high exposure sensitivity to be achieved.
The exposure method is not particularly limited as long as it is a method that exposes at least a portion of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

<Post-exposure baking step>
The film may be subjected to a step of heating after exposure (post-exposure baking step).
That is, the method for producing a cured product of the present invention may include a post-exposure baking step in which the film exposed in the exposure step is heated.
The post-exposure baking step can be carried out after the exposure step and before the development step.
The heating temperature in the post-exposure baking step is preferably 50°C to 140°C, and more preferably 60°C to 120°C.
The heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, more preferably from 1 minute to 10 minutes.
The temperature rise rate in the post-exposure heating step from the starting temperature to the maximum heating temperature is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min.
The temperature rise rate may be changed during heating as needed.
The heating means in the post-exposure baking step is not particularly limited, and known means such as a hot plate, an oven, and an infrared heater can be used.
It is also preferable that the heating be carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

<Developing process>
After exposure, the film may be subjected to a development step in which it is developed with a developer to form a pattern.
That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed with a developer to form a pattern.
Development removes either the exposed or unexposed portions of the film, forming a pattern.
Here, development in which the non-exposed portions of the film are removed by the development process is called negative development, and development in which the exposed portions of the film are removed by the development process is called positive development.

[Developer]
The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

When the developer is an alkaline aqueous solution, examples of basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred examples include 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, with TMAH being more preferred. When TMAH is used, the content of the basic compound 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, of the total mass of the developer.

When the developer contains an organic solvent, the organic solvent may be an ester, for example, 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, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxypropionate, methyl 2-alkyloxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvic acid Methyl, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like; and ethers such as 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 ether ... Suitable examples of suitable solvents 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 aromatic hydrocarbons such as toluene, xylene, and anisole, and 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 isobutyl carbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the developer contains an organic solvent, the organic solvent can be used alone or in combination. 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 weight of the developer is preferably 50% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more, and particularly preferably 90% by weight or more. The above content may also be 100% by weight.

The developer may further contain other components.
Examples of other components include known surfactants and known defoaming agents.

[Method of Supplying Developer]
The method of supplying the developer is not particularly limited as long as it can form a desired pattern, and includes a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to a film formed on a substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred.
Alternatively, a process may be employed in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate, and this process may be repeated multiple times.
As a method for supplying the developer in the development step, a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated on the substrate by ultrasonic waves or the like, or a step in which these are combined can be used.

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

In the development process, after treatment with the developer, the pattern may be further washed (rinsed) with a rinse solution. Alternatively, a rinse solution may be supplied before the developer in contact with the pattern has completely dried.

[Rinse solution]
When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

When the rinse solution contains an organic solvent, examples of the organic solvent include esters 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, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxypropionic acid, propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyrubicin, Examples of suitable ethers include methyl phosphate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like, as well as ethers such as 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 monomethyl ether, Suitable examples of suitable solvents 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 aromatic hydrocarbons such as toluene, xylene, and anisole, and 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 isobutyl carbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, with cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME being more preferred, and cyclohexanone and PGMEA being even more preferred.

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

The rinse solution may further contain other ingredients.
Examples of other components include known surfactants and known defoaming agents.

[Method of supplying rinse liquid]
The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like.
From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, the rinse liquid can be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, a spray nozzle, etc.
That is, the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle.
As a method for supplying the rinse liquid in the rinsing step, a step in which the rinse liquid is continuously supplied to the substrate, a step in which the rinse liquid is kept substantially stationary on the substrate, a step in which the rinse liquid is vibrated on the substrate by ultrasonic waves or the like, or a step in which any of these is combined can be used.

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, more preferably 18 to 30°C.

<Heating process>
The pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated.
That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step.
The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without performing a development step, or a film obtained in the film-forming step.
In the heating step, the resin such as the polyimide precursor is cyclized to form a resin such as a polyimide.
Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in a crosslinking agent other than the specific resin also proceeds.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, still more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of a base generated from the base generator due to heating.

The heating step is preferably carried out at a temperature increase rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the temperature increase rate to 1°C/min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C/min or less, it is possible to alleviate residual stress in the cured product.
Additionally, in the case of a rapid heating oven, the heating rate from the initial temperature to the maximum heating temperature is preferably 1 to 8°C/sec, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature begins. 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 raise the temperature 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 adhesion between layers, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher.
The upper limit of the heating temperature is preferably 350°C or less, more preferably 250°C or less, and even more preferably 240°C or less.

Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C/min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C/min, and held at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film properties. The pretreatment step may be performed for a short period of time, preferably from 10 seconds to 2 hours, more preferably from 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, a first pretreatment step may be performed in the range of 100 to 150°C, followed by a second pretreatment step in the range of 150 to 200°C.
Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C./min.

The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

<Post-development exposure step>
The pattern obtained by the development step (or the pattern after rinsing if a rinsing step is performed) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light, instead of or in addition to the heating step.
That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step. The method for producing a cured product of the present invention may include both a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
In the post-development exposure step, for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure of a photobase generator to light, or a reaction in which elimination of an acid-decomposable group progresses due to exposure of a photoacid generator to light, can be promoted.
In the post-development exposure step, it is sufficient that at least a part of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed.
The exposure dose in the post-development exposure step is preferably 50 to 20,000 mJ/cm ² , more preferably 100 to 15,000 mJ/cm ² , in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity.
The post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

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

There are no particular limitations on the metal layer, 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, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. Examples of suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations of these. More specific examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using copper sulfate or copper cyanide plating solutions.

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

<Application>
Examples of fields to which the method for producing a cured product of the present invention or the cured product of the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include etching patterns for sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and insulating films for packaging applications such as those described above. For these applications, see, for example, Science & Technology Co., Ltd.'s "High Performance Polyimide and Application Technology" (April 2008), edited by Masaaki Kakimoto, CMC Technical Library's "Fundamentals and Development of Polyimide Materials" (November 2011), and the Japan Polyimide and Aromatic Polymer Research Association's "Latest Polyimide Fundamentals and Applications" (NTS, August 2010).

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

(Laminate and method for manufacturing laminate)
The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention.
The laminate of the present invention is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers.
Of the two or more layers made of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

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

The laminate of the present invention preferably includes two or more layers made of a cured product, and a metal layer between any two of the layers made of the cured product. The metal layer is preferably formed by the metal layer-forming step.
That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on the layer made of the cured product, between the steps for producing a cured product that are performed multiple times. Preferred aspects of the metal layer-forming step are as described above.
As the laminate, for example, a laminate including at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order, can be mentioned as a preferred example.
It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

<Lamination process>
The method for producing the laminate of the present invention preferably includes a lamination step.
The lamination process is a series of processes including (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) at least one of a heating process and a post-development exposure process, which are carried out again on the surface of the pattern (resin layer) or metal layer in this order. However, it is also possible to repeat at least one of the film formation process (a) and the heating process and the post-development exposure process (d). Furthermore, after at least one of the heating process and the post-development exposure process (d), a metal layer formation process (e) may be included. It goes without saying that the lamination process may further include the above-mentioned drying process, etc. as appropriate.

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

The lamination step is preferably carried out 2 to 20 times, more preferably 2 to 9 times.
For example, a structure of 2 to 20 resin layers, such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred.
The above layers may be the same or different in composition, shape, film thickness, etc.

In a particularly preferred embodiment of the present invention, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer. Specific examples include an embodiment in which the following steps are repeated in this order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step; or an embodiment in which the following steps are repeated in this order: (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step. By alternately performing the lamination step of laminating layers of the resin composition of the present invention (resin layers) and the metal layer formation step, it is possible to alternately laminate layers of the resin composition of the present invention (resin layers) and metal layers.

(Surface activation treatment step)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
The surface activation treatment step is usually performed after the metal layer formation step, but the resin composition layer may be subjected to the surface activation treatment step after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) and then the metal layer formation step may be performed.
The surface activation treatment may be performed on at least a portion of the metal layer, or 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. The surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, it is possible to improve the adhesion with the resin composition layer (film) provided on the surface.
In addition, it is preferable to perform the surface activation treatment on a part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with a metal layer or a resin layer provided on the surface that has been surface-activated. In particular, when performing negative development, etc., if the resin composition layer is cured, it is less susceptible to damage by the surface treatment and adhesion is likely to be improved.
Specific examples of surface activation treatments include plasma treatment with various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching with _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , or _NF3 / _O2 , surface treatment using ultraviolet (UV) ozone, immersion in an aqueous hydrochloric acid solution to remove the oxide film followed by immersion in an organic surface treatment agent containing a compound having at least one amino group and one thiol group, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the source gas is particularly preferred. For 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 .

(Semiconductor device and its manufacturing method)
The present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention.
The present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product of the present invention or the method for producing the laminate of the present invention.
As specific examples of semiconductor devices using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer, the descriptions in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357 can be referred to, and the contents of these can be incorporated into this specification.

(compound)
The compound of the present invention is a compound represented by the following formula (1-1).
In formula (1-1), each R ¹ independently represents a hydrogen atom or a monovalent organic group, each R ² independently represents an aromatic heterocycle, each R ³ independently represents a hydrogen atom or a monovalent organic group, each L ¹ independently represents a divalent linking group, n represents an integer of 1 or more, and L ² represents an n-valent linking group.

Preferred embodiments of the compound of the present invention are the same as the preferred embodiments of the specific compound contained in the resin composition of the present invention described above.

The present invention will be explained in more detail below with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are by weight.

Synthesis Example 1: Synthesis of polybenzoxazole precursor PBO-1 from 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4-oxydibenzoyl chloride
28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 200 g of N-methylpyrrolidone with stirring. Subsequently, 12.1 g (153 mmol) of pyridine was added, and a solution of 20.7 g (70.1 mmol) of 4,4'-oxydibenzoyl chloride in 75 g of N-methylpyrrolidone was added dropwise over 1 hour while maintaining the temperature at -10 to 0°C. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added and stirred for an additional 60 minutes. The polybenzoxazole precursor resin was then precipitated in 6 L of water, and the water-polybenzoxazole precursor resin mixture was stirred at 500 rpm for 15 minutes. The polybenzoxazole precursor resin was filtered off, stirred again in 6 L of water for 30 minutes, and filtered again. The resulting polybenzoxazole precursor resin was then dried under reduced pressure at 45°C for 3 days to obtain polybenzoxazole precursor PBO-1, which had a weight average molecular weight (Mw) of 21,500.
The structure of the polybenzoxazole precursor PBO-1 is presumed to be a structure represented by the following formula (PBO-1).

<Synthesis Example 2: Synthesis of polyimide precursor PI-1 from pyromellitic dianhydride, 4,4-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate>
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 10 hours. 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was then added and stirred for 2 hours to produce the diester of pyromellitic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and 16.12 g (135.5 mmol) of _SOCl2 was added over 10 minutes while maintaining the temperature at -10±4°C. The viscosity increased during the addition of _SOCl2 . After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 20 minutes at -5 to 0°C. The reaction mixture was then reacted at 0°C for 1 hour, after which 70 g of ethanol was added and stirred at room temperature overnight. The polyimide precursor was then precipitated in 5 L of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was collected by filtration, stirred again in 4 L of water for 30 minutes, and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45°C for 3 days to obtain polyimide precursor PI-1. The weight-average molecular weight of this polyimide precursor PI-1 was 19,000. The obtained polyimide precursor PI-1 is presumed to contain a repeating unit represented by the following formula (PI-1).

Synthesis Example 3: Synthesis of polyimide precursor (PI-2) from 3,3',4,4'-biphenyltetracarboxylic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate
20.0 g (64.5 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride (dried at 140 °C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglyme were mixed (water content: 88 ppm) and stirred at 60 °C for 10 hours. 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was then added and stirred for 2 hours to produce a diester of 3,3',4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with SOCl ₂ and converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 2, yielding polyimide precursor PI-2 in the same manner as in Synthesis Example 2. The weight average molecular weight of this polyimide precursor PI-2 was 20,000. The obtained polyimide precursor PI-2 is presumed to contain a repeating unit represented by the following formula (PI-2).

Synthesis Example 4: Synthesis of polyimide precursor (PI-3) from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether, and 2-hydroxyethyl methacrylate
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 100 g of diglyme were mixed and stirred at 60°C for 10 hours. 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was then added and stirred for 2 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with _SOCl2 and converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 2, yielding a polyimide precursor in the same manner as in Synthesis Example 2. The weight-average molecular weight of this polyimide precursor was 18,000. The obtained polyimide precursor PI-3 is presumed to contain a repeating unit represented by the following formula (PI-3).

Synthesis Example 5: Synthesis of polyimide precursor (PI-4) from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotolidine), and 2-hydroxyethyl methacrylate
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 100 g of diglyme were mixed (water content: 67 ppm) and stirred at 60°C for 10 hours. 0.84 g (6.45 mmol) of 2-hydroxyethyl methacrylate was then added and stirred for 2 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with _SOCl2 and converted to a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 2, yielding polyimide precursor PI-4 in the same manner as in Synthesis Example 2. The weight average molecular weight of this polyimide precursor PI-4 was 19,000. The obtained polyimide precursor PI-4 is presumed to contain a repeating unit represented by the following formula (PI-4).

<Synthesis Example: Synthesis of Polyimide PBI-1>
In a flask equipped with a condenser and a stirrer, 22.2 g (50 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.02 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 100.0 g of N-methylpyrrolidone (NMP) while removing water. Next, 11.9 g (45 mmol) of diamine (AA-1) described below was added, and the mixture was stirred at 25°C for 3 hours, and then stirred at 45°C for an additional 3 hours. Next, 15.8 g (200 mmol) of pyridine, 12.8 g (125 mmol) of acetic anhydride, and 50 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80°C for 3 hours. 50 g of N-methylpyrrolidone (NMP) was added and diluted.
The reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was filtered off, stirred again in 1 liter of methanol for 30 minutes, and filtered again. The resulting resin was dried under reduced pressure at 40°C for 1 day to obtain polyimide PBI-1. The molecular weight of PBI-1 was Mw = 19,000.
The structure of polyimide PBI-1 is presumed to be a structure represented by the following formula (PBI-1).

<Synthesis Example AA-1: Synthesis of diamine (AA-1)>
In a flask equipped with a condenser and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (Fujifilm Wako Pure Chemical Industries, Ltd.) and 17.4 g (0.22 mol) of dehydrated pyridine (Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 78 g of ethyl acetate and cooled to below 5°C. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate, and this solution was added dropwise to the flask using a dropping funnel over 1 hour. After completion of the dropwise addition, the mixture was stirred at below 10°C for 30 minutes, then heated to 25°C and stirred for 3 hours. Next, the reaction solution was diluted with 600 mL of ethyl acetate (CH ₃ COOEt), transferred to a separatory funnel, and washed sequentially with 300 mL of water, 300 mL of saturated sodium bicarbonate water, 300 mL of dilute hydrochloric acid, and 300 mL of saturated saline. After separation and washing, the mixture was dried over 30 g of magnesium sulfate, concentrated using an evaporator, and dried in vacuum to obtain 61.0 g of dinitro compound (A-1).
Into a flask equipped with a condenser and a stirrer, 27.9 g (500 mmol) of reduced iron (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 5.9 g (110 mmol) of ammonium chloride (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 3.0 g (50 mmol) of acetic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and 0.03 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were weighed, and 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred.
Next, 16.2 g of the dinitro compound (A-1) was added in small portions over 1 hour, and the mixture was stirred for 30 minutes. Next, the external temperature was raised to 85°C, stirred for 2 hours, cooled to 25°C or below, and then filtered using Celite (registered trademark). The filtrate was concentrated using a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separatory funnel and washed twice with 300 mL of saturated aqueous sodium bicarbonate, followed by washing with 300 mL of water and 300 mL of saturated brine in that order. After separation and washing, the mixture was dried over 30 g of magnesium sulfate, concentrated using an evaporator, and vacuum dried to obtain 11.0 g of diamine (AA-1). Its identity as diamine (AA-1) was confirmed by NMR spectrum.
¹ H-NMR data (d-chloroform, 400 MHz, internal standard: tetramethylsilane)
δ (ppm) = 1.95 (s, 3H), 3.68 (s, 4H), 4.45-4.47 (m, 2H), 4.50-4.53 (m, 2H), 5.58 (s, 1H), 6.14 (s, 1H), 6.19-6.20 (t, 1H), 6.77-6.78 (d, 2H)

Examples and Comparative Examples
In each example, the components shown in the table below were mixed to obtain a resin composition. In each comparative example, the components shown in the table below were mixed to obtain a comparative composition.
Specifically, the content (blending amount) of each component shown in the table other than the solvent is the amount (parts by mass) shown in the "parts by mass" column of each column in the table.
The solvent contents (amounts blended) were set so that the solid content concentration of the composition was the value (mass %) of "Solid content concentration" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of solvents was the ratio shown in the "Ratio" column in the table.
The resulting resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore width of 0.8 μm.
In the table, "-" indicates that the composition does not contain the corresponding component.

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

[Resin (cyclized resin or precursor thereof)]
Resins PI-1 to PI-4, PBO-1, and PBI-1: PI-1 to PI-4, PBO-1, and PBI-1 obtained in the above synthesis examples

[Thermal base generator]
B-1 to B-5: Compounds represented by the following formulas (B-1) to (B-5)

[Polymerization initiator]
C-1: IRGACURE OXE 01 (manufactured by BASF)
C-2: IRGACURE OXE 02 (manufactured by BASF)
C-3: IRGACURE 369 (manufactured by BASF)
C-4: Compound of the following structure

[Polymerizable compound]
・D-1: A-DPH (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
D-2: SR-209 (manufactured by Sartomer, compound having the following structure)
・D-3: A-TMMT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[Polymerization inhibitor]
E-1: 2-nitroso-1-naphthol (Tokyo Chemical Industry Co., Ltd.)
E-2: Parabenzoquinone (Tokyo Chemical Industry Co., Ltd.)
E-3: paramethoxyphenol (Tokyo Chemical Industry Co., Ltd.)
E-4: Compound of the following structure

[Specific Compound or Migration Inhibitor]
F-1 to F-21: Compounds having the following structures. F-1 to F-21 are compounds that fall under the specific compounds described above.
CF-1 to CF-2: Compounds having the following structures. CF-1 to CF-2 are compounds that do not fall under the category of the specific compounds described above.
In the above F-22, one of ^R1 is a hydrogen atom and the other is the following structure, and one of ^R2 is a hydrogen atom and the other is the following structure: In the following structure, * represents the bonding site with the oxygen atom in F-22.

<Synthesis example F-1>
In a three-neck flask, 30 g (0.19 mol, Tokyo Chemical Industry Co., Ltd.), 600 mL of 1-butanol, and 100 mL of water were mixed. After dissolving by stirring at room temperature, 130 mL of ethylenediamine (Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 1 hour. After the addition was completed, the reaction was continued at 80°C for 2 hours. After the reaction was completed, the mixture was cooled to room temperature and concentrated using a rotary evaporator. After concentration, a mixed solvent of 390 mL of diisopropyl ether and 90 mL of methanol was added to precipitate crystals. 28.3 g (yield 82%) of pale yellow powder F-1a (CF-1) was obtained. ^{The 1} H-NMR data of F-1a is shown below. ¹ H-NMR (BRUKER, AVANCE NEO 400): δ (ppm, D2O) 7.98 (1H, s), 7.91 (1H, s), 3.65-3.57 (2H, t), 3.10-3.00 (2H, t)
Next, 5.29 g (35.7 mmol, Tokyo Chemical Industry Co., Ltd.) of 3,4-dihydrocoumarin, 7.00 g (39.3 mmol) of F-1a, and 105 mL of water were mixed in a three-necked flask. The reaction was continued at 60°C for 6 hours. After completion of the reaction, the precipitated white powder was collected by filtration. The white powder was washed in the flask by stirring with 200 mL of water for 1 hour and with 200 mL of diisopropyl ether for 1 hour, repeatedly to obtain 8.27 g (71% yield) of white powder F-1. ^{The 1} H-NMR data of F-1 is shown below. ¹ H-NMR: δ (ppm, DMSO-d6): 12.7 (1H, s), 9.37 (1H, s), 8.19 (1H, s), 8.10 (1H, s), 7.99 (1H, t), 7.70-7.43 (1H), 7.10-6.90 (2H), 6.81-6.71 (1H, d), 6.70-6.59 (1H, t), 3.35-3.20 (4H), 2.78-2.65 (2H, t), 2.39-2.26 (2H, t)

<Synthesis examples F-2, F-3>
F-2 and F-3 were obtained in the same manner as in the synthesis of F-1, except that the ethylenediamine used in the synthesis of Intermediate F-1a in Synthesis Example F-1 was changed to 1,4-diaminobutane (Tokyo Chemical Industry Co., Ltd.) or 1,2-bis(2-aminoethoxy)ethane (Tokyo Chemical Industry Co., Ltd.).

<Synthesis example F-4>
F-4 was obtained in the same manner as in Synthesis Example F-1, except that 3,4-dihydrocoumarin used in F-1 was replaced with 2-coumaranone (Tokyo Chemical Industry Co., Ltd.).

<Synthesis example F-5>
4.89 g (15.0 mmol) of F-1 and 30 mL of methacrylic anhydride (Tokyo Chemical Industry Co., Ltd.) were mixed in a three-neck flask. The reaction was continued at 80°C for 10 hours. After completion of the reaction, the reaction solution was added dropwise to 200 mL of diisopropyl ether, and after stirring for 1 hour, 3.27 g (yield 55%) of white powder F-5 was obtained by suction filtration. ^{The 1} H-NMR data of F-5 is shown below. ¹ H-NMR: δ (ppm, DMSO-d6): 9.34 (1H, s), 8.18 (1H, s), 8.10 (1H, s), 7.99 (1H, t), 7.70-7.43 (1H), 7.10-6.90 (2H), 6.81-6.71 (1H, d), 6.70-6.59 (1H, t), 6.06 (1H), 6.00 (1H), 3.35-3.20 (4H), 2.78-2.65 (2H, t), 2.39-2.26 (5H)

<Synthesis examples F-6, F-7, F-8>
F-6, F-7 and F-8 were obtained in the same manner as in Synthesis Example F-1, except that 6-chloropurine used in the synthesis of Intermediate F-1a was changed to 2-chloropyridine, 5-chloro-2H-tetrazole, or 3-chloro-1,2,4-triazole.

<Synthesis examples F-9, F-11, F-12>
F-9, F-11, and F-12 were obtained in the same manner as in Synthesis Example F-1, except that 3,4-dihydrocoumarin used in F-1 was changed to δ-valerolactone (Tokyo Chemical Industry Co., Ltd.), 3-isochromanone (Tokyo Chemical Industry Co., Ltd.), or phthalide (Tokyo Chemical Industry Co., Ltd.), respectively.

<Synthesis example F-10>
In a three-necked flask, 6.34 g (35.2 mmol) of 3-(2-methoxyphenyl)propionic acid, 7.0 g (39.3 mmol) of F-1a, and 100 mL of methanol were mixed. While stirring at room temperature, 10.9 g (38.5 mmol) of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride was added to the flask. The reaction was continued at room temperature for 6 hours. After completion of the reaction, 100 mL of aqueous hydrochloric acid (1.0 N) and 100 mL of ethyl acetate were added and the mixture was separated. The organic layer was concentrated under reduced pressure and then washed with 200 mL of diisopropyl ether in the flask with stirring. 5.3 g (yield 48.5%) of pale yellow powder F-10 was obtained. ^{The 1} H-NMR data of F-10 is shown below. H-NMR: δ (ppm, DMSO-d6): 12.7 (1H, s), 8.19 (1H, s), 8.10 (1H, s), 7.99 (1H, t), 7.70-7.43 (1H), 7.10-6.90 (2H), 6.81-6.71 (1H, d), 6.70-6.59 (1H, t), 3.90-3.72 (3H, s), 3.35-3.20 (4H), 2.78-2.65 (2H, t), 2.39-2.26 (2H, t)

<Synthesis example F-13>
F-13 was obtained in the same manner as in Synthesis Example F-5, except that the methacrylic anhydride used in F-5 was changed to isobutyric anhydride (Tokyo Chemical Industry Co., Ltd.).

<Synthesis example F-14>
F-14 was obtained in the same manner as in Synthesis Example F-1, except that 3,4-dihydrocoumarin and ethylenediamine used in F-1 were changed to 3-isochromanone and 1,4-diaminobutane, respectively.

<Synthesis example F-15>
F-15 was obtained in the same manner as in the synthesis of F-5, except that F-1 used in Synthesis Example F-5 was changed to F-11 and methacrylic anhydride was changed to acetic anhydride (Tokyo Chemical Industry Co., Ltd.).

<Synthesis example F-16>
F-16 was obtained in the same manner as in Synthesis Example F-1, except that the ethylenediamine used in the synthesis of intermediate F-1a in F-1 was changed to 2,2'-oxybis(ethylamine) (Tokyo Chemical Industry Co., Ltd.).

<Synthesis example F-17>
F-17 was obtained in the same manner as in Synthesis Example F-5, except that F-1 was replaced with F-4 and methacrylic anhydride was replaced with isobutyric anhydride.

<Synthesis example F-18>
In a three-neck flask, 3.0 g (13.1 mmol) of (2-hydroxyphenyl)methyl N-(2-chloroethyl)carbamate, 1.8 g (13.1 mmol) of adenine, 35 mL of dimethylformamide, and 15 mL of water were mixed. The reaction was continued at 80°C for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and added dropwise to 100 mL of an 8% by mass saturated aqueous sodium bicarbonate solution. The resulting white powder was collected by filtration and washed with stirring using 200 mL of diisopropyl ether. 2.1 g (yield 48.8%) of white powder F-18 was obtained. ^{The 1} H-NMR data for F-18 is shown below. ¹ H-NMR: δ (ppm, DMSO-d6): 12.7 (1H, s), 9.37 (1H, s), 8.19 (1H, s), 8.10 (1H, s), 7.50-7.23 (2H), 7.10-6 90 (2H), 6.81-6.71 (1H, d), 6.70-6.59 (1H, t), 4.75-4.50 (2H), 2.78-2.65 (2H, t), 2.39-2.26 (2H, t)

<Synthesis example F-19>
10.0 g (56.1 mmol) of F-1a and 150 mL of dichloromethane were mixed in a three-neck flask. While stirring at 0-5°C or below, 12.7 g of chloroacetyl chloride (112.2 mmol, Tokyo Chemical Industry Co., Ltd.) was added dropwise to the flask over 1 hour. After the addition was complete, the reaction was continued at room temperature for 4 hours. After the reaction was complete, the reaction solution was added to 200 mL of water, and the organic layer was recovered. After further separation with water, the organic layer was concentrated under reduced pressure using a rotary evaporator. After reducing the pressure, the resulting white powder was washed with 200 mL of diisopropyl ether and stirred. 11.5 g of white powder (yield 80.4%) was obtained.
Next, 5.0 g (19.6 mmol) of the white powder, 7.86 g (44.1 mmol) of 3,4-dihydroxystyrene, 2.98 g (21.6 mmol) of potassium carbonate, and 150 mL of acetone were mixed in a three-neck flask. The reaction was continued at 40°C for 6 hours. After completion of the reaction, 200 mL of aqueous hydrochloric acid (1.0 N) and 200 mL of ethyl acetate were added and the mixture was separated. The organic layer was concentrated under reduced pressure using a rotary evaporator. After reducing the pressure, the obtained white powder was washed with stirring using 200 mL of diisopropyl ether. 5.3 g (yield 76.3%) of white powder was obtained. ^{The 1} H-NMR data for F-19 is shown below. ¹ H-NMR: δ(ppm, DMSO-d6): 12.7 (1H, s), 9.57 (1H, s), 8.19 (1H, s), 8.10 (1H, s), 7.99 (1H, t), 7.25-6.95 (3H ), 6.60-6.41 (2H), 5.90-5.75 (1H), 5.35-5.15 (1H) 4.45-4.20 (2H), 2.78-2.65 (2H, t), 2.39-2.26 (2H, t)

<Synthesis example F-20>
F-20 was obtained in the same manner as in Synthesis Example F-1, except that 3,4-dihydrocoumarin used in F-1 was replaced with coumarin (Tokyo Chemical Industry Co., Ltd.).

<Synthesis example F-21>
10.0 g (67.5 mmol) of 3,4-dihydrocoumarin and 250 mL of ethanol were mixed in a three-neck flask. 15.0 g (202.5 mmol, Tokyo Chemical Industry Co., Ltd.) of N-methylethylenediamine was added dropwise to the flask over one hour while stirring at room temperature. The reaction was continued at room temperature for six hours. After completion of the reaction, 100 mL of aqueous hydrochloric acid (1.0 N) and 200 mL of ethyl acetate were added and the mixture was separated. The organic layer was concentrated under reduced pressure and then washed with 200 mL of diisopropyl ether in the flask with stirring. 10.4 g of a white powder was obtained (yield 74.1%).
Next, 5.0 g (24.0 mmol) of the obtained white powder, 3.37 g (21.8 mmol) of 6-chloropurine, 150 mL of 1-butanol, and 25 mL of water were mixed in a three-neck flask. The reaction was continued at 80°C for 12 hours. After the reaction was completed, the precipitated white powder was collected by filtration under reduced pressure. The collected powder was suspended and washed in a mixed solvent of 200 mL of ethyl acetate and 200 mL of hexane, and then suspended and washed in 300 mL of diisopropyl ether to obtain 5.5 g (74.1%) of F-21. ^{The 1} H-NMR data of F-21 is shown below. ¹ H-NMR: δ(ppm, DMSO-d6): 12.7 (1H, s), 9.37 (1H, s), 8.19 (1H, s), 8.10 (1H, s), 7.99 (1H, t), 7.10-6. 90 (2H), 6.81-6.71 (1H, d), 6.70-6.59 (1H, t), 3.35-3.20 (7H), 2.78-2.65 (2H, t), 2.39-2.26 (2H, t)

<Synthesis example F-22>
F-22 was obtained in the same manner as in Synthesis Example F-19, except that 3,4-dihydroxystyrene used in F-19 was changed to 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane (Tokyo Chemical Industry Co., Ltd.).

<Synthesis example F-23>
In a three-neck flask, 10.0 g (55.5 mmol) of 2-carboxyphenylacetic acid, 6.6 g (55.5 mmol) of thionyl chloride, 8.99 g (50.5 mmol) of F-1a, and 250 mL of toluene were mixed. While stirring at room temperature, 5.11 g (55.5 mmol) of triethylamine was added dropwise to the flask. The reaction was continued at 90°C for 3 hours. After completion of the reaction, the toluene was distilled off by concentration under reduced pressure. 200 mL of methanol was added to the flask, followed by 10.6 g (55.5 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and the reaction was continued at room temperature for 7 hours. After completion of the reaction, 100 mL of 1.0 N aqueous hydrochloric acid and 200 mL of ethyl acetate were added and the mixture was separated. The organic layer was concentrated under reduced pressure and then washed with 200 mL of diisopropyl ether in the flask with stirring. 9.2 g of a white powder (yield 51.4%) was obtained. ^{The 1} H-NMR data for F-23 is shown below. ¹ H-NMR: δ (ppm, DMSO-d6): 12.7 (1H, s), 8.19 (1H, s), 8.10 (1H, s), 7.99 (1H, t), 7.70-7.43 (1H), 7.10-6.90 (2H), 6.81-6.71 (1H, d), 6.70-6.59 (1H, t), 4.10-3.75 (5H), 2.78-2.65 (2H, t), 2.39-2.26 (2H, t)

<Synthesis example F-24>
F-24 was obtained in the same manner as in Synthesis Example F-1, except that the ethylenediamine used in the synthesis of intermediate F-1a in F-1 was changed to p-xylylenediamine (Tokyo Chemical Industry Co., Ltd.).

The pKa of the conjugate acid before and after decomposition for F-1 to F-24 (before decomposition: pKa of the conjugate acid of the specific compound itself, after decomposition: pKa of the conjugate acid of the base generated by decomposition) was calculated using software ACD pKa (ver. 8.0) from ACD/labs. The calculation results are shown in the table below.

[Silane coupling agent (metal adhesion improver)]
G-1 to G-4: Compounds having the following structures: In the following structural formulas, Et represents an ethyl group.

[Other additives]
I-1: Compound represented by the following formula (I-1) I-2: N-phenyldiethanolamine

〔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 each resin composition or comparative composition in each Example or Comparative Example was measured using an E-type viscometer. The resin composition was allowed to stand in a sealed container at 25°C in the dark for 14 days, and then the viscosity (day 14) was measured again using an E-type viscometer. The viscosity fluctuation rate (%) was calculated using the following formula. Evaluation was performed from the obtained viscosity fluctuation rate according to the following evaluation criteria, and the evaluation results are shown in the "Storage stability" column in the table. The lower the viscosity fluctuation rate, the higher the storage stability.
Viscosity fluctuation rate (%) = |100 × {1 - (viscosity (14 days) / viscosity (0 days))}|
The viscosity was measured at 25°C, and other measurements were in accordance with JIS Z 8803:2011.
-Evaluation criteria-
A: The viscosity fluctuation rate was 10% or less.
B: The viscosity fluctuation rate was more than 10% but not more than 15%.
C: Viscosity fluctuation rate exceeded 15%.

[Elongation at break]
In each example and comparative example, each resin composition or comparative composition was applied in the form of a layer to a silicon wafer by spin coating to form a resin composition layer or comparative composition layer. The silicon wafer to which the resulting resin composition layer or comparative composition layer was applied was dried on a hot plate at 100°C for 5 minutes to form a uniform resin composition layer or comparative composition layer with a thickness of 20 μm on the silicon wafer. The resin composition layer or comparative composition layer on the silicon wafer was exposed to light using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/ ^cm2 . The exposed resin composition layer or comparative composition layer was heated at a heating rate of 10°C/min under a nitrogen atmosphere until it reached the temperature listed in the "Cure Temperature (°C)" column in the table. This temperature was maintained for the time listed in the "Cure Time (min)" column in the table to obtain a cured resin layer. The cured resin layer was immersed in a 4.9 mass % hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer, thereby obtaining a resin film 1.
The breaking elongation of the resin film 1 was measured in accordance with JIS-K6251:2017 using a tensile tester (Tensilon) at a crosshead speed of 300 mm/min, a sample width of 10 mm, and a sample length of 50 mm in the longitudinal direction of the film under an environment of 25°C and 65% relative humidity (RH). The breaking elongation was calculated as _Eb (%) = ( _Lb - _L0 ) / _L0 x 100 ( _Eb : elongation at break, _L0 : length of the test piece before the test, _Lb : length of the test piece when the test piece was broken). The breaking elongation in the longitudinal direction was measured 10 times, and the arithmetic mean value of the total 10 breaking elongations ( _Eb ) was used as the index value. Evaluation was performed according to the following evaluation criteria. The larger the _Eb value, the better the breaking elongation. The evaluation results are shown in the "Breaking Elongation" column in the table.
-Evaluation criteria-
A: The index value exceeded 60%.
B: The index value was more than 40% and 60% or less.
C: The index value was 40% or less.

[Evaluation of Metal Adhesion]
The resin composition or comparative composition prepared in each Example and Comparative Example was applied to a copper substrate by spin coating to form a layer of the resin composition or comparative composition. The copper substrate on which the resulting resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes to form a resin composition layer or comparative composition layer having a uniform thickness on the copper substrate, as shown in the "Film Thickness (μm)" column in the table. The resin composition layer or comparative composition layer on the copper substrate was exposed to i-rays using a stepper (Nikon NSR 2005 i9C) at an exposure energy of 500 mJ/ ^cm2 using a photomask with a 100 μm square unmasked area. The layer was then developed for 60 seconds with the developer shown in the "Developer" column in the table, and rinsed with propylene glycol monomethyl ether acetate (PGMEA), to obtain a 100 μm square resin layer. Furthermore, the coating was heated in a nitrogen atmosphere at the temperature shown in the "Cure temperature (°C)" column of the table for the time shown in the "Cure time (min)" column of the table using a heating oven to form a resin layer (pattern).
The shear force of a 100 μm square resin layer on a copper substrate was measured using a bond tester (CondorSigma, manufactured by XYZTEC Corporation) under an environment of 25° C. and 65% relative humidity (RH). The greater the shear force, the better the metal adhesion (copper adhesion) of the cured film. In all examples and comparative examples, the shear force exceeded 30 gf.

[Evaluation of Adhesion Strength After HTS (High Temperature Storage Test)]
The resin layer and copper substrate were heated at the temperature shown in the "Cure temperature (°C)" column for the time shown in the "Cure time (min)" column of the table, and then left to stand in a thermostatic chamber at 175°C for 1000 hours. The shear force was measured and the metal adhesion after heating was evaluated in the same manner as in the evaluation of metal adhesion described above, except that the resin layer and copper substrate were then heated at the temperature shown in the "Cure temperature (°C)" column of the table for the time shown in the "Cure time (min)" column of the table, and then left to stand for 1000 hours in a thermostatic chamber at 175°C. Evaluation was performed based on the measured shear force according to the following evaluation criteria, and the evaluation results are shown in the "Post-HTS adhesion" column of the table. It can be said that the greater the shear force, the better the metal adhesion (copper adhesion) of the cured film. Furthermore, if the post-HTS adhesion result is excellent, it can be said that peeling between the cured film and the metal is less likely to occur even after a long period of time has passed.
-Evaluation criteria-
A: The shear force exceeded 30 gf.
B: The shear force was greater than 25 gf and equal to or less than 30 gf.
C: The shear force was 25 gf or less.
Also, 1 gf is 0.00980665 N.

[Evaluation of void amount after HTS]
A square resin layer of 100 μm square was formed on a copper substrate using the same method as in the evaluation of metal adhesion described above.
The resin layer and copper substrate were heated at the temperature shown in the "Cure temperature (°C)" column for the time shown in the "Cure time (min)" column in the table, and then left in a thermostatic chamber at 175°C for 1000 hours. After that, cross-sectional SEM (scanning electron microscope) measurement was performed to evaluate the void area ratio between the copper substrate and the resin layer. The void area ratio was calculated using the following formula.
Void area ratio (%)=(area of voids observed by SEM measurement)/(total area of resin layer)×100
The obtained void area ratio value was evaluated according to the following evaluation criteria. The evaluation results are shown in the column "Amount of voids after HTS" in the table. The smaller the void area ratio, the better the reliability of the cured film after HTS, and the less likely voids are to occur between the metal layer and the cured product even after a long period of time has passed.
-Evaluation criteria-
A: The void area ratio was 0.5% or less.
B: The void area ratio was more than 0.5% and 2% or less.
C: The void area ratio exceeded 2%.

(Example 101)
A film was prepared under the same conditions as in Example 1, except that an infrared lamp heating device (RTP-6, manufactured by Advance Riko Co., Ltd.) was used as the curing means.
The same results as in Example 1 were obtained in terms of storage stability, elongation at break, adhesion strength after HTS, and void amount after HTS.

(Example 102)
A curable resin composition was prepared in Example 8, except that the resin was changed to a resin comprising a repeating unit represented by the following formula (PI-5), and the thermal base generator B-1 was changed to the following photobase generator B-7. The obtained curable resin composition was used to evaluate its storage stability, post-HTS adhesion, and post-HTS void volume.
The storage stability was evaluated in the same manner as in Example 8.
The adhesion and void amount evaluation after HTS were performed in the same manner as in Example 8, except that the photomask was changed to a photomask having a square mask portion with a side length of 100 μm, development was performed using a 2.38 mass % aqueous solution of tetramethylammonium hydroxide for 30 seconds, and rinsing was performed with pure water to form a pattern.
When the same evaluations as in Example 8 were carried out, the same results were obtained for the storage stability, adhesion after HTS, and amount of voids in the positive type.

(Example 103)
In Example 1, the polymerization initiator C-1, the polymerization inhibitor E-2, and the silane coupling agent G-1 were removed, and the amount of resin PI-3 was changed from 80 parts by mass to 86.7 parts by mass. A resin composition was prepared in the same manner as in Example 1.
Using the above resin composition, the storage stability, adhesion after HTS, and void amount after HTS were evaluated in the same manner as in Example 1, and the same results as in Example 1 were obtained in all evaluation items.

From the above results, it is clear that the resin composition of the present invention can provide a cured product with excellent reliability.
The comparative composition in Comparative Example 1 does not contain the specific compound. In such an embodiment, it is clear that the reliability of the resulting cured product is poor.

<Example 201>
The resin composition used in Example 1 was applied in the form of a layer by spin coating to the surface of the thin copper layer of a resin substrate having a thin copper layer formed on its surface, and dried at 100°C for 5 minutes to form a photosensitive film with a thickness of 20 μm. This was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The exposure was carried out 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 in cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
Next, the temperature was increased at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 180 minutes to form an interlayer insulating film for a rewiring layer. This interlayer insulating film for a rewiring layer had excellent insulating properties.
Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for rewiring layers, it was confirmed that they operated without any problems.

Claims (14)

At least one resin selected from the group consisting of cyclized resins and precursors thereof;
and a compound represented by the following formula (1-1):
the cyclized resin is at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor,
A resin composition, wherein the content of the compound represented by the following formula (1-1) is 0.05 to 10 mass % relative to the total solid content of the resin composition.
In formula (1-1), each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; each R ² independently represents an imidazole structure, a triazole structure, a tetrazole structure, a purine structure, or a structure represented by the following formula (R2); provided that the imidazole structure, the triazole structure, the tetrazole structure, the purine structure, or the structure represented by formula (R2) in R ² does not form a fused ring structure with another ring; each R ³ independently represents a hydrogen atom; each L ¹ independently represents a structure represented by the following formula (L1-1); n is 1; and L ² independently represents a group represented by the following formula (L2-1) or a saturated aliphatic hydrocarbon group having a hydroxy group.
In formula (L1-1), L ^L1 represents an alkylene group having 2 to 4 carbon atoms, a group represented by a combination of an alkylene group having 2 to 4 carbon atoms and a phenylene group, or a group represented by a combination of an alkylene group having 2 to 4 carbon atoms and -O-, # represents the bonding site to the nitrogen atom to which R ³ in formula (1-1) is bonded, and * represents the bonding site to the nitrogen atom to which R ¹ in formula (1-1) is bonded.
In formula (L2-1), Ar represents an aromatic hydrocarbon group, ^L represents a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by a combination of an alkylene group having 1 to 10 carbon atoms and —O—, ^R represents a hydrogen atom, a hydroxy group, a hydroxyalkyl group, an alkoxy group, a carboxy group, or an alkoxycarbonyl group, and * represents the bonding site with the carbonyl group in formula (1-1). The resin composition according to claim 1, wherein R ² in formula (1-1) includes the imidazole structure, the triazole structure, the tetrazole structure, or the purine structure. The resin composition according to claim 1 or 2, wherein R ² in formula (1-1) contains the purine structure. The resin composition according to any one of claims 1 to 3, wherein the compound represented by formula (1-1) is a compound that generates a base when exposed to light or heat. The resin composition according to any one of claims 1 to 4, wherein the resin is at least one resin selected from polyimide and polyimide precursors. The resin composition according to any one of claims 1 to 5, which is used to form an interlayer insulating film for a redistribution layer. A cured product obtained by curing the resin composition described in any one of claims 1 to 6. A laminate comprising two or more layers made of the cured product according to claim 7, and including a metal layer between any of the layers made of the cured product. A method for producing a cured product, comprising a film-forming step of applying the resin composition described in any one of claims 1 to 6 onto a substrate to form a film. The method for producing a cured product according to claim 9, comprising an exposure step of selectively exposing the film to light and a development step of developing the film using a developer to form a pattern. The method for producing a cured product according to claim 10, further comprising a heating step of heating the pattern obtained by the development at 150 to 450°C. A method for producing a laminate, comprising the method for producing a cured product according to any one of claims 9 to 11. A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of claims 9 to 11, or the method for producing a laminate according to claim 12 . A semiconductor device comprising the cured product of claim 7 or the laminate of claim 8.