WO2024128111A1

WO2024128111A1 - Resin composition, cured product, laminate, cured product production method, laminate production method, semiconductor device production method, and semiconductor device

Info

Publication number: WO2024128111A1
Application number: PCT/JP2023/043782
Authority: WO
Inventors: 大輔浅川; 和則濁川; 友小澤; 厚志稲垣; 享平崎田
Original assignee: 富士フイルム株式会社
Priority date: 2022-12-13
Filing date: 2023-12-07
Publication date: 2024-06-20

Abstract

Provided is a resin composition comprising: at least one resin selected from the group consisting of cyclization resins and precursors thereof; and a compound A that satisfies condition 1 and condition 2. Condition 1: The compound has two or more aromatic heterocycles which include, as a ring member, one or more atoms selected from among an oxygen atom, a nitrogen atom, and a sulfur atom, in which a hydrogen atom may be substituted, and which may be condensed ring structures. Condition 2: The compound has an aromatic amino group. Also provided are a cured product, a laminate, a cured product production method, a laminate production method, a semiconductor device production method, and a semiconductor device.

Description

Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, and semiconductor device

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

2. Description of the Related Art Nowadays, resin materials produced from resin compositions containing resins are being used in various fields.
For example, cyclized resins such as polyimide are used in various applications because of their excellent heat resistance and insulating properties. The applications are not particularly limited, but for example, in the case of semiconductor devices for mounting, they can be used as insulating films, sealing materials, or protective films. They are also used as base films or coverlays for flexible substrates.

For example, in the applications mentioned above, the cyclized resin, such as a polyimide, is used in the form of a resin composition that includes the cyclized resin or 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 performed 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.
Since the resin composition can be applied by a known coating method, etc., it can be said to have excellent adaptability in manufacturing, for example, high degree of freedom in designing the shape, size, application position, etc. of the resin composition when applied. In addition to the high performance of cyclized resins such as polyimide, from the viewpoint of such excellent adaptability in manufacturing, industrial application development of the above-mentioned resin composition is expected to continue.
Furthermore, such resin materials are required to have excellent adhesion to substrates, and various methods for improving adhesion to substrates have been investigated.

For example, Patent Document 1 describes a retardation film that contains a cellulose derivative and a compound with a specific structure.

International Publication No. 2012/120897

There is a demand for resin compositions containing cyclized resins or their precursors to produce cured products that have excellent adhesion to substrates over a long period of time (and also after accelerated testing).

The present invention aims to provide a resin composition that can give a cured product that has excellent adhesion to a substrate over a long period of time, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product.

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, and
A resin composition comprising a compound A that satisfies the following conditions 1 and 2:
Condition 1: The compound A has two or more aromatic heterocycles each of which contains one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom as a ring member, and which may be substituted with a hydrogen atom or may have a condensed ring structure. Condition 2: The compound A has an aromatic amino group. <2> The resin composition according to <1>, wherein the compound A is a compound represented by the following formula (A-1):

In formula (A-1), the ring structures represented by Het each independently represent an aromatic heterocycle which may have a substituent and which may be condensed with another ring, and R ¹ represents a hydrogen atom or a monovalent organic group.
<3> The resin composition according to <1> or <2>, wherein the ring structures represented by Het in formula (A-1) are each independently any of structures represented by the following formulas (A-1-1) to (A-1-3).

In formula (A-1-1), Y ¹ to Y ⁴ each independently represent -CR ² = or -N=, R ² represents a hydrogen atom or an arbitrary organic group, and when two or more of Y ¹ to Y ⁴ represent -CR ² =, at least two of R ² may be linked to form a ring structure, and * represents a bonding site with the nitrogen atom to which R ¹ in formula (A-1) is bonded.
In formula (A-1-2), ^Y5 to ^Y7 each independently represent ^-CR2 = or -N=, ^R2 represents a hydrogen atom or an arbitrary organic group, and when two or more of ^Y5 to ^Y7 represent ^-CR2 =, at least two of ^R2 may be linked to form a ring structure, and * represents a bonding site with the nitrogen atom to which ^R1 in formula (A-1) is bonded.
In formula (A-1-3), X represents -O-, -S- or -NR ³ -; R ³ represents a hydrogen atom or any organic group; Y ⁸ and Y ⁹ each independently represent -CR ² = or -N=; R ² represents a hydrogen atom or any organic group; when Y ⁸ and Y ⁹ are -CR ² =, two R ² may be linked to form a ring structure; and * represents a bonding site with the nitrogen atom to which R ¹ in formula (A-1) is bonded.
<4> The resin composition according to any one of <1> to <3>, wherein compound A is a compound represented by formula (A-2):

In formula (A-2), R ²¹ is a hydrogen atom or a monovalent organic group, Y ²¹ to Y ²⁶ are each -CR ²⁴ = or -N=, R ²⁴ is a hydrogen atom, an alkyl group, a hydroxyl group, or a carbamoyl group, and R ²² and R ²³ are each independently a hydrogen atom, an alkyl group, or a carbamoyl group.
<5> The resin composition according to any one of <1> to <4>, wherein the cyclized resin or the cyclized resin precursor is a polyimide or a polyimide precursor.
<6> The resin composition according to any one of <1> to <5>, further comprising a photopolymerization initiator.
<7> The resin composition according to any one of <1> to <6>, further comprising a compound having an aromatic heterocycle, the compound being different from compound A.
<8> The resin composition according to any one of <1> to <7>, which is used for forming an interlayer insulating film for a redistribution layer.
<9> A cured product obtained by curing the resin composition according to any one of <1> to <8>.
<10> A laminate comprising two or more layers made of the cured product according to <9>, and a metal layer between any two adjacent layers made of the cured product.
<11> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of <1> to <8> onto a substrate to form a film.
<12> The method for producing a cured product according to <11>, 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.
<13> A method for producing a cured product according to <11> or <12>, comprising a heating step of heating the film at 50 to 450° C.
<14> A method for producing a laminate, comprising the method for producing a cured product according to any one of <11> to <13>.
<15> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <11> to <13>.
<16> A semiconductor device comprising the cured product according to <9>.

The main embodiments of the present invention will be described below, however, 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 limit and upper limit, respectively.
In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes, so long as the process can achieve its intended effect.
In the description of groups (atomic groups) in this specification, when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, an "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
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 represented by an excimer laser, 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 total solid content refers to the total mass of all components of the composition excluding the solvent, and in this specification, the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) unless otherwise specified, and are defined as polystyrene equivalent values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series as columns. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, when THF is not suitable as the eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can also be used. In addition, unless otherwise specified, detection in GPC measurement is performed using a UV (ultraviolet) ray (wavelength 254 nm detector).
In this specification, when the positional relationship of each layer constituting the 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 noted. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer. Unless otherwise specified, the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "upper", and the opposite direction is referred to as "lower". Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper" direction in this specification may be different from the vertical upward direction.
In this specification, unless otherwise specified, the 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 pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
As used herein, combinations of preferred aspects are more preferred aspects.

(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 A that satisfies the following conditions 1 and 2.
Condition 1: The compound has two or more aromatic heterocycles which contain one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom as a ring member, and in which a hydrogen atom may be substituted and which may have a condensed ring structure. Condition 2: The compound has an aromatic amino group.

The resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent.
The resin composition of the present invention can be used, for example, to form an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer.
The resin composition of the present invention 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 a development in which the non-exposed areas are removed by development during exposure and development, and positive development refers to a development in which the exposed areas are removed by development.
As the above-mentioned exposure method, the developer, and the development method, for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the production method of the cured product described later can be used.

According to the resin composition of the present invention, a cured product having excellent adhesion to a substrate over a long period of time can be obtained.
The mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.

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 A that satisfies conditions 1 and 2.
Compound A has at least two aromatic heterocycles and an aromatic amino group, and therefore contains a heteroatom in the aromatic heterocycle and a nitrogen atom in the aromatic amino group in the structure.
It is believed that the nitrogen atom and the heteroatom strongly interact with the polar group contained in the cyclized resin or the precursor of the cyclized resin.
In addition, such compound A has a high interactivity with metal substrates such as copper.
As described above, it is believed that compound A strongly interacts with both the metal substrate and the cyclized resin, and therefore the cured product obtained from the composition of the present invention has excellent adhesion to the metal substrate over a long period of time (and after accelerated testing), and furthermore, the occurrence of voids is suppressed over a long period of time (and after accelerated testing).
Furthermore, by such an interaction between compound A and the cyclized resin or a precursor thereof, when a pattern is formed by exposure and development, the generation of development residues is suppressed, and thus there is an effect that a fine pattern can be formed.
In particular, when compound A has a structure represented by formula (A-2) described below, it is believed that a complex can be formed with copper ions, which further suppresses the migration of copper ions into the cured product.

Patent Document 1 does not describe a composition containing at least one resin selected from the group consisting of cyclized resins and their precursors and compound A.

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 term "main chain" refers to the relatively longest bonding chain in a resin molecule, and the term "side chain" refers to any other bonding chain.
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 preferably contains, as the specific resin, at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor.
The resin composition preferably contains a polyimide or a polyimide precursor as the specific resin.
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, more preferably contains a radical polymerization initiator and a radical crosslinking agent. If necessary, it can further contain a sensitizer. For example, a negative photosensitive film is formed from such a resin composition.
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 preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive-type photosensitive film or negative-type 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 ^-NRz- , ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, and ^Rz represents a hydrogen atom or a monovalent organic group.

In formula (2), A ¹ and A ² each independently represent an oxygen atom or —NR ^z —, and preferably an oxygen atom.
^Rz represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.
R ¹¹¹ in formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group. A linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The 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 R ¹¹¹ in formula (2) include groups represented by -Ar- and -Ar-L-Ar-, and a group represented by -Ar-L-Ar- is preferred. Here, 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 of these are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of 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, R ¹¹¹ is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom. 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 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-, -C(=O)-, -S-, or -SO ₂ -, and further preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -.
In the formula, * represents a bonding site with other structures.

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, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl phenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 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, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4,4'-diaminoparaterphenyl , 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-di Ethyl-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, 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-dihydro 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-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-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4 and at least one diamine selected from 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 resulting organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Here, 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 -. The aliphatic hydrocarbon group here 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 viewpoints of i-line transmittance and ease of availability, R 111 is more preferably a divalent organic group represented by formula (61).
Equation (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 represents 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 for R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).

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 formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.

In formula (2), R ¹¹⁵ represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
In formula (5) or (6), each * independently represents a bonding site to another structure.

In formula (5), R ¹¹² is a single bond or a divalent linking group and is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, -NHCO-, and a combination thereof, more preferably a single bond, or 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 tetracarboxylic acid residues remaining after removal of anhydride groups from tetracarboxylic dianhydride. The polyimide precursor may contain only one type of tetracarboxylic dianhydride residue or two or more types of tetracarboxylic 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'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl methane tetracarboxylic dianhydride, 2 ,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2 ,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalene tetracarboxylic dianhydride, 2,2',3,3'-diphenyl tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,8,9,10-phenanthrene tetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride, and their alkyl and alkoxy derivatives having 1 to 6 carbon atoms.

Furthermore, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.

In the 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.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. In addition, it is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferable that both contain a polymerizable group. 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 crosslinking by the action of heat, radicals, etc., and is preferably a radical 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. As the radical polymerizable group of the polyimide precursor, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

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 with 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 group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CH ₂ CH(OH)CH ₂ -, and polyalkyleneoxy groups, of which alkylene groups such as ethylene group and propylene group, -CH ₂ CH(OH)CH ₂ -, cyclohexyl group, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy groups are even more preferred.
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 of the substituent, when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2.
The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.
From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.In the group in which multiple ethyleneoxy groups and multiple 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 embodiment of the number of repetitions of the ethyleneoxy group in these groups is 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. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity 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 order 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 the diamine.

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). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the 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 preferable 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 range is 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). The polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).

One embodiment of the polyimide precursor of the present invention is one in which the content of the repeating unit 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 more than 90 mol%. There is no particular upper limit to the total content, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) of the polyimide precursor 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 has a molecular weight dispersity of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, 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 dispersity of molecular weight is a value calculated by weight average molecular weight/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 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 one resin are each within the above 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, the alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C., and from the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferable, and a polyimide that dissolves at 1.0 g or more is more preferable. The upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less.
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.

-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, for example, 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 fluorinated alkyl group 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.
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 R ¹³¹ in the repeating unit represented by formula (4) described later, and more preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later as an organically modified (poly)siloxane structure described later.
The silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass % or more, and more preferably 20 mass % or less.

- 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 the side chain.
The ethylenically unsaturated bond is preferably radically polymerizable.
The ethylenically unsaturated bond is preferably contained in R ¹³² or R ¹³¹ in the repeating unit represented by formula (4) described below, and more preferably contained in R ¹³² or R ¹³¹ as a group having an ethylenically unsaturated bond.
Among these, the ethylenically unsaturated bond is preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described below, and more preferably contained in R ¹³¹ as a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

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 in the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group consisting of a combination of two or more of these.
The alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, and alkylene groups represented by a combination thereof.
The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.

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 with another structure; and ● represents a bonding site with the oxygen atom to which ^R21 in formula (IV) is bonded.
In formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L are the same as the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as R ²¹ in formula (IV).
In formula (R1), X is preferably an oxygen atom.
In formulae (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, etc.).
The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.).

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 the polymerizable group other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
The polymerizable group other than the group having an ethylenically unsaturated bond is preferably included in, 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 in 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 later, 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.
When the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development"), the acid value of the polyimide is preferably from 1 to 35 mgKOH/g, more preferably from 2 to 30 mgKOH/g, and even more preferably from 5 to 20 mgKOH/g.
The acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
The acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability.
pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa. In this specification, pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified. For pKa, the value listed in "Revised 5th Edition Chemistry Handbook: Basics" compiled by the Chemical Society of Japan may be referred to.
When the acid group is a polyacid, such as phosphoric acid, the pKa is the first dissociation constant.
As such an acid group, the polyimide preferably contains at least one type selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

-Phenol hydroxy group-
From the viewpoint of ensuring an appropriate development speed 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 or R ¹³¹ in the repeating unit represented by formula (4) described below.
The amount of the phenolic hydroxy group relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

The polyimide used in the present invention is not particularly limited as long as it is a polymeric compound having an imide structure, but it is preferable that the polyimide 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 the polyimide has a polymerizable group, the polymerizable group may be located 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 are the same as those in formula (4).
Formula (4-2)

At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and when 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 range is also the same.
R ¹³¹ may be a diamine residue remaining after removal of the amino group of the diamine. The diamine may be an aliphatic, cycloaliphatic or aromatic diamine. Specific examples include the example of R ¹¹¹ in the formula (2) of the polyimide precursor.

R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain in order to more effectively suppress 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.

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

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 range is also the same.
For example, the four bonds of the tetravalent organic group exemplified as R ¹¹⁵ bond to the four —C(═O)— portions in formula (4) to form a condensed ring.

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

It is also preferable that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, 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 (DA-1) to (DA-18), and more preferred examples of R ¹³² include the above (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 more preferably 20% by mass or less.

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

In order 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, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a 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, 1-carboxy -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, 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.

-Imidization rate (ring closure rate)-
From the viewpoints of the film strength, insulating properties, etc. of the resulting organic film, the imidization rate of the polyimide (also referred to as the "ring closure rate") is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less.
The imidization rate is measured, for example, by the following method.
The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm ⁻¹ , which is an absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350° C. for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1377 cm ⁻¹ . Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated 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) in which all of the repeating units have the same combination of R ¹³¹ and R ¹³² , or may contain repeating units represented by the above formula (4) containing two or more different combinations of R ¹³¹ and R ^132. 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, for example, by reacting tetracarboxylic dianhydride with diamine (partially substituted with a terminal blocking agent that is a monoamine) at low temperature, by reacting tetracarboxylic dianhydride (partially substituted with a terminal blocking agent that is an acid anhydride, monoacid chloride compound, or monoactive ester compound) with diamine at low temperature, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine) in the presence of a condensing agent, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine), or by using a method in which a polyimide precursor is obtained and then completely imidized using a known imidization reaction method, or by stopping the imidization reaction midway and introducing a partial imide structure, or by blending a completely imidized polymer with the polyimide precursor to partially introduce an imide structure. Other known methods for synthesizing polyimides can also be applied.

The weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties (e.g., breaking elongation), the weight average molecular weight is particularly preferably 15,000 or more.
The number average molecular weight (Mn) of the polyimide is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000.
The polyimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the polyimide molecular weight dispersity is not particularly limited, but is 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 ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimides as one resin are each within the above ranges.

[Polybenzoxazole precursor]
The polybenzoxazole precursor includes the compounds described in paragraphs 0073 to 0095 of WO 2022/145355. The above descriptions are incorporated herein by reference.

[Polybenzoxazole]
Examples of polybenzoxazoles include compounds described in paragraphs 0096 to 0103 of WO 2022/145355. The above descriptions are incorporated herein by reference.

[Polyamide-imide precursor]
Examples of polyamideimide precursors include compounds described in paragraphs 0104 to 0119 of WO 2022/145355. The above descriptions are incorporated herein by reference.

[Polyamide-imide]
Examples of polyamideimides include the compounds described in paragraphs 0120 to 0133 of WO 2022/145355. The above descriptions are incorporated herein by reference.

[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 diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine, etc. Among the above-mentioned production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine, is more preferable.
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, phosphorus oxychloride, and the like.
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 type or two or more types.
The organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone.
In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types.
The basic compound can be appropriately determined depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

-End-capping agent-
In the method for producing 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 in order to further improve storage stability. When capping the carboxylic acid anhydride and acid anhydride derivative remaining at the resin terminal, examples of the terminal capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and it is more preferable to use monoalcohols, phenols, or monoamines in terms of reactivity and film stability. Preferred examples of monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of such an acid include 2-carboxy-7-aminonaphthalene, 2-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 a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
In addition, when the amino group at the resin terminal is blocked, it is possible to block it with a compound having a functional group capable of reacting with the amino group. Preferred blocking agents for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides. Preferred compounds of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, and the like. Preferred examples of the carboxylic acid chloride 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 method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid, and then dried to obtain a polyimide precursor or the like. In order to improve the degree of purification, the polyimide precursor or the like may be repeatedly subjected to operations such as redissolving, reprecipitation, and drying. Furthermore, the method 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. The content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition.
The resin composition of the present invention may contain only one specific resin, or may contain two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.

It is also preferable that the resin composition of the present invention 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 preferably contains, 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, simply referred to as "another resin").
Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
For example, by further adding a (meth)acrylic resin, a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
For example, instead of or in addition to the polymerizable compound described later, 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 content of polymerizable groups per 1 g of resin is 1×10 ⁻³ mol/g or more) to the resin composition, the coatability of the resin composition and the solvent resistance of the pattern (cured product) can be improved.

When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition.
The content of other resins in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, still more preferably 60 mass% or less, and even more preferably 50 mass% or less, based on the total solid content of the resin composition.
As a preferred embodiment of the resin composition of the present invention, the content of the other resin may be low. In the above 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 within the above range.

<Compound A>
The resin composition of the present invention contains compound A.
Compound A is a compound that satisfies the following conditions 1 and 2.
Condition 1: The compound has two or more aromatic heterocycles (hereinafter, also referred to as "specific aromatic heterocycles") which contain one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom as a ring member and which may be substituted with a hydrogen atom and may have a condensed ring structure. Condition 2: The compound has an aromatic amino group.

[Condition 1]
The specific aromatic heterocycle is preferably an aromatic heterocycle containing at least one nitrogen atom as a ring member, and more preferably an aromatic heterocycle containing at least two nitrogen atoms as ring members.
In addition, it is also one of the preferred embodiments of the present invention that the aromatic heterocycle described in condition 1 does not contain an oxygen atom or a sulfur atom as a ring member, but contains only a nitrogen atom and a carbon atom as ring members.
When the specific aromatic heterocycle has a substituent, the substituent is preferably an alkyl group, a hydroxyl group, or a carbamoyl group.
The specific aromatic heterocycle preferably has any of the structures represented by formulae (A-1-1) to (A-1-3) described below.
In condition 1, when the aromatic heterocycle is a condensed ring structure, even if the condensed ring structure contains two or more aromatic heterocycles, all of the ring structures contained in the condensed ring structure are collectively counted as one specific aromatic heterocycle.
The number of specific aromatic heterocycles contained in compound A may be 2 or more, and is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 to 3.
In addition, an embodiment in which compound A has only two specific aromatic heterocycles is also one of the preferred embodiments of the present invention.
Furthermore, the total number of nitrogen atoms contained as ring members in all heteroaromatic heterocycles contained in compound A is preferably 2 to 10, more preferably 3 to 8, and even more preferably 2 to 6.

[Condition 2]
The aromatic amino group refers to an amino group that is bonded to a carbon atom constituting an aromatic ring by a single bond, but does not constitute an aromatic ring. The carbon atom constituting an aromatic ring is a carbon atom that is a ring member of the aromatic ring, and the amino group that is not a ring member of an aromatic ring is an amino group that is not a ring member of an aromatic ring.
The aromatic ring in the aromatic amino group may be an aromatic hydrocarbon ring or an aromatic heterocycle, but is preferably an aromatic heterocycle. The aromatic heterocycle is preferably an aromatic heterocycle containing one or more heteroatoms selected from oxygen, sulfur, and nitrogen atoms as ring members, and more preferably an aromatic heterocycle containing one or more nitrogen atoms as ring members.
The aromatic heterocycle is preferably an aromatic ring corresponding to the specific aromatic heterocycle described above.
The aromatic hydrocarbon ring is preferably an aromatic hydrocarbon ring group having 6 to 20 carbon atoms, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.
The aromatic amino group may be a primary amino group, a secondary amino group, or a tertiary amino group, but is preferably a secondary amino group or a tertiary amino group, and more preferably a tertiary amino group.
A primary amino group refers to an amino group in which the nitrogen atom is bonded to one organic group and two hydrogen atoms via single bonds, a secondary amino group refers to an amino group in which the nitrogen atom is bonded to two organic groups and one hydrogen atom via single bonds, and a tertiary amino group refers to an amino group in which the nitrogen atom is bonded to three organic groups via single bonds.

The nitrogen atom in the aromatic amino group is preferably bonded at a bond other than the bond to the aromatic ring to a hydrogen atom, a carbon atom in a hydrocarbon group, a carbon atom in an aliphatic heterocycle, or a protecting group for the amino group.
In the above-mentioned hydrocarbon group or aliphatic heterocycle, a hydrogen atom may be substituted with another structure.
Examples of the protecting group include known protecting groups for amino groups, such as t-butoxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, etc.

That is, the aromatic amino group is preferably a group represented by the following formula (AM-1).

In formula (AM-1), Ar represents an aromatic ring, and each * independently represents a bonding site to another structure.
The preferred embodiments of the aromatic ring in Ar are as described above.
The other structure indicated by * is preferably a hydrogen atom, a carbon atom in a hydrocarbon group, a carbon atom in an aliphatic heterocycle, or a protecting group for an amino group. Preferred embodiments of these structures are as described above.

The number of aromatic amino groups in compound A may be 1 or more, but is preferably 1 to 4, and more preferably 1 or 2. In addition, an embodiment in which the number of aromatic amino groups is 1 is also one of the preferred embodiments of the present invention.

[Formula (A-1)]
Compound A is preferably a compound represented by the following formula (A-1).

In formula (A-1), the ring structures represented by Het each independently represent an aromatic heterocycle which may have a substituent and which may be condensed with another ring, and R ¹ represents a hydrogen atom or a monovalent organic group.

In formula (A-1), at least one of the ring structures represented by Het is preferably the above-mentioned specific aromatic heterocyclic structure, and more preferably both are the above-mentioned specific heterocyclic structures.
The amino group bonded to R ¹ through a single bond in the formula (A-1) corresponds to the aromatic amino group in the above condition 2.

It is preferable that the ring structures represented by Het are each independently any of the structures represented by the following formulae (A-1-1) to (A-1-3), and it is more preferable that at least one of them is a structure represented by formula (A-1-1) and the other is any of the structures represented by formula (A-1-1) to (A-1-3). In addition, it is also one of the preferable aspects of the present invention that both of the ring structures represented by Het are structures represented by formula (A-1-1).

In formula (A-1-1), Y ¹ to Y ⁴ each independently represent -CR ² = or -N=, R ² represents a hydrogen atom or an arbitrary organic group, and when two or more of Y ¹ to Y ⁴ represent -CR ² =, at least two of R ² may be linked to form a ring structure, and * represents a bonding site with the nitrogen atom to which R ¹ in formula (A-1) is bonded.
In formula (A-1-2), ^Y5 to ^Y7 each independently represent ^-CR2 = or -N=, ^R2 represents a hydrogen atom or any organic group, and when two or more of ^Y5 to ^Y7 represent ^-CR2 =, at least two of ^R2 may be linked to form a ring structure, and * represents a bonding site with the nitrogen atom to which ^R1 in formula (A-1) is bonded.
In formula (A-1-3), X represents -O-, -S- or -NR ³ -; R ³ represents a hydrogen atom or any organic group; Y ⁸ and Y ⁹ each independently represent -CR ² = or -N=; R ² represents a hydrogen atom or any organic group; when Y ⁸ and Y ⁹ are -CR ² =, two R ² may be linked to form a ring structure; and * represents a bonding site with the nitrogen atom to which R ¹ in formula (A-1) is bonded.

In the present invention, the description -CR ² = means that of the four bonds of the carbon atom, one is bonded to another structure via a single bond, one is bonded to R ² via a single bond, and two are bonded to another structure via double bonds.
The description -N= indicates that of the three bonds of the nitrogen atom, one is bonded to another structure via a single bond and the other two are bonded to another structure via double bonds.
However, when the carbon atom in -CR ² = or the nitrogen atom in -N = is included as a ring member in an aromatic ring, the single bond and the double bond are shown separately for convenience, but both of these bonds contribute to the formation of a so-called conjugated double bond, and it may not be possible to distinguish between a single bond and a double bond.

In formula (A-1-1), it is preferable that at least one of Y ¹ to Y ⁴ is -N=, more preferably 1 to 3 are -N=, and further preferably 1 or 2 are -N=.
When one of Y ¹ to Y ⁴ is -N=, it is preferable that Y ¹ or Y ³ is -N=, and it is more preferable that Y ¹ is -N=.
When two of Y ¹ to Y ⁴ are -N=, it is preferred that Y ¹ and Y ³ are -N=.
When three of Y ¹ to Y ⁴ are -N=, it is preferred that Y ¹ to Y ³ are -N=.
In formula (A-1-1), when two or more of Y ¹ to Y ⁴ are -CR ² =, at least two of R ² may be linked to form a ring structure. The ring structure formed may be an aromatic ring structure or an aliphatic ring structure, but is preferably an aromatic ring structure. The aromatic ring structure may be an aromatic hydrocarbon ring structure or an aromatic heterocyclic structure, but is preferably an aromatic heterocyclic structure.
The aromatic heterocyclic structure is not particularly limited, but is preferably a 5-membered ring structure or a 6-membered ring structure, and more preferably a 5-membered ring structure.
Examples of the heteroatom that is a ring member in the aromatic heterocyclic structure include a nitrogen atom, an oxygen atom, and a sulfur atom. It is preferable that the aromatic heterocyclic structure contains at least a nitrogen atom, and it is more preferable that the aromatic heterocyclic structure contains two or more nitrogen atoms.
Among these, the ring structure formed by combining at least two of ^R2 is preferably a five-membered aromatic heterocyclic structure containing a nitrogen atom as a ring member.
The five-membered aromatic heterocyclic structure containing a nitrogen atom as a ring member is preferably a five-membered aromatic heterocyclic structure containing two or more nitrogen atoms as ring members, and more preferably a triazole ring structure or a tetrazole ring structure.
In addition, in formula (A-1-1), when two or more of Y ¹ to Y ⁴ are -CR ² =, it is preferable that R ² in two adjacent ring members among Y ¹ to Y ⁴ are bonded to form a ring structure, and it is preferable that at least Y ¹ and Y ² are -CR ² =, and R ² in Y ¹ and Y ² are bonded to form a ring structure.
In formula (A-1-1), R ² is preferably a hydrogen atom, an alkyl group, a hydroxy group or a carbamoyl group, and more preferably a hydrogen atom, a hydroxy group or a carbamoyl group.

In formula (A-1-2), it is preferable that at least one of Y ⁵ to Y ⁷ is -N=, and it is more preferable that at least two of them are -N=.
When two of Y ⁵ to Y ⁷ are -N=, it is preferred that Y ⁵ and Y ⁷ are -N=.
In formula (A-1-2), R ² is preferably a hydrogen atom, an alkyl group, a hydroxyl group or a carbamoyl group, and more preferably a hydrogen atom.
In formula (A-1-2), when two or more of Y ⁵ to Y ⁷ are -CR ² =, at least two of R ² may be linked to form a ring structure. The ring structure formed may be an aromatic ring structure or an aliphatic ring structure, but is preferably an aromatic ring structure. The aromatic ring structure may be an aromatic hydrocarbon ring structure or an aromatic heterocyclic ring structure, but is preferably an aromatic hydrocarbon ring structure.
The aromatic hydrocarbon ring structure is not particularly limited, but is preferably a benzene ring structure or a naphthalene ring structure, and more preferably a benzene ring structure.
In the case of an aromatic heterocyclic structure, examples of the heteroatom that is a ring member include a nitrogen atom, an oxygen atom, and a sulfur atom. It is preferable that the ring contains at least a nitrogen atom, and it is more preferable that the ring contains two or more nitrogen atoms.
In addition, in formula (A-1-3), when two or more of Y ⁵ to Y ⁷ are -CR ² =, it is preferable that R ² in two adjacent ring members among Y ⁵ to Y ⁷ are bonded to form a ring structure, and it is preferable that at least Y ⁶ and Y ⁷ are -CR ² =, and R ² in Y ⁶ and Y ⁷ are bonded to form a ring structure.

In formula (A-1-3), X is preferably —NR ³ — or —S—.
In formula (A-1-3), R ³ is preferably a hydrogen atom. When R ³ is an organic group, examples of R ³ include an alkyl group.
In formula (A-1-3), Y ⁸ and Y ⁹ are preferably —CR ² .
In formula (A-1-3), R ² is preferably a hydrogen atom, an alkyl group, a hydroxyl group or a carbamoyl group, and more preferably a hydrogen atom.
The alkyl group in ^R2 or ^R3 may be linear, branched, cyclic, or a structure represented by a combination thereof, but is preferably linear. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
In formula (A-1-3), when ^Y8 and ^Y9 are ^-CR2 =, the two ^R2 may be bonded to form a ring structure. The ring structure formed may be an aromatic ring structure or an aliphatic ring structure, but is preferably an aromatic ring structure. The aromatic ring structure may be an aromatic hydrocarbon ring structure or an aromatic heterocyclic ring structure, but is preferably an aromatic hydrocarbon ring structure.
The aromatic hydrocarbon ring structure is not particularly limited, but is preferably a benzene ring structure or a naphthalene ring structure, and more preferably a benzene ring structure.

Specific examples of the ring structure represented by Het are shown below, but the present invention is not limited to these. In the following structures, * represents the bonding site with the nitrogen atom in formula (A-1).

In formula (A-1), R ¹ is preferably a hydrogen atom, an alkyl group, an aryl group, or an alkoxycarbonyl group (which may have a substituent), more preferably a hydrogen atom or an alkoxycarbonyl group, and even more preferably a hydrogen atom or a t-butoxycarbonyl group.
The alkyl group may be linear, branched, cyclic, or a structure represented by a combination thereof, but is preferably linear. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
R ¹ is also preferably a thermally decomposable group. Specifically, it is preferable that R ¹ is decomposed by heating to form a structure in which the nitrogen atom and the hydrogen atom bonded to R ¹ are bonded by a single bond without a linking group.

Compound A is also preferably a compound represented by the following formula (A-2):

In formula (A-2), R ²¹ is a hydrogen atom or a monovalent organic group, Y ²¹ to Y ²⁶ are each -CR ²⁴ = or -N=, R ²⁴ is a hydrogen atom, an alkyl group, a hydroxyl group, or a carbamoyl group, and R ²² and R ²³ are each independently a hydrogen atom, an alkyl group, or a carbamoyl group.
In formula (A-2), a circle written in the center of a ring structure indicates that this ring structure is an aromatic ring structure.

In formula (A-2), preferred embodiments of Y ²¹ to Y ²³ are the same as the preferred embodiments of Y ¹ to Y ³ in formula (A-1-1), respectively.
In formula (A-2), preferred embodiments of Y ²⁴ to Y ²⁶ are the same as the preferred embodiments of Y ¹ to Y ³ in formula (A-1-1), respectively.
In formula (A-2), the preferred embodiments of R ²¹ are the same as the preferred embodiments of R ¹ in formula (A-1).
In formula (A-2), it is preferable that R ²² and R ²³ each independently represent a hydrogen atom or a carbamoyl group.
When R ²² or R ²³ is an alkyl group, the alkyl group may be linear, branched, cyclic, or a structure represented by a combination thereof, but is preferably linear. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
In formula (A-2), the preferred embodiments of R ²⁴ are the same as the preferred embodiments of R ² in formula (A-1-1).

If compound A has a structure represented by A-2, it can form a complex with copper ions, for example, as shown below, and therefore it is believed that migration of copper ions into the cured product is easily suppressed.

Compound A may be a compound represented by any one of the following formulas (A-3) to (A-5).

In formula (A-3), the ring structures represented by Het each independently represent an aromatic heterocycle which may have a substituent and which may be condensed with another ring, R ¹ represents a hydrogen atom or a monovalent organic group, and L ³¹ represents a divalent linking group.
In formula (A-4), the ring structures represented as Het are each independently an aromatic heterocycle which may have a substituent and which may be condensed with another ring, L ⁴¹ is a divalent linking group, L ⁴² is a single bond or a divalent linking group in which the bonding site with the nitrogen atom to which R ⁴¹ and R ⁴² are bonded is an aromatic ring, and R ⁴¹ and R ⁴² are each independently a hydrogen atom or a monovalent organic group.
In formula (A-5), the ring structures represented by Het are each independently an aromatic heterocycle which may have a substituent and which may be condensed with another ring, L ⁵¹ is a trivalent linking group in which the bonding site with the nitrogen atom to which R ⁵¹ and R ⁵² are bonded is an aromatic ring, and R ⁵¹ and R ⁵² are each independently a hydrogen atom or a monovalent organic group.

In formula (A-3), a preferred embodiment of the ring structure represented as Het in formula (A-1) is similar to the preferred embodiment of the ring structure represented as Het in formula (A-1), except that the description of "the bonding site to the nitrogen atom to which R ¹ in formula (A-1) is bonded" needs to be read as "the bonding site to the ^{nitrogen atom to which R 1} ⁱⁿ formula (A-3) is bonded" or "the bonding site to L 31".
In formula (A-3), L ³¹ is preferably a hydrocarbon group or a group in which a hydrocarbon group is bonded to at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N -.
Here, the bonding site to the nitrogen atom in L ³¹ is preferably a hydrocarbon group.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms.
R ^{3 N} is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
In formula (A-3), the preferred embodiments of R ¹ are the same as the preferred embodiments of R ¹ in formula (A-1).

In formula (A-4), a preferred embodiment of the ring structure represented as Het in formula (A-1) is similar to the preferred embodiment of the ring structure represented as Het in formula (A-1), except that in the ring structure represented as Het, the description of "the bonding site to the nitrogen atom to which R ¹ in formula (A-1) is bonded" needs to be read as "the bonding site to L ⁴¹ ", and in one of the ring structures represented as Het, any one of the hydrogen atoms bonded to a ring member by a single bond not via a linking group needs to be read as the bonding site to L ⁴² .
For example, when the ring structure represented by Het in formula (A-4) is any of the structures represented by formulas (A-1-1) to (A-1-3) above, any of Y ¹ to Y ⁴ , Y ⁵ to Y ⁷ , Y ⁸ and Y ⁹ is -CR ² =, and R ² is the bonding site with L ⁴² .
In formula (A-4), L ⁴¹ is preferably a hydrocarbon group or a group in which a hydrocarbon group is bonded to at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N -, and more preferably a hydrocarbon group. The preferred aspects of R ^N are as described above.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms.
In formula (A-4), L ⁴² is preferably a single bond or a group represented by the following formula (L42).

In formula (L42), Ar represents a divalent aromatic group, ^L43 represents a single bond or a divalent linking group, * represents a bonding site with the nitrogen atom to which ^R41 and ^R42 are bonded in formula (A-4), and # represents a bonding site with the ring structure represented as Het in formula (A-4).
In formula (L42), Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group, preferably an aromatic hydrocarbon group, more preferably a phenylene group, and particularly preferably a 1,4-phenylene group.
In formula (L42), ^L43 is preferably a hydrocarbon group or a group in which a hydrocarbon group is bonded to at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N -, and more preferably a hydrocarbon group. The preferred embodiments of R ^N are as described above.
In formula (A-4), R ⁴¹ and R ⁴² each independently preferably represent a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom.

In formula (A-5), a preferred embodiment of the ring structure represented as Het is the same as the preferred embodiment of the ring structure represented as Het in formula (A-1), except that in the ring structure represented as Het, the description of "the bonding site to the nitrogen atom to which R ¹ in formula (A-1) is bonded" needs to be read as "the bonding site to L ⁵¹ ". It is the same as the preferred embodiment of the ring structure represented as Het in formula (A-1).
In formula (A-5), L ⁵¹ is preferably a group represented by the following formula (L51).

In formula (L51), Ar represents a divalent aromatic group, ^L52 represents a trivalent linking group, * represents a bonding site with the nitrogen atom to which ^R51 and ^R52 are bonded in formula (A-5), and # represents a bonding site with the ring structure represented as Het in formula (A-5).
In formula (L51), Ar represents an aromatic hydrocarbon group or an aromatic heterocyclic group, preferably an aromatic hydrocarbon group, more preferably a phenylene group, and particularly preferably a 1,4-phenylene group.
In formula (L51), L ⁵² is preferably a hydrocarbon group or a group in which a hydrocarbon group is bonded to at least one group selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O) ₂ -, and -NR ^N -, and more preferably a hydrocarbon group.
In formula (A-5), R ⁵¹ and R ⁵² each independently preferably represent a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom.

[Molecular weight]
The molecular weight of compound A is not particularly limited, but is preferably 147 or more, more preferably 150 or more, and even more preferably 160 or more, for example.
The molecular weight is not particularly limited, but is preferably, for example, 2,000 or less, more preferably 1,000 or less, and even more preferably 500 or less.

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

〔Concrete example〕
Specific examples of compound A include, but are not limited to, the compounds used in the examples described below.

〔Content〕
The content of compound A relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 10 mass%. The lower limit is more preferably 0.02 mass% or more, even more preferably 0.05 mass% or more, and particularly preferably 0.10 mass% or more. The upper limit is more preferably 8 mass% or less, even more preferably 6 mass% or less, and particularly preferably 3 mass% or less.
The content of compound A relative to the total mass of the specific resin is preferably 0.02 to 12% by mass. The lower limit is more preferably 0.03% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.06% by mass or more. The upper limit is more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 4% by mass or less.
When the resin composition contains a polymerization initiator, the content of compound A relative to the total mass of the polymerization initiator is preferably 0.5 to 200 mass%. The lower limit is more preferably 1.0 mass% or more, even more preferably 2.0 mass% or more, and particularly preferably 4.0 mass% or more. The upper limit is more preferably 180 mass% or less, even more preferably 150 mass% or less, and particularly preferably 120 mass% or less.
Compound A may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.

<Organometallic Complex>
From the viewpoint of chemical resistance, the resin composition of the present invention may contain an organometallic complex.
The organometallic complex is not particularly limited as long as it is an organic complex compound containing a metal atom. However, it is preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated to a metal atom, and further preferably a metallocene compound.
The metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives, which may have a substituent, as η5-ligands.
The organic group is not particularly limited, but is preferably a hydrocarbon group or a group consisting of a combination of a hydrocarbon group and a heteroatom, preferably an oxygen atom, a sulfur atom, or a nitrogen atom.
At least one of the organic groups is preferably a cyclic group, and more preferably at least two of the organic groups are cyclic groups.
The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group.
The cyclic group may be a hydrocarbon ring or a heterocyclic ring, with a hydrocarbon ring being preferred.
The five-membered cyclic group is preferably a cyclopentadienyl group.
The organometallic complex preferably contains 2 to 4 cyclic groups in one molecule.

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

The organometallic complex may contain two or more metal atoms or only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one type of metal atom, or it may contain two or more types of metal atoms.

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

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

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

Preferred examples of the organometallic complex include compounds represented by the following formula (P).

In formula (P), M is a metal atom, and each R is independently a substituent.
It is preferred that each R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

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

Specific examples of the organometallic complex include, but are not limited to, tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds.

Further examples include the compounds described in paragraphs 0078 to 0088 of WO 2018/025738, the contents of which are incorporated herein by reference.

The content of the organometallic complex is preferably 0.1 to 30% by mass based on the total solid content of the resin composition. The lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less.
The organometallic complexes 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.

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

[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 containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds. The radical crosslinking agent may have three or more ethylenically unsaturated bonds.
As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is even more preferable.
From the viewpoint of the film strength of the obtained 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 above-mentioned compound having three or more ethylenically unsaturated bonds.

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

Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids are also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. As another example, it is also possible to use a compound group in which the above unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021/112189, the contents of which are incorporated herein by reference.

Preferable radical crosslinking agents other than those mentioned above include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021/112189, the contents of which are incorporated herein by reference.

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

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

As radical crosslinking agents, urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also suitable. As radical crosslinking agents, compounds having an amino structure or sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, can also be used.

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

The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, more preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, the agent has excellent handling properties during manufacturing and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoints of pattern resolution and film stretchability, it is preferable to use a difunctional methacrylate or acrylate for the resin composition.
Specific examples of the compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexyl ... Xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, 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 necessary.
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 of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional radical crosslinking agent, 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, polypropylene glycol mono(meth)acrylate, and other (meth)acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether are preferably used. As the monofunctional radical crosslinking agent, a compound having a boiling point of 100° C. or more under normal pressure is also preferred in order to suppress volatilization before exposure.
Other examples of the difunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

When a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0 mass% and not more than 60 mass% based on the total solid content of the resin composition. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50 mass% or less, and even more preferably 30 mass% or less.

The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount is within the above range.

[Other crosslinking agents]
The resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
The other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photoacid generator or photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
Other cross-linking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022/145355, the disclosures of which are incorporated herein by reference.

[Polymerization initiator]
The resin composition of the present invention preferably contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable that the resin composition contains a photopolymerization initiator.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

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

Any known compound can be used as the photoradical polymerization initiator. For example, 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 aminoacetophenones, α-hydroxyketone compounds such as hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. For details of these, please refer to the descriptions in paragraphs 0165 to 0182 of JP 2016-027357 A and paragraphs 0138 to 0151 of WO 2015/199219, the contents of which are incorporated herein by reference. Further examples include the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A and JP 6301489 A, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 60p, 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 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. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

α-Hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

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

As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of WO 2021/112189 can also be suitably used. The contents of this specification are incorporated herein.

As a photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it becomes possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.

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

Preferred oxime compounds include, for example, compounds having the following structure, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

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

As the photoradical polymerization initiator, for example, an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of WO 2021/112189, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, or an oxime compound having a fluorine atom can be used.
In addition, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group-containing substituent bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of WO 2021/020359 can also be used. The contents of these compounds are incorporated herein by reference.

As the photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^OX1 in which an electron-withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used. The electron-withdrawing group of the aromatic ring group Ar ^OX1 includes 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. An acyl group and a nitro group are preferred, and an acyl group is more preferred because it is easy to form a film with excellent light resistance, and a benzoyl group is 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 further 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 the formula (OX1) and the compounds represented by the formula (OX2), and more preferably the compound represented by the formula (OX2).

In the formula, R ^X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group;
R ^X2 represents an alkyl group, 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 each a hydrogen atom.

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.

Particularly preferred oxime compounds include oxime compounds having specific substituents as disclosed in JP 2007-269779 A and oxime compounds having thioaryl groups as disclosed in JP 2009-191061 A, the contents of which are incorporated herein by reference.

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.

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

As the photoradical polymerization initiator, the compounds described in paragraphs [0175] to [0179] of WO 2021/020359 and the compounds described in paragraphs [0048] to [0055] of WO 2015/125469 can also be used, the contents of which are incorporated herein by reference.

As the photoradical polymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time, and improving the stability of the resin composition over time. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015/004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017/033680, paragraphs 0039 to 0055; compound (E) and compound (G) described in WO-T-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Publication No. 4963, the oxime ester photoinitiators described in paragraph 0007 of JP-T-2017-523465, the photoinitiators 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 photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

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

[Sensitizer]
The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and are decomposed to generate a radical, an acid, or a base.
Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based compounds, and the like.
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-dimethylaminocinnamylidene indanone, and p-dimethylaminobenzylidene indanone. Non, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoethylaminobenzoate Examples of such an alkyl ester 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, the description in paragraphs [0161] to [0163] of JP2016-027357A can be referred to, 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 mass % relative to the total solid content of the resin composition, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %. The sensitizer may be used alone or in combination of two or more types.

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

In addition, the chain transfer agent may be the compound described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.

When the resin composition 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 solid content of the resin composition. The chain transfer agent may be one type or two or more types. When there are two or more types of chain transfer agents, the total is preferably within the above range.

<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 include a thermal base generator and a photobase generator.
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, and the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package can be improved.
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 is not particularly limited, and a known base generator can be used. Examples of known base generators include 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, iminium salts, 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 the compounds described in paragraphs 0249 to 0275 of WO 2022/145355. The above descriptions are incorporated herein by reference.

Base generators include, but are not limited to, the following compounds:

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, but are not limited to, the following compounds:

Specific examples of iminium salts include, but are not limited to, the following compounds:

In addition, the base generator is preferably an amine in which the amino group is protected by a t-butoxycarbonyl group, from the viewpoints of storage stability and generating a base by deprotection during curing.

Amine compounds protected by a t-butoxycarbonyl group include, for example, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, Diol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethano diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis(3-aminopropyl)ethane ether, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl)ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or a derivative thereof is protected with a t-butoxycarbonyl group, but are not limited to these.

When the resin composition 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. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 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.

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

Esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2- Suitable examples of alkyloxypropionic acid alkyl esters include 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.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

Suitable 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.

Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

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

As an example of a sulfoxide, dimethyl sulfoxide is preferred.

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

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

From the standpoint of improving the properties of the coating surface, it is also preferable to mix two or more types of solvents.

In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, 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 solvents, is preferred. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. An embodiment in which toluene is further added to these combined solvents in an amount of about 1 to 10% by mass based on the total mass of the solvent is also one of the preferred embodiments of the present invention.
In particular, from the viewpoint of storage stability of the resin composition, an embodiment containing γ-valerolactone as a solvent is one of the preferred embodiments of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit of the content is not particularly limited and may be 100% by mass. The content may be determined in consideration of the solubility of components such as a specific resin contained in the resin composition, etc.
Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide, relative to the total mass of the solvent.

From the viewpoint of coatability, the content of the solvent is preferably an amount that results in a total solids concentration of the resin composition of the present invention of 5 to 80 mass%, more preferably an amount that results in a total solids concentration of 5 to 75 mass%, even more preferably an amount that results in a total solids concentration of 10 to 70 mass%, and even more preferably an amount that results in a total solids concentration of 20 to 70 mass%. The content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method. When two or more types of solvents are contained, the total amount is preferably within the above range.

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

〔Silane coupling agent〕
Examples of the silane coupling agent include the compounds described in paragraph 0316 of International Publication No. 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein. In addition, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group. In addition, the following R includes a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent may be selected according to the desorption temperature, and examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of setting the desorption temperature at 160 to 180 ° C., caprolactam and the like are preferred. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (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.
Furthermore, an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
Examples of such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1).

In formula (S-1), R ^{1 S1} represents a monovalent organic group, R ^{1 S2} represents a hydrogen atom, a hydroxyl group or an alkoxy group, and n represents an integer of 0 to 2.
R ^S1 is preferably a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group. Of these, a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, a vinylphenyl group or a (meth)acryloyloxy group is more preferred, and a (meth)acryloyloxy group is even more preferred.
R ^S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
n represents an integer of 0 to 2, and is preferably 1.
Here, the structures of the repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same.
Here, among the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, it is preferable that n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and further preferably that n is 1 in at least two.
As such oligomer type compounds, commercially available products can be used, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[Aluminum-based adhesion promoter]
Examples 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. By making the content equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer will be good, and by making the content equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern will be good. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.

<Migration Inhibitor>
The resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively suppressed.

The resin composition of the present invention preferably contains a compound having an aromatic heterocycle, which is different from compound A. Such a compound is not particularly limited, and examples thereof include compounds having a heterocycle (a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, or a tetrazine ring).
Other examples of the migration inhibitor include compounds having a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring, or a 6H-pyran 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 can be preferably used.

As a migration inhibitor, an ion trapping agent that captures anions such as halogen ions can also be used.

Other migration inhibitors that can be used include the rust inhibitors described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compounds described in paragraph 0052 of JP 2011-059656 A, the compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520 A, and the compounds described in paragraph 0166 of WO 2015/199219 A, the contents of which are incorporated herein by reference.

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.

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

<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 examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. The contents of this document 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 mass % relative to the total solid content of the resin composition, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %.

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

<Light absorber>
The resin composition of the present invention also preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.
Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022/202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of which are incorporated herein by reference.

The content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.

<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, photoacid generators, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained. In addition, the resin composition of the present invention may contain a urea compound, a carbodiimide compound or an isourea compound. By appropriately incorporating these components, properties such as film properties can be adjusted. For these components, for example, the description in paragraphs 0183 and after of JP-A-2012-003225 (corresponding to paragraph 0237 of US Patent Application Publication No. 2013/0034812), and the description in paragraphs 0101 to 0104, 0107 to 0109, etc. of JP-A-2008-250074 can be taken into consideration, and the contents of these are incorporated herein. When these additives are blended, the total content is preferably 3 mass % or less of the solid content of the resin composition of the present invention.
These other additives include the compounds described in paragraphs 0316 to 0358 of WO 2022/145355, the disclosures of which are incorporated herein by reference.

<Characteristics of Resin Composition>
The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, it is preferably 1,000 mm ² /s to 12,000 mm ² /s, more preferably 2,000 mm ² /s to 10,000 mm ² /s, and even more preferably 2,500 mm ² /s to 8,000 mm ² /s. If it is within the above range, it is easy to obtain a coating film with high uniformity. If it is 1,000 mm ² /s or more, it is easy to apply it with a film thickness required for, for example, a rewiring insulating film, 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 insulation, 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, nickel, etc., but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, it is preferable that the total of these metals is within the above range.

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

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 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion.Among them, those present in the form of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.Halogen atoms include chlorine atoms and bromine atoms.It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range.
A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

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

<Cured Product of Resin Composition>
By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
The cured product of the present invention is a cured product obtained by curing a resin composition.
The resin composition is preferably cured by heating, and the heating temperature is more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and can be selected according to the application, such as film-like, rod-like, spherical, pellet-like, etc. In the present invention, the cured product is preferably in the form of a film. By pattern processing of the resin composition, the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function. The film thickness of the cured product (film made of the cured product) is preferably 0.5 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 the volume change before and after curing of the resin composition, and can be calculated by 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.

<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 a conventionally known method.
Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank.
The temperature during mixing is preferably from 10 to 30°C, more preferably from 15 to 25°C.

In order to remove foreign matter such as dust and fine particles from the resin composition of the present invention, it is preferable to perform filtration using a filter. The filter pore size is, for example, preferably 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, it is more preferable that it is HDPE (high density polyethylene). The filter may be used after being washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be used in combination. As an example of a connection mode, an HDPE filter with a pore size of 1 μm as the first stage and an HDPE filter with a pore size of 0.2 μm as the second stage may be connected in series. In addition, various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be performed. Filtration may also be performed under pressure. When filtration is performed under pressure, the pressure to be applied is, for example, preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.
In addition to filtration using a filter, impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent may be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used.
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 the cured product)
The method for producing a cured product of the present invention preferably includes a film formation step of applying the resin composition onto a substrate to form a film.
It is more preferable that the method for producing a cured product includes the above-mentioned film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern.
It is particularly preferable that the method for producing a cured product includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step.
The method for producing a cured product preferably includes the film-forming step and a step of heating the film.
Each step will be described in detail below.

<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 onto a substrate to form a film.
The method for producing a cured product of the present invention preferably includes a film formation step of applying the resin composition onto a substrate to form a film.

〔Base material〕
The type of substrate can be appropriately determined according to the application, and is not particularly limited. Examples of substrates include semiconductor-prepared substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals and substrates in which a metal layer is formed by plating, vapor deposition, etc.), paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates of plasma display panels (PDPs). The substrate is preferably a semiconductor-prepared substrate, more preferably a silicon substrate, a Cu substrate, or a mold substrate.
These substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface.
The shape of the substrate is not particularly limited, and may be circular or rectangular.
The size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular, and is preferably, for example, a short side length of 100 to 1000 mm, more preferably 200 to 700 mm, if it is rectangular.
As the substrate, for example, a plate-shaped substrate, preferably a panel-shaped substrate (substrate) is used.

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

The resin composition is preferably applied to a substrate by coating.
Specific examples of the means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet methods. From the viewpoint of uniformity of the thickness of the film, spin coating, slit coating, spray coating, or inkjet methods are preferred, and from the viewpoint of uniformity of the thickness of the film and productivity, spin coating and slit coating are more preferred. A film of a desired thickness can be obtained by adjusting the solid content concentration and coating conditions of the resin composition according to the means to be applied. In addition, the coating method can be appropriately selected depending on the shape of the substrate, and if the substrate is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and if the substrate is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred. In the case of the spin coating method, for example, it can be applied for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm.
Alternatively, a coating film formed by applying the coating material to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate.
As for 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.
Also, a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinse (EBR) and back rinse.
A pre-wetting step may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

<Drying process>
After the film-forming step (layer-forming step), the above-mentioned film may be subjected to a step of drying the formed film (layer) (drying step) in order 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 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.
The method for producing a cured product may include an exposure step of selectively exposing the film formed in the film formation step to light.
Selective exposure means that only a portion of the film is exposed, and selective exposure results in exposed and unexposed areas of the film.
The amount of exposure light is not particularly limited as long as it can cure the resin composition of the present invention, but is preferably 50 to 10,000 mJ/cm ² , and more preferably 200 to 8,000 mJ/cm ² , calculated as exposure energy at a wavelength of 365 nm.

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

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

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

<Developing process>
The film after exposure may be subjected to a development step in which the film 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 one of the exposed and unexposed areas of the film to form a pattern.
Here, development in which the non-exposed portion of the film is removed by the development process is called negative development, and development in which the exposed portion of the film is 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 are 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, and more preferably TMAH. 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, based on the total mass of the developer.

When the developer contains an organic solvent, the compounds described in paragraph 0387 of WO 2021/112189 can be used as the organic solvent. The contents of this specification are incorporated herein by reference. In addition, examples of alcohols that are suitable include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and examples of amides that are suitable include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethylsulfoxide, 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 dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

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

When the developer contains an organic solvent, the developer may further contain at least one of a basic compound and a base generator. When at least one of the basic compound and the base generator in the developer permeates the pattern, the performance of the pattern, such as the breaking elongation, may be improved.

As the basic compound, from the viewpoint of reliability when it remains in the cured film (adhesion to a substrate when the cured product is further heated), an organic base is preferred.
As the basic compound, a basic compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, or the like is preferable. In order to promote the imidization reaction, a primary amine, a secondary amine, a tertiary amine, or an ammonium salt is preferable, a secondary amine, a tertiary amine, or an ammonium salt is more preferable, a secondary amine or a tertiary amine is further more preferable, and a tertiary amine is particularly preferable.
From the viewpoint of the mechanical properties (elongation at break) of the cured product, it is preferable for the basic compound to be one that is unlikely to remain in the cured film (obtained cured product), and from the viewpoint of promoting cyclization, it is preferable for the basic compound to be one that is unlikely to decrease in the amount remaining before heating due to vaporization, etc.
Therefore, the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and even more preferably 100°C to 230°C at normal pressure (101,325 Pa).
The boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C. from the boiling point of the organic solvent contained in the developer, and more preferably higher than the boiling point of the organic solvent contained in the developer.
For example, when the boiling point of the organic solvent is 100° C., the basic compound used preferably has a boiling point of 80° C. or higher, and more preferably has a boiling point of 100° C. or higher.
The developer may contain only one kind of basic compound, or may contain two or more kinds of basic compounds.

Specific examples of basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diamino Examples include pentane, N-methylhexylamine, N-methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, spermidine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperazine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, and N,N,N,N-tetramethyl-1,3-propanediamine.

The preferred embodiment of the base generator is the same as the preferred embodiment of the base generator contained in the composition described above. In particular, it is preferred that the base generator is a thermal base generator.

When the developer contains at least one of a basic compound and a base generator, the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the developer. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
When the basic compound or base generator is a solid in the environment in which the developer is used, the content of the basic compound or base generator is preferably 70 to 100% by mass based on the total solid content of the developer.
The developer may contain at least one of a basic compound and a base generator, or may contain two or more of them. When at least one of a basic compound and a base generator is two or more, the total amount of them is preferably within the above range.

The developer may further comprise other components.
Examples of other components include known surfactants and known defoamers.

[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 is formed in the developer, a paddle development method in which a 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 adopted in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate. This process may be repeated multiple times.
Methods of supplying the developer in the development step include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated by ultrasonic waves or the like on the substrate, and a combination of these steps.

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

In the development process, after treatment with the developer, the pattern may be washed (rinsed) with a rinse solution. Also, a method may be adopted in which a rinse solution is supplied before the developer in contact with the pattern has completely dried.

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

When the rinsing liquid contains an organic solvent, examples of the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent.
The organic solvent contained in the rinse liquid is preferably different from the organic solvent contained in the developer, and more preferably has a lower solubility for the pattern than the organic solvent contained in the developer.

When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, γ-butyrolactone, dimethylsulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.

When the rinse solution contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the rinse solution. Furthermore, the organic solvent may account for 100% by mass, based on the total mass of the rinse solution.

The rinse liquid may contain at least one of a basic compound and a base generator.
Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinsing liquid contains an organic solvent and at least one of a basic compound and a base generator is also one of the preferred embodiments of the present invention.
Examples of the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained in the above-mentioned developer containing an organic solvent, and preferred embodiments thereof are also the same.
The basic compound and base generator contained in the rinse solution may be selected in consideration of the solubility in the solvent in the rinse solution.

When the rinse solution contains at least one of a basic compound and a base generator, the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the rinse solution. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
When the basic compound or base generator is a solid in the environment in which the rinse liquid is used, the content of the basic compound or base generator is also preferably 70 to 100 mass % based on the total solid content of the rinse liquid.
When the rinse solution contains at least one of a basic compound and a base generator, the rinse solution may contain only one kind of at least one of the basic compound and the base generator, or may contain two or more kinds. When at least one of the basic compound and the base generator contains two or more kinds, the total amount thereof is preferably within the above range.

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

[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 of the method include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like.
From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, the rinse liquid may be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, while from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.
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.
The method of supplying the rinsing liquid in the rinsing step may be a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept substantially stationary on the substrate, a step in which the rinsing liquid is vibrated on the substrate by ultrasonic waves or the like, or a combination of these steps.

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

The development step may include a step of contacting the pattern with a processing liquid after treatment with a developer or after washing the pattern with a rinse liquid. Also, a method may be employed in which the processing liquid is supplied before the developer or rinse liquid in contact with the pattern is completely dried.

The treatment liquid includes a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator.
Preferred aspects of the organic solvent, and at least one of the basic compound and the base generator are the same as the preferred aspects of the organic solvent, and at least one of the basic compound and the base generator used in the above-mentioned rinse solution.
The method of supplying the processing liquid to the pattern can be the same as the above-mentioned method of supplying the rinsing liquid, and the preferred embodiments are also the same.

The content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the treatment liquid. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
In addition, when the basic compound or base generator is a solid in the environment in which the treatment liquid is used, the content of the basic compound or base generator is preferably 70 to 100 mass % based on the total solid content of the treatment liquid.
When the treatment liquid contains at least one of a basic compound and a base generator, the treatment liquid may contain only one kind of at least one of the basic compound and the base generator, or may contain two or more kinds. When at least one of the basic compound and the base generator contains two or more kinds, the total amount thereof is preferably within the above range.

<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 developing step.
The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without carrying out a development step, or a film obtained in a film formation step.
In the heating step, the resin such as the polyimide precursor is cyclized to become a resin such as a polyimide.
Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in the crosslinking agent other than the specific resin also proceeds.
The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

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

The heating step is preferably performed at a temperature rise rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature. The temperature rise rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min. By setting the temperature rise rate at 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 rise rate at 12° C./min or less, it is possible to alleviate the residual stress of the cured product.
In addition, in the case of an oven capable of rapid heating, the temperature is increased from the starting temperature to the maximum heating temperature at a rate of preferably 1 to 8° C./sec, more preferably 2 to 7° C./sec, and even more preferably 3 to 6° C./sec.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature begins. For example, when the resin composition of the present invention is applied to a substrate and then dried, it is the temperature of the film (layer) after drying, and it is preferable to raise the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

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

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

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

<Metal Layer Forming Process>
The pattern obtained by the development step (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 by the development step (preferably subjected to at least one of a heating step and a post-development exposure step).

The metal layer can be made of any existing metal type without any particular limitations, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. 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. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations of these methods are possible. More specifically, there are patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electrolytic plating. A preferred embodiment of plating is electrolytic plating using copper sulfate or copper cyanide plating solution.

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

<Applications>
Examples of the method for producing the cured product of the present invention or the fields in which the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include etching patterns of sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or insulating films for mounting applications such as those described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd. "High-performance and Applied Technology of Polyimides" April 2008, supervised by Masaaki Kakimoto, CMC Technical Library "Basics and Development of Polyimide Materials" published in November 2011, and Japan Polyimide and Aromatic Polymer Research Association/editor "Latest Polyimides Basics 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 for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, and for producing protective lacquers and dielectric layers in electronics, especially microelectronics.

(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 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 the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention multiple times.

The laminate of the present invention preferably includes two or more layers made of a cured product, and includes a metal layer between any two of the layers made of the cured product. The metal layer is preferably formed by the metal layer forming step.
That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer made of a cured product between the steps for producing a cured product which are performed multiple times. A preferred embodiment of the metal layer forming step is as described above.
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.
The layer made of the first cured product and the layer made of the second cured product are preferably layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

<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 performing at least one of (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) a heating process and a post-development exposure process again on the surface of the pattern (resin layer) or metal layer in this order. However, at least one of (a) the film formation process and (d) the heating process and the post-development exposure process may be repeated. In addition, after at least one of (d) the heating process and the post-development exposure process, (e) a metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying process and the like as appropriate.

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 the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

The lamination step is preferably carried out 2 to 20 times, and more preferably 2 to 9 times.
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 layers may be the same or different in composition, shape, film thickness, etc.

In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer. Specifically, the following may be repeated in this order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step; or (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step. By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) of the present invention and the metal layer can be laminated alternately.

(Surface activation treatment process)
The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
The surface activation treatment step is usually carried out after the metal layer formation step, but after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be subjected to a surface activation treatment step before the metal layer formation step is carried out.
The surface activation treatment may be performed on at least a part of the metal layer, or on at least a part of the resin composition layer after exposure, or on at least a part of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the area of the metal layer on which the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface can be improved.
It is preferable to perform the surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface that has been surface-activated. In particular, when performing negative development, etc., when the resin composition layer is cured, it is less likely to be damaged by the surface treatment, and the adhesion is likely to be improved.
The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021/112189, the contents of which are incorporated herein by reference.

(Semiconductor device and its manufacturing method)
The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention.
The present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product or the method for producing the laminate of the present invention.
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 are incorporated herein by reference.

The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing contents, processing procedures, etc. shown in the following examples can be changed 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. "Parts" and "%" are based on mass unless otherwise specified.

<Method for producing a precursor of cyclized resin>
[Synthesis Example 1: Synthesis of Cyclized Resin Precursor (Resin 1)]
23.48 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27 g of bisphthalic dianhydride (BPDA) were placed in a separable flask, 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of tetrahydrofuran were added, and the mixture was stirred at room temperature (25°C), and 24.66 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generation due to the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.
Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes while stirring, followed by the addition of a suspension of 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) in 119.73 g of tetrahydrofuran over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethyl alcohol was added and stirred for 1 hour, and then 136.83 g of tetrahydrofuran was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
The obtained reaction solution was added to 716.21 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered off and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 8470.26 g of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to obtain 80.3 g of powdered resin 1. The molecular weight of resin 1 was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000. It was confirmed by ¹ H-NMR that the structure of resin 1 was a structure represented by the following formula (P-1).

[Synthesis Example 2: Synthesis of Cyclized Resin Precursor (Resin 2)]
21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and 17.0 g of thionyl chloride was added over 60 minutes while maintaining the temperature at -10±5°C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -10±5°C over 60 minutes, and the mixture was stirred at room temperature for 2 hours. Then, 10.0 g of ethanol was added and stirred at room temperature for 1 hour.
Next, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was collected by filtration and dissolved in 500 g of tetrahydrofuran. 6000 g of water (poor solvent) was added to the obtained solution to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was filtered again and dried at 45° C. under reduced pressure for 3 days.
After dissolving 46.6 g of the dried powder in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added and stirred at room temperature for 35 minutes. Then, 3000 g of ethanol was added, and the precipitate was collected by filtration. The obtained precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) were added thereto, and the mixture was stirred for 4 hours. Then, the ion exchange resin was removed by filtration, and the obtained polymer solution was added to 5,600 g of water to obtain a precipitate. The precipitate was collected by filtration and dried at 45 ° C. under reduced pressure for 24 hours, to obtain 45.1 g of resin 2.
It was confirmed by ¹ H-NMR that the structure of resin 2 was a structure represented by the following formula (P-2). The molecular weight of resin 2 was measured by gel permeation chromatography (standard polystyrene equivalent) and found to have a weight average molecular weight (Mw) of 20,000. Resin 2 with Mw of 5,000, resin 2 with Mw of 10,000, and resin 2 with Mw of 30,000 were also synthesized by appropriately adjusting the equivalent of 4,4'-diaminodiphenyl ether.

[Synthesis Examples 3 to 9, 12: Synthesis of Cyclized Resin Precursors (Resins 3 to 9, and 12)]
Resins 3 to 9 and 12 having structures represented by any one of the following formulas (P-3) to (P-9) were synthesized in the same manner as in Synthesis Example 2, except that the compounds used were appropriately changed.
Resin 3 had an Mw of 20,000, resin 4 had an Mw of 20,000, resin 5 had an Mw of 20,000, resin 6 had an Mw of 20,000, resin 7 had an Mw of 20,000, resin 8 had an Mw of 20,000, resin 9 had an Mw of 20,000, and resin 12 had an Mw of 20,000.

Synthesis Example 10: Synthesis of cyclized resin (resin 10)
In a flask equipped with a condenser and a stirrer, 18.0 g (40.5 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP) while removing moisture. Then, 7.95 g (39.7 mmol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 3 hours and further stirred at 45°C for 3 hours. Then, 12.8 g (160 mmol) of pyridine, 10.3 g (101 mmol) of acetic anhydride, and 40.0 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80°C for 3 hours, and diluted with 50 g of N-methylpyrrolidone (NMP).
The reaction solution was precipitated in 1 liter of methanol and stirred at a speed of 3000 rpm for 15 minutes. The resin was collected by filtration, stirred again in 1 liter of methanol for 30 minutes, and filtered again. The obtained resin was dried at 40°C under reduced pressure for one day to obtain resin 10. The molecular weight of resin 10 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 20,000. It was confirmed by ¹ H-NMR that the structure of resin 10 was a structure represented by the following formula (P-10).

[Synthesis Example 11: Synthesis of cyclized resin (resin 11)]
Resin 11 having a structure represented by the following formula (P-11) was synthesized in the same manner as in Synthesis Example 10, except that the compounds used were appropriately changed.
Resin 11 had a Mw of 20,000.

<Examples and Comparative Examples>
In each of the examples, the components shown in the following table were mixed to obtain a resin composition. In each of the comparative examples, the components shown in the following table were mixed to obtain a comparative composition.
Specifically, the content (blended 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 contents (amounts) of the solvents were set so that the solids concentration of the composition was the value (mass %) of "Solids concentration" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvents was the ratio shown in the "Ratio" column in the table.
The obtained resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter having a pore width of 0.8 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〕
Resins 1 to 12: Resins 1 to 12 obtained by the above synthesis examples

[Monomer (polymerizable compound)]
M-1 to M-2: Compounds having the following structures, where the subscripts in parentheses indicate the number of repetitions.

[Polymerization initiator or photoacid generator]
I-1 to I-5: Compounds having the following structure I-6: Omnirad 1312 (manufactured by IGM)
・ I-7: Omnirad TPO H (manufactured by IGM)

[Thermal Base Generator]
A-1 to A-3: Compounds having the following structures

[Polymerization inhibitor]
B-1 to B-4: Compounds having the following structure

[Silane coupling agent (metal adhesion improver)]
C-1 to C-3: Compounds having the following structures: In the following formulas, Et represents an ethyl group.
C-4: X-12-1293 (silane coupling agent with an isocyanate group protected, manufactured by Shin-Etsu Chemical Co., Ltd.)
C-5: KR-513 (a silane coupling agent which is an acrylic group-containing oligomer, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Migration Inhibitor]
D-1 to D-5: Compounds having the following structure

〔Additive〕
E-1 to E-6, E-9, E-11 to E-14: Compounds of the following structure E-7: Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid E-8: The following synthetic product E-10: Benzoyl peroxide

<Other Additives: Synthesis of Diazonaphthoquinone Compound E-8>
29.72 g (70 mmol) of 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene)bisphenol (Tris-PA, manufactured by Honshu Chemical Industry Co., Ltd.) was added to the flask. Then, 46.93 g (174.9 mmol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride and 17.9 g of triethylamine were dissolved in 300 g of acetone with stirring, and the mixture was dropped into the flask using a dropping funnel over 30 minutes, and stirred for 30 minutes at an internal temperature of 30°C. Then, hydrochloric acid was dropped and the mixture was stirred for another 30 minutes. Then, a solution of 1640 g of pure water and 30 g of hydrochloric acid was prepared in a beaker, and the filtrate obtained by filtering the hydrochloride in the reaction solution was dropped into this, and the precipitate was filtered, washed with water, and vacuum dried at 40°C for 50 hours to obtain a diazonaphthoquinone compound E-8.

[Compound A]
F-1 to F-46: Compounds having the following structure. F-1 to F-46 are compounds corresponding to compound A.
FR-1 to FR-2: Compounds having the following structures. FR-1 to FR-2 are compounds not corresponding to compound A.

-Synthesis of F-1-

N,N-diisopropylethylamine (15 mL) was added to 2-chloropyrimidine (5.0 g) and 2-aminopyrimidine (3.8 g), and the mixture was stirred at 140° C. for 8 hours. After cooling to room temperature, N,N-diisopropylethylamine was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (chloroform:methanol=100:0→96:4) and recrystallized from ethanol (50 mL) to obtain crystals of compound F-1 (0.7 g). Melting point: 227° C.
^1H -NMR, 400MHz, δ(DMSO-d6) ppm: 7.04 (2H, t, J=5 Hz), 8.58 (4H, d, J=5 Hz), 10.24 (1H, s).

F-2 to F-46 were also synthesized using a method similar to that used to synthesize F-1.

〔solvent〕
NMP: N-methyl-2-pyrrolidone EL: Ethyl lactate DMSO: Dimethyl sulfoxide GBL: γ-butyrolactone GVL: γ-valerolactone MDMPA: 3-methoxy-N,N-dimethylpropanamide toluene: Toluene

<Evaluation>
[Evaluation of adhesion after heat resistance test]
The resin composition or comparative composition prepared in each Example and Comparative Example was applied in a layer form on a copper substrate by spin coating, to form a resin composition layer or comparative composition layer. The copper substrate on which the obtained resin composition layer or comparative composition layer was formed was dried on a hot plate at 100° C. for 5 minutes to form a resin composition layer or comparative composition layer having a uniform thickness on the copper substrate, the thickness of which is described in the “Film Thickness (μm)” column of the table. The resin composition layer or comparative composition layer on the copper substrate was exposed to light of the exposure wavelength ( ^nm) described in the “Exposure Wavelength (nm)” column of the table, using a photomask with a 100 μm square unmasked portion formed in the examples described in the “Development Conditions” column of the table as “Negative” and a photomask with a 100 μm square masked portion formed in the examples described in the “Development Conditions” column of the table as “Positive” at an exposure energy of 500 mJ/cm 2.
In the examples marked with "M" in the exposure condition column, exposure was performed using a stepper as the light source.
In the examples marked with "D" in the exposure conditions column, a direct exposure device (ADTECH DE-6UH III) was used as the light source, and laser direct imaging exposure was performed in an area of 100 μm square without using a photomask.
Thereafter, the resist was developed for 60 seconds with a developer shown in the table to obtain a square resin layer having a length of 100 μm on each side. The description of "aqueous TMAH solution" in the table means an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide.
In the examples in which a numerical value is given in the "Cure temperature" column, the resin composition layer after exposure was heated at a heating rate of 10°C/min in a nitrogen atmosphere using a hot plate. After reaching the temperature given in the "Cure temperature (°C)" column in the table, the temperature was maintained for the time given in the "Cure time (min)" column in the table to obtain a cured product.
In the examples in which "IR" is written in the "Cure temperature (°C)" column, the resin film obtained in each Example was heated at a heating rate of 10°C/min in a nitrogen atmosphere using an infrared lamp heating device (Advance Riko Co., Ltd., RTP-6). After reaching 230°C, the above temperature was maintained for the time indicated in the "Cure time (min)" in the table, and a cured product was obtained.
The copper substrate with the obtained cured product was left in a tank at 175°C under atmospheric pressure for 192 hours. The shear force of the 100 μm square cured product on the copper substrate was measured using a bond tester (CondorSigma, manufactured by XYZTEC) under an environment of 25°C and 65% relative humidity (RH), and evaluated according to the following evaluation criteria. The evaluation results are shown in the column "Adhesion after heat resistance test" in the table. It can be said that the greater the shear force, the better the adhesion of the cured film after the heat resistance test.
-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 greater than 20 gf and not more than 25 gf.
D: The shear force was 20 gf or less.
Also, 1 gf is 0.00980665 N.

[Evaluation of voids at the copper substrate interface after heat resistance test]
The resin composition or comparative composition prepared in each Example and Comparative Example was applied in a layer form by spin coating onto an 8-inch Si wafer with a Cu wiring pattern that had not been pretreated (a Si wafer with a (comb-shaped) Cu wiring pattern of L/S 10 μm (thickness 5 μm)), to form a resin composition layer or a comparative composition layer. The Si wafer on which the obtained resin composition layer or comparative composition layer had been formed was dried on a hot plate at 100° C. for 5 minutes, and a resin composition layer or comparative composition layer having a uniform thickness and having the thickness shown in the “Film Thickness (μm)” column in the table was formed on the substrate (Si wafer). The resin composition layer or the comparative composition layer on the Si wafer was exposed to light with an exposure wavelength ( ^nm ) shown in the "Exposure wavelength (nm)" column of the table, using a photomask with a square unmasked portion of 100 μm on each side in the examples described as "negative" in the "Development conditions" column of the table, and a photomask with a square masked portion of 100 μm on each side in the examples described as "positive" in the "Development conditions" column of the table, with an exposure energy of 500 mJ/cm2.
In the examples marked with "M" in the exposure condition column, exposure was performed using a stepper as the light source.
In the examples marked with "D" in the exposure conditions column, a direct exposure device (ADTECH DE-6UH III) was used as the light source, and laser direct imaging exposure was performed in an area of 100 μm square without using a photomask.
Thereafter, the resist was developed for 60 seconds with a developer shown in the table to obtain a square resin layer having a length of 100 μm on each side. The description of "aqueous TMAH solution" in the table means an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide.
In the examples in which a numerical value is given in the "Cure temperature" column, the resin composition layer after exposure was heated at a heating rate of 10°C/min in a nitrogen atmosphere using a hot plate. After reaching the temperature given in the "Cure temperature (°C)" column in the table, the temperature was maintained for the time given in the "Cure time (min)" column in the table to obtain a cured product.
In the examples in which "IR" is written in the "Cure temperature (°C)" column, the resin film obtained in each Example was heated at a heating rate of 10°C/min in a nitrogen atmosphere using an infrared lamp heating device (Advance Riko Co., Ltd., RTP-6). After reaching 230°C, the above temperature was maintained for the time indicated in the "Cure time (min)" in the table, and a cured product was obtained.
The copper substrate with the obtained cured product was left in a tank at 175° C. in the atmosphere for 192 hours.
Cross-sectional SEM (scanning electron microscope) measurement was carried out to evaluate the void area ratio between the Cu wiring pattern and the cured product. The void area ratio was calculated according to the following formula.
Void area ratio (%)=(area of voids observed by SEM measurement)/(total area of cured material)×100
From the obtained void area ratio, evaluation was performed according to the following evaluation criteria. The evaluation results are shown in the column "Adhesion after heat resistance test" in the table. The smaller the void area ratio, the better the adhesion of the cured film after the heat resistance test, 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 1% or less.
C: The void area ratio was more than 1% but not more than 2%.
D: The void area ratio exceeded 2%.

[Evaluation of resolution on copper substrate]
In each of the Examples and Comparative Examples, a resin substrate having a thin copper layer formed on its surface was used instead of a Si wafer, and the exposure range of the photomask or laser direct imaging exposure was set so that the exposed area would be a line and space pattern in 1 μm increments from 5 μm to 25 μm, and a cured product was obtained in the same manner as in the above-mentioned "Evaluation of adhesion after heat resistance test".
The obtained line pattern of the cured product was observed using a scanning electron microscope (SEM) to determine the minimum line width. Evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the "Resolution on copper substrate" column in the table. It can be said that the smaller the minimum line width formed, the better the resolution.
Evaluation criteria:
A: The minimum line width of the line and space pattern formed was less than 10 μm.
B: The minimum line width of the line and space pattern formed was 10 μm or more and less than 20 μm.
C: The minimum line width of the line and space pattern formed was 20 μm or more, or no pattern was obtained.

From the above results, it is evident that the cured product formed from the resin composition of the present invention has excellent adhesion over a long period of time.
The comparative compositions according to Comparative Examples 1 and 2 do not contain a compound corresponding to compound A. It is clear that such comparative compositions have poor adhesion even after a long period of time has elapsed.

<Example 101>
The resin composition used in Example 1 was applied in a layer form by spin coating on the surface of the thin copper layer of the resin substrate on which the thin copper layer was formed, and dried at 100° C. for 5 minutes to form a photosensitive film with a thickness of 20 μm, which was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line and space pattern and a line width of 10 μm). After the exposure, the layer was developed with cyclopentanone 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 a semiconductor device was manufactured using this interlayer insulating film for redistribution layers, it was confirmed that the device operated without any problems.

Claims

At least one resin selected from the group consisting of cyclized resins and precursors thereof, and
A resin composition comprising a compound A that satisfies the following conditions 1 and 2:
Condition 1: The compound has two or more aromatic heterocycles which contain one or more atoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom as a ring member, and in which a hydrogen atom may be substituted and which may have a condensed ring structure. Condition 2: The compound has an aromatic amino group.
The resin composition according to claim 1, wherein compound A is a compound represented by the following formula (A-1):

In formula (A-1), the ring structures represented by Het each independently represent an aromatic heterocycle which may have a substituent and which may be condensed with another ring, and R 1 represents a hydrogen atom or a monovalent organic group.
The ring structures represented by Het in formula (A-1) are each independently any of the structures represented by the following formulas (A-1-1) to (A-1-3). The resin composition according to claim 1 or 2.

In formula (A-1-1), Y 1 to Y 4 each independently represent -CR 2 = or -N=, R 2 represents a hydrogen atom or an arbitrary organic group, and when two or more of Y 1 to Y 4 represent -CR 2 =, at least two of R 2 may be linked to form a ring structure, and * represents a bonding site with the nitrogen atom to which R 1 in formula (A-1) is bonded.
In formula (A-1-2), Y5 to Y7 each independently represent -CR2 = or -N=, R2 represents a hydrogen atom or any organic group, and when two or more of Y5 to Y7 represent -CR2 =, at least two of R2 may be linked to form a ring structure, and * represents a bonding site with the nitrogen atom to which R1 in formula (A-1) is bonded.
In formula (A-1-3), X represents -O-, -S- or -NR3- ; R3 represents a hydrogen atom or any organic group; Y8 and Y9 each independently represent -CR2 = or -N=; R2 represents a hydrogen atom or any organic group; when Y8 and Y9 are -CR2 =, two R2 may be linked to form a ring structure; and * represents a bonding site with the nitrogen atom to which R1 in formula (A-1) is bonded.
The resin composition according to claim 1 or 2, wherein compound A is a compound represented by formula (A-2).

In formula (A-2), R 21 is a hydrogen atom or a monovalent organic group, Y 21 to Y 26 are each -CR 24 = or -N=, R 24 is a hydrogen atom, an alkyl group, a hydroxyl group, or a carbamoyl group, and R 22 and R 23 are each independently a hydrogen atom, an alkyl group, or a carbamoyl group.
The resin composition according to claim 1 or 2, wherein the cyclized resin or the cyclized resin precursor is a polyimide or a polyimide precursor.
The resin composition according to claim 1 or 2, further comprising a photopolymerization initiator.
The resin composition according to claim 1 or 2, further comprising a compound having an aromatic heterocycle and different from compound A.
The resin composition according to claim 1 or 2, which is used to form an interlayer insulating film for a rewiring layer.
A cured product obtained by curing the resin composition according to claim 1 or 2.
A laminate comprising two or more layers of the cured product according to claim 9, and a metal layer between any of the layers of the cured product.
A method for producing a cured product, comprising a film-forming step of applying the resin composition according to claim 1 or 2 onto a substrate to form a film.
The method for producing the cured product according to claim 11, 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.
The method for producing the cured product according to claim 11 includes a heating step in which the film is heated at 50 to 450°C.
A method for producing a laminate, comprising the method for producing a cured product according to claim 11.
A method for manufacturing a semiconductor device, comprising the method for manufacturing the cured product according to claim 11.
A semiconductor device comprising the cured product according to claim 9.