TW202419523A - Resin composition, cured article, laminate, method for producing cured article, method for producing laminate, method for producing semiconductor device, and semiconductor device - Google Patents

Abstract

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. The resin composition comprises: at least one resin selected from the group consisting of cyclized resins and precursors thereof; and a compound A represented by formula (A-1) having a total carbon number of 3 to 30, wherein ^R1 represents a monovalent organic group, the bonding site of ^R1 to the nitrogen atom described in formula (A-1) is a carbon atom, ^R2 represents a hydrogen atom or a monovalent organic group, ^R3 represents a monovalent organic group, and ^R2 and ^R3 may bond to form a ring structure.

Description

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

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

Nowadays, the technology of resin materials made from resin compositions containing resins is being used in various fields. For example, cyclic resins such as polyimide are excellent in heat resistance and insulation, and are therefore suitable for various uses. The above uses are not particularly limited, and if semiconductor components for mounting are used as an example, they can be used as insulating films, sealing materials, or protective films. In addition, they can also be used as base films and cover films for flexible substrates.

For example, in the above-mentioned applications, cyclized resins such as polyimide are used in the form of resin compositions containing cyclized resins or precursors of cyclized resins such as polyimide precursors. For example, such resin compositions are applied to a substrate by coating to form a photosensitive film, and then exposed, developed, heated, etc. as needed to form a cured product on the substrate. The precursors of the above-mentioned cyclized resins such as polyimide precursors are cyclized by heating, for example, and become cyclized resins such as polyimide in the cured product. The resin composition can be applied by a known coating method, etc., so it can be said that the resin composition has excellent manufacturing adaptability, such as high design freedom in the shape, size, and application position of the resin composition. In addition to the high performance of cyclic resins such as polyimide, this manufacturing adaptability is also excellent. The expansion of the application of the above-mentioned resin composition in the industry is increasingly expected.

For example, Patent Document 1 discloses a curable resin composition comprising (A) an alkali-soluble resin, (B) a copolymer resin, (C) a photopolymerization initiator that generates free radicals and alkali, (D) an epoxy resin, and (E) a black colorant, wherein the alkali-soluble resin (A) contains (A1) a carboxyl group-containing amide resin, and the content of the black colorant (E) is 1.0 mass % or more relative to the total mass of the solid components of the curable resin composition.

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-186659

The resin composition used to obtain the cured product is required to have excellent adhesion to the substrate even after being exposed to high temperature conditions.

The object of the present invention is to provide a resin composition in which the obtained cured product has excellent adhesion to a substrate even after being exposed to high temperature conditions, a cured product obtained by curing the above resin composition, a laminate including the above cured product, a method for producing the above cured product, a method for producing the above laminate, a method for producing a semiconductor device including the method for producing the above cured product, and a semiconductor device including the above cured product.

Representative embodiments of the present invention are shown below. <1> A resin composition comprising: at least one resin selected from the group consisting of cyclized resins and precursors thereof; and a compound A represented by the following formula (A-1) having a total carbon number of 3 to 30. [Chemical Formula 1] In formula (A-1), ^R1 represents a monovalent organic group, the bonding site of ^R1 to the nitrogen atom described in formula (A-1) is a carbon atom, ^R2 represents a hydrogen atom or a monovalent organic group, ^R3 represents a monovalent organic group, and ^R2 and ^R3 may bond to form a ring structure. <2> The resin composition as described in <1>, which contains a compound represented by the following formula (A-2) as the above-mentioned compound A. [Chemical Formula 2] In formula (A-2), Ar ¹ and Ar ² are each independently an aromatic group which may have a substituent and has at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms and phosphorus atoms at at least one of the ring members of the aromatic group and the substituent, and R ² represents a hydrogen atom or a monovalent organic group. <3> The resin composition as described in <2>, wherein at least one of Ar ¹ , Ar ² and R ² has a phenolic hydroxyl group. <4> The resin composition as described in <2> or <3>, wherein at least one of Ar ¹ , Ar ² and R ² has a heterocyclic structure. <5> The resin composition as described in any one of <1> to <4>, wherein the resin is a polyimide or a polyimide precursor. <6> The resin composition as described in any one of <1> to <5>, further comprising a photopolymerization initiator and a polymerizable compound. <7> The resin composition as described in any one of <1> to <6>, which is used to form an interlayer insulating film for a redistribution layer. <8> A cured product obtained by curing the resin composition as described in any one of <1> to <7>. <9> A laminate comprising two or more layers composed of the cured product as described in <8>, and comprising a metal layer between any of the layers composed of the cured product. <10> A method for producing a cured product, comprising a film forming step of applying the resin composition as described in any one of <1> to <7> to a substrate to form a film. ＜11＞A method for producing a cured product as described in ＜10＞, comprising: an exposure step of selectively exposing the above-mentioned film; and a developing step of developing the above-mentioned film using a developer to form a pattern. ＜12＞A method for producing a cured product as described in ＜10＞ or ＜11＞, comprising a heating step of heating the above-mentioned film at 50 to 450°C. ＜13＞A method for producing a laminate, comprising the method for producing a cured product as described in any one of ＜10＞ to ＜12＞. ＜14＞A method for producing a semiconductor element, comprising the method for producing a cured product as described in any one of ＜10＞ to ＜12＞. ＜15＞A semiconductor element comprising the cured product as described in ＜8＞. [Effect of the Invention]

According to the present invention, there are provided a resin composition in which the obtained cured product has excellent adhesion to a substrate even after being exposed to high temperature conditions, 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.

The main embodiments of the present invention are described below. However, the present invention is not limited to the embodiments indicated. In this specification, the numerical range represented by the symbol "～" means a range including the numerical values recorded before and after "～" as the lower limit and the upper limit, respectively. In this specification, the term "step" means not only independent steps, but also steps that cannot be clearly distinguished from other steps as long as the expected effect of the step can be achieved. In the marking of the base (atomic group) in this specification, the marking without the mark of substituted and unsubstituted includes the base (atomic group) without substituents and also includes the base (atomic group) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, as light used for exposure, the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active light or radiation such as electron beams can be listed. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic acid" means both or either of "acrylic acid" and "methacrylic acid", and "(meth)acryloyl" means both or either of "acryloyl" and "methacryloyl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. In addition, in this specification, the solid content concentration is the mass percentage of the other components excluding the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) and are defined as polystyrene conversion values. In this specification, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) is used as a column by connecting the protective column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) in series to obtain the weight average molecular weight (Mw) and number average molecular weight (Mn). Unless otherwise specified, the molecular weights are measured using THF (tetrahydrofuran) as an eluent. In the case of low solubility, when THF is not suitable as an eluent, NMP (N-methyl-2-pyrrolidone) can also be used. In addition, unless otherwise specified, a UV ray (ultraviolet) detector with a wavelength of 254nm is used for detection in GPC measurement. In this specification, when the positional relationship of each layer constituting the laminate is recorded as "upper" or "lower", it is sufficient as long as there are other layers on the upper or lower side of the layer that serves as the reference among the multiple layers concerned. That is, a third layer or element may be further inserted between the layer that serves as the reference and the other layers mentioned above, and the layer that serves as the reference and the other layers mentioned above do not need to be in contact. Unless otherwise specified, the direction of stacking layers on the substrate is called "upper", or when there is a resin component layer, the direction from the substrate toward the resin component layer is called "upper", and the opposite direction is called "lower". Furthermore, this setting of the up and down directions is for the convenience of explaining this specification. In actual forms, the "upper" direction in this specification may also be different from the vertical upward direction. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to the component as each component contained in the composition. In addition, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325Pa (1 atmosphere), and the relative humidity is 50%RH. In this specification, a combination of a preferred embodiment is a more preferred embodiment.

(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 represented by the following formula (A-1) having a total carbon number of 3 to 30. [Chemical formula 3] In formula (A-1), ^R1 represents a monovalent organic group, the bonding site of ^R1 to the nitrogen atom described in formula (A-1) is a carbon atom, ^R2 represents a hydrogen atom or a monovalent organic group, ^R3 represents a monovalent organic group, and ^R2 and ^R3 may bond to form a ring structure.

The resin composition of the present invention is preferably used to form a photosensitive film (for exposure and development), and is preferably used to form a film (for 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 of a semiconductor element, 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. In particular, the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, which is also one of the better embodiments of the present invention. In addition, the resin composition of the present invention can be used to form a photosensitive film for positive development, and can also be used to form a photosensitive film for negative development. In the present invention, negative development refers to development in which the non-exposed portion is removed by development during exposure and development, and positive development refers to development in which the exposed portion is removed by development. As the above-mentioned exposure method, the above-mentioned developer, and the above-mentioned developing method, for example, the exposure method described in the exposure step in the description of the method for producing a hardened product described later, the developer and the developing method described in the developing step can be used.

According to the resin composition of the present invention, a hardened material having excellent adhesion to a substrate (particularly a metal substrate, and further a copper substrate) can be obtained even after exposure to high temperature conditions. The mechanism for achieving the above effect is not yet clear, but it is speculated as follows.

The resin composition of the present invention contains a compound A having a specific structure. Conventionally, in order to improve the adhesion between a cured product formed from a resin composition and a substrate, a technique of blending a compound having a nitrogen atom into a resin composition has been conducted. Here, it is considered that the adhesion can be further improved by increasing the number of nitrogen atoms in the above-mentioned compound. However, the above-mentioned compound sometimes has low thermal stability, and sometimes cannot maintain adhesion when exposed to high temperature conditions, for example. For example, 2-pyridinecarbaldehyde = 2-pyridyl hydrazone is described in the previous document 1, but the compound has a structure in which a nitrogen atom is directly bonded to a nitrogen atom in a C=N bond as a Schiff base site by a single bond. It is known that a compound having such a structure is easily decomposed under high temperature conditions. In this specification, a certain structure directly bonds to another structure means that the structures are bonded to each other without a linking group or the like. The compound A of the present invention has a structure represented by formula (A-1). It is believed that since the compound represented by formula (A-1) is directly bonded to the nitrogen atom in the C=N bond as the Schiff base site, not the nitrogen atom as described above, the heat resistance is excellent, and compound A is not easily decomposed under high temperature conditions. As a result, it is believed that the cured product obtained from the resin composition of the present invention has excellent adhesion to the substrate (especially the metal substrate, and further the copper substrate) even after being exposed to high temperature conditions. In general, when it is desired to improve the adhesion to the substrate, measures to increase the number of nitrogen atoms in the compound are sometimes adopted. However, it was found that the present invention does not simply increase the number of nitrogen atoms, but introduces a structure in which carbon atoms are directly bonded to the nitrogen atoms in the C=N bond of the Schiff base site as described above, thereby achieving an effect of improving the adhesion to the substrate even after exposure to high temperature conditions. This effect could not be expected from previous literature. In addition, as described above, the compound A of the present invention is a compound with high thermal stability, and it is believed that this compound is not easy to decompose during the storage of the composition. It is believed that, as a result, the stability of the composition itself (composition stability) of the composition containing this compound A is also excellent.

Here, Patent Document 1 does not describe a composition containing a precursor of a cyclized resin and compound A.

Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

<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 their precursors. 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, "main chain" means the longest bond in the resin molecule, and "side chain" means other bonds. Examples of cyclized resins include polyimide, polybenzoxazole, polyamide imide, etc. The precursor of the cyclized resin refers to a resin that changes its chemical structure due to external stimulation and becomes a cyclized resin. It is more preferred that the resin changes its chemical structure due to heat and it is more preferred that the resin forms a cyclized resin by forming a ring structure due to heat-induced ring closing reaction. As the precursor of the cyclized resin, polyimide precursors, polybenzoxazole precursors, polyamide imide precursors, etc. can be listed. That is, the resin composition preferably contains at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide imide and polyamide imide precursor as the specific resin. The resin composition preferably contains polyimide or polyimide precursor as the specific resin. The specific resin preferably has a polymerizable group, and more preferably contains a free radical polymerizable group. When the specific resin has a free radical polymerizable group, the resin composition of the present invention preferably contains a free radical polymerization initiator, and more preferably contains a free radical polymerization initiator and a free radical crosslinking agent. If necessary, it can further contain a sensitizer. This resin composition, for example, forms a negative photosensitive film. In addition, the specific resin may have a polar conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, it is preferred that the resin composition contains a photoacid generator. This resin composition, for example, forms a positive photosensitive film or a negative photosensitive film of a chemically amplified type.

[Polyimide Precursor] The type of the polyimide precursor used in the present invention is not particularly limited, but it is preferably a polyimide precursor containing a repeating unit represented by the following formula (2). [Chemical Formula 4] 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.

^A1 and ^A2 in formula (2) each independently represent an oxygen atom or ^-NRz- , preferably an oxygen atom. ^Rz represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom. ^R111 in formula (2) represents a divalent organic group. Examples of the divalent organic group include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, preferably linear or branched aliphatic groups having 2 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 3 to 20 carbon atoms or groups composed of a combination thereof, and more preferably groups containing aromatic groups having 6 to 20 carbon atoms. The alkyl groups in the chain of the above-mentioned straight or branched aliphatic groups may be substituted by groups containing heteroatoms, and the alkyl groups of the ring members of the above-mentioned cyclic aliphatic groups and aromatic groups may be substituted by groups containing heteroatoms. Examples of R ¹¹¹ in formula (2) include groups represented by -Ar- and -Ar-L-Ar-, and groups represented by -Ar-L-Ar- are preferred. Here, Ar is independently an aromatic group, and L is a single bond or a fluorine-substituted aliphatic alkyl group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a group composed of a combination of two or more of the above. The preferred ranges 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 diamine may be used, or two or more diamines 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 composed of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The alkyl group in the chain of the linear or branched aliphatic group may be substituted with a group containing a heteroatom, and the alkyl group of the ring member of the cyclic aliphatic group and the aromatic group may be substituted with a group containing a heteroatom. As examples of the group containing an aromatic group, the following groups can be cited.

[Chemical formula 5] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO ₂ -, -NHCO-, or a combination thereof, more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO ₂ -, 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.

As the diamine, specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane can be cited; 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 can be cited; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4’- or 3,3’-diaminobiphenyl, 4,4’- or 3,3’-diaminodiphenyl ether, 4,4’- or 3,3’-diaminodiphenylmethane, 4,4’- or 3,3’-diaminodiphenyl sulfide, 4,4’- or 3,3’-diaminodiphenyl sulfide, 4,4’- or 3,3’-diaminobenzophenone, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 3,3’-dimethoxy 4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-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)sulfonate, bis(4-amino-3-hydroxyphenyl)sulfonate, 4,4'-diaminobiphenyl 4-(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfonate, bis[4-(3-aminophenoxy)phenyl]sulfonate, bis[4-(2-aminophenoxy)phenyl]sulfonate, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfonate, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)anthracene )benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1, 5-Diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- or 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, diaminotrifluorotoluene, 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, At least one of the following diamines: 4’-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4’-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3’,5,5’-tetramethyl-4,4’-diaminobiphenyl, 4,4’-diamino-2,2’-bis(trifluoromethyl)biphenyl, 2,2’,5,5’,6,6’-hexafluorotoluidine or 4,4’-diaminoquaternaryl.

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

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

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

Furthermore, from the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 6] In formula (51), R ⁵⁰ to R ⁵⁷ are independently a hydrogen atom, a fluorine atom or a monovalent organic group, at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (2). Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. [Chemical Formula 7] In formula (61), R ⁵⁸ and R ⁵⁹ are independently a fluorine atom, a methyl group or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that impart a 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, and 4,4'-diaminooctafluorobiphenyl. These can be used alone or in combination of two or more.

R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * independently represents a bonding site with other structures. [Chemical Formula 8] In formula (5), R ¹¹² is a single bond or a divalent linking group, preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO ₂ - and -NHCO-, and combinations thereof, more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -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 -.

Specifically, R ¹¹⁵ can be exemplified by tetracarboxylic acid residues remaining after the anhydride group is removed from tetracarboxylic acid dianhydride. As a structure corresponding to R ¹¹⁵ , the polyimide precursor may contain only one tetracarboxylic acid dianhydride residue or may contain two or more tetracarboxylic acid dianhydride residues. The tetracarboxylic acid dianhydride is preferably represented by the following formula (O). [Chemical Formula 9] In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as the preferred range of R ¹¹⁵ in formula (2).

Specific examples of tetracarboxylic dianhydrides include pyromelitic acid dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane tetracarboxylic dianhydride, 2,3,4,4'-bis(3,4-dicarboxyphenyl)propane tetracarboxylic ...4,4'-bis(3,4-dicarboxyphenyl)propane tetracarboxylic dianhydride, 2,3,4,4'-bis(3, 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-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-6 alkyl and C1-6 alkoxy derivatives thereof.

Moreover, as a more preferred example, tetracarboxylic dianhydride (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be cited.

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may have an OH group. More specifically, as R ¹¹¹ , a residual group of a diaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ in formula (2) each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, an aromatic group or a polyalkylene group is preferred. Furthermore, at least one of R ¹¹³ and R ¹¹⁴ preferably contains a polymerizable group, and it is more preferred that both contain a polymerizable group. It is also preferred that at least one of R ¹¹³ and R ¹¹⁴ contains two or more polymerizable groups. As the polymerizable group, a group capable of undergoing a crosslinking reaction by the action of heat, free radicals, etc. is preferred. A free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having ethylenic unsaturated bonds, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, cyclohexyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As free radical polymerizable groups possessed by the polyimide precursor, groups having ethylenic unsaturated bonds are preferred. As groups having ethylenic unsaturated bonds, vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having aromatic rings directly bonded to vinyl groups (e.g., vinylphenyl groups), (meth)acrylamide groups, (meth)acryloxy groups, groups represented by the following formula (III), etc. are preferred. Groups represented by the following formula (III) are preferred.

[Chemical formula 10]

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred. In formula (III), * represents a bonding site with other structures. 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 polyalkylene group. Preferred examples of R ²⁰¹ include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH ₂ CH (OH) CH ₂ -, and a polyalkylene group. Alkylene groups such as ethylene and propylene, -CH ₂ CH (OH) CH ₂ -, cyclohexyl, and a polyalkylene group are more preferred. Alkylene groups such as ethylene and propylene or a polyalkylene group are further preferred. In the present invention, a polyalkoxyl group refers to a group in which two or more alkoxyl groups are directly bonded. The alkylene groups in the multiple alkoxyl groups contained in the polyalkoxyl group may be the same or different. When the polyalkoxyl group contains multiple alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, an arrangement with blocks, or an arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is further preferred, 2 or 3 is further preferred, and 2 is particularly preferred. In addition, the above-mentioned alkylene group may have a substituent. As preferred substituents, alkyl groups, aryl groups, halogen atoms, etc. can be listed. Furthermore, the number of alkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, and further preferably 2 to 6. As the polyalkoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is preferred, polyethyleneoxy or polypropyleneoxy is more preferred, and polyethyleneoxy is further preferred. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in alternating patterns. The preferred aspects of the number of repetitions of the ethyleneoxy groups and the like in the groups are as described above.

In formula (2), when R ¹¹³ is a hydrogen atom or R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugate 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 polar 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 hydroxyl group or a carboxyl group. An acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, and the like are preferred. 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 tertiary butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tertiary butoxycarbonylmethyl group, a trimethylsilyl ether group, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuryl group is preferred.

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

In order to improve the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as diamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

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 containing the repeating unit represented by formula (2-A) in the polyimide precursor, the width of the exposure latitude can be further increased. Formula (2-A) [Chemical Formula 11] In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of ^R113 and ^R114 is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.

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

The polyimide precursor may contain one or more types of repeating units represented by formula (2). Furthermore, it may contain structural isomers of the repeating units represented by formula (2). In addition to the repeating units represented by the above formula (2), the polyimide precursor may also contain other types of repeating units.

As an embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, more preferably 90 mol% or more, and even more preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all the repeating units in the polyimide precursor except the terminal can be the 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 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 more preferably 4,000 to 20,000. The molecular weight dispersion of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and more preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly specified, but for example, 7.0 or less is preferred, 6.5 or less is more preferred, and 6.0 or less is further preferred. In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight/number average molecular weight. In addition, when the resin composition contains a plurality of polyimide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight and dispersion of at least one polyimide precursor are within the above ranges. In addition, it is also preferred that the weight average molecular weight, number average molecular weight and dispersion calculated using the above-mentioned plurality of polyimide precursors as one resin are within the above ranges.

[Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer having an organic solvent as a main component. In this specification, an alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23°C. From the viewpoint of pattern formation, it is preferred to dissolve 0.5 g or more of the polyimide, and it is further preferred to dissolve 1.0 g or more of the polyimide. The upper limit of the above-mentioned dissolution amount is not particularly limited, but it is preferably 100 g or less. From the viewpoint of the membrane strength and insulation of the obtained organic membrane, polyimide having multiple imide structures in the main chain is preferred.

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

-Silicon Atoms- From the viewpoint of the film strength of the obtained organic film, it is also preferable that the polyimide has silicon atoms. The silicon atoms are preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later, and are more preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later as an organic modified (poly)siloxane structure described later. The above silicon atoms or the above organic modified (poly)siloxane structure may also be contained in the side chain of the polyimide, but are 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.

-Ethylenic unsaturated bond- From the viewpoint of the membrane strength of the obtained organic membrane, it is preferable that the polyimide has an ethylenic unsaturated bond. The polyimide may have an ethylenic unsaturated bond at the end of the main chain or in the side chain, but it is preferable that it has an ethylenic unsaturated bond in the side chain. It is preferable that the above-mentioned ethylenic unsaturated bond has free radical polymerizability. It is preferable that the ethylenic unsaturated bond is contained in R ¹³² or R ¹³¹ in the repeating unit represented by formula (4) described later, and it is more preferable that it is contained in R ¹³² or R ¹³¹ as a group having an ethylenic unsaturated bond. Among them, the ethylenically unsaturated bond is preferably contained in ^R131 in the repeating unit represented by the formula (4) described later, and is more preferably contained in ^R131 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 vinylphenyl group, a group having a vinyl group which is directly bonded to an aromatic ring and may be substituted, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

[Chemical formula 12]

In formula (IV), R ²⁰ represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, and a hydrogen atom or a methyl group is preferred.

In formula (IV), ^R21 represents an alkylene group having 2 to 12 carbon atoms, -O- _CH2CH (OH) _CH2- , -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms, and the number of repetitions of the alkyleneoxy group is 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), or a combination of two or more of these groups. The alkylene group having 2 to 12 carbon atoms may be any of a linear, branched, cyclic, or a combination thereof. The alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and particularly preferably an alkylene group having 2 to 4 carbon atoms.

Among them, ^R21 is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1). [Chemical Formula 13] In formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbon atoms, a (poly)alkoxyene group having 2 to 30 carbon atoms, or a group in which two or more of these groups are bonded, X represents an oxygen atom or a sulfur atom, * represents a bonding site to another structure, and ● represents a bonding site to the oxygen atom to which R ²¹ 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)alkoxyene group having 2 to 30 carbon atoms as L are the same as preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms as R ²¹ in formula (IV). In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and the preferred embodiment is also the same. The structure represented by formula (R1) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenic unsaturated bond (for example, 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenic unsaturated bond (for example, 2-hydroxyethyl methacrylate). The structure represented by the formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenic unsaturated bond (for example, glycidyl methacrylate).

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

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

-Polymerizable groups other than groups having ethylenic unsaturated bonds- Polyimide may contain polymerizable groups other than groups having ethylenic unsaturated bonds. Examples of polymerizable groups other than groups having ethylenic unsaturated bonds include cyclic ether groups such as epoxy groups, cyclohexane groups such as oxybutane groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups. The polymerizable groups other than groups having ethylenic unsaturated bonds are preferably contained in ^R131 in the repeating unit represented by formula (4) described later. The amount of polymerizable groups other than groups having ethylenic 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 ^R113 and ^R114 in the above formula (2), and the preferred embodiment is also the same. The polarity conversion group is included in, for example, ^R131 and ^R132 in the repeating unit represented by the formula (4) described later, the terminal of the polyimide, etc.

-Acid value- When polyimide is subjected to alkaline development, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more from the viewpoint of improving the developability. The above acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and more preferably 200 mgKOH/g or less. When polyimide is subjected to development using a developer having an organic solvent as a main component (e.g., "solvent development"), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, more preferably 2 to 30 mgKOH/g, and more preferably 5 to 20 mgKOH/g. The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992. As the acid group contained in the polyimide, from the viewpoint of both storage stability and developing property, the acid group with a pKa of 0 to 10 is preferred, and the acid group with a pKa of 3 to 8 is more preferred. pKa is the equilibrium constant Ka expressed by its negative common logarithm pKa in consideration of the dissociation reaction of releasing hydrogen ions from the acid. In this manual, unless otherwise specified, pKa is a calculated value based on ACD/ChemSketch (registered trademark). pKa can also refer to the value published in the "Fifth Revised Edition of Chemical Handbook Basic Edition" compiled by the Chemical Society of Japan. When the acid group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

- Phenolic hydroxyl group - From the viewpoint of making the developing speed using an alkaline developer appropriate, it is preferred that the polyimide has a phenolic hydroxyl group. The polyimide may have a phenolic hydroxyl group at the end of the main chain or at the side chain. The phenolic hydroxyl group is preferably contained in R ¹³² or R ¹³¹ in the repeating unit represented by formula (4) described later. The amount of the phenolic hydroxyl group relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but preferably contains a repeating unit represented by the following formula (4). [Chemical Formula 14] In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When there is a polymerizable group, the polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , as shown in the following formula (4-1) or formula (4-2), or may be located at the end of the polyimide. Formula (4-1) [Chemical Formula 15] In formula (4-1), R ¹³³ is a polymerizable group, and the other groups have the same meanings as in formula (4). Formula (4-2) [Chemical formula 16] At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group. When it is not a polymerizable group, it is an organic group. The other groups have the same meanings as in formula (4).

As the polymerizable group, there can be listed a group containing the above-mentioned ethylenic unsaturated bond or a crosslinking group other than the group having the above-mentioned ethylenic unsaturated bond. R ¹³¹ represents a divalent organic group. As the divalent organic group, there can be listed the same as R ¹¹¹ in formula (2), and the preferred range is also the same. As R ¹³¹ , there can be listed a diamine residue remaining after removing the amino group of the diamine. As the diamine, there can be listed aliphatic, cycloaliphatic or aromatic diamines, etc. As a specific example, there can be listed the example of R ¹¹¹ in formula (2) of the polyimide precursor.

From the viewpoint of more effectively suppressing the warping during calcination, R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain. More preferably, it is a diamine residue containing two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule, and further preferably, it is a diamine residue containing the above diamines and no aromatic ring.

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

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group include the same ones as those for R ¹¹⁵ in formula (2), and the preferred range is also the same. For example, four bonders of the tetravalent organic group exemplified as R ¹¹⁵ are bonded to four -C(=O)- moieties in the above formula (4) to form a condensed ring.

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

It is also preferred that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, as R ¹³¹ , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above-mentioned (DA-1) to (DA-18) can be cited as preferred examples, and as R ¹³² , the above-mentioned (DAA-1) to (DAA-5) can be cited as more preferred examples.

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

In order to improve the adhesion to the substrate, polyimide can be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. can be mentioned.

In order to improve the storage stability of the resin composition, the main chain terminal of the polyimide is preferably capped with a capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, a monoactive ester compound, etc. Among them, it is more preferred to use a monoamine. As preferred compounds of the monoamine, 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 ...6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1- Naphthalene, 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 a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Imidization rate (ring closure rate)- From the viewpoint of the film strength and insulation of the obtained organic film, the imidization rate (also called "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. The upper limit of the above-mentioned imidization rate is not particularly limited, and it can be 100% or less. For example, the above-mentioned imidization rate can be measured by the following method. The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377cm ^-1 , which is the absorption peak originating from the imide structure. Then, after the polyimide is heat-treated at 350°C for 1 hour, the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1377cm ^-1 . The obtained peak intensities P1 and P2 can be used to calculate the imidization rate of polyimide according to 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 the combinations of ^R131 and ^R132 of all repeating units are the same, or may contain repeating units represented by the above formula (4) in which the combinations of ^R131 and ^R132 are different from each other. In addition to the repeating units represented by the above formula (4), the polyimide may contain other types of repeating units. Examples of other types of repeating units include repeating units represented by the above formula (2).

Polyimide can be synthesized by, for example, the following methods: a method of reacting tetracarboxylic dianhydride with diamine (part of which is substituted with a monoamine end-capping agent) at low temperature; a method of reacting tetracarboxylic dianhydride (part of which is substituted with an acid anhydride or a monoacyl chloride compound or a monoactive ester compound end-capping agent) with diamine at low temperature; a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting the diester with diamine (part of which is substituted with a monoamine end-capping agent) in the presence of a condensing agent; a method of reacting tetracarboxylic dianhydride with an alcohol and reacting the diester with a diamine (part of which is substituted with a monoamine end-capping agent) in the presence of a condensing agent; A method of obtaining a polyimide precursor by a method such as obtaining a diester from a carboxylic acid dianhydride and an alcohol, then acylchlorinating the remaining dicarboxylic acid, and reacting the resulting product with a diamine (part of which is substituted with a monoamine end-capping agent), and then completely imidizing the product using a known imidization reaction method; or a method of stopping the imidization reaction midway and introducing a portion of the imide structure; and a method of introducing a portion of the imide structure by mixing a completely imidized polymer with the polyimide precursor. In addition, 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 more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., elongation at break), the weight average molecular weight is particularly preferably 15,000 or more. The number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and more preferably 4,000 to 20,000. The molecular weight dispersion of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and more preferably 2.0 or more. The upper limit of the molecular weight dispersion of the polyimide is not particularly specified, but for example, 7.0 or less is preferred, 6.5 or less is more preferred, and 6.0 or less is more preferred. When the resin composition contains a plurality of polyimides as specific resins, the weight average molecular weight, number average molecular weight and dispersion of at least one polyimide are preferably within the above ranges. It is also preferred that the weight average molecular weight, number average molecular weight and dispersion calculated for the plurality of polyimides as one resin are respectively within the above ranges.

[Polybenzoxazole precursor] As polybenzoxazole precursors, compounds described in paragraphs 0073 to 0095 of International Publication No. 2022/145355 can be cited. The above description is incorporated into this specification.

[Polybenzoxazole] As polybenzoxazole, compounds described in paragraphs 0096 to 0103 of International Publication No. 2022/145355 can be cited. The above description is incorporated into this specification.

[Polyamide imide precursor] As polyamide imide precursors, compounds described in paragraphs 0104 to 0119 of International Publication No. 2022/145355 can be cited. The above description is incorporated into this specification.

[Polyamide imide] As polyamide imide, the compounds described in paragraphs 0120 to 0133 of International Publication No. 2022/145355 can be cited. The above description is incorporated into this specification.

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

-Capping agent- In the manufacturing method of polyimide precursors, in order to further improve the storage stability, it is preferred to cap the carboxylic anhydride, anhydride derivative or amine group remaining at the end of the resin of the polyimide precursor. When capping the carboxylic anhydride and anhydride derivative remaining at the end of the resin, monoalcohols, phenols, thiols, thiophenols, monoamines, etc. can be listed as the capping agent. In terms of reactivity and film stability, monoalcohols, phenols, and monoamines are more preferred. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol, secondary alcohols such as isopropanol, 2-butanol, cyclohexanol, cyclopentanol, and 1-methoxy-2-propanol, and tertiary alcohols such as tertiary butanol and adamantanol. Preferred phenol compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene. Moreover, as preferred monoamine compounds, there can be mentioned 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 can be used, and multiple different terminal groups can be introduced by reacting multiple end-capping agents. In addition, when the amine group at the end of the resin is capped, it can be capped with a compound having a functional group that can react with the amine group. Preferable end-capping agents for amino groups are carboxylic anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic anhydride, etc., and carboxylic acid anhydride and carboxylic acid chloride are more preferred. Preferable compounds of carboxylic anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, etc. Preferable compounds of carboxylic acid chloride include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, neopentanoyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyl chloride, stearyl chloride, benzoyl chloride, etc.

-Solid precipitation- When manufacturing a polyimide precursor, etc., a solid precipitation step may be included. Specifically, after filtering the water absorption byproduct of the dehydration condensation agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohol or a mixture thereof to precipitate the polymer component, thereby precipitating it as a solid and drying it to obtain a polyimide precursor. In order to improve the purity, the polyimide precursor may be repeatedly subjected to redissolution, reprecipitation, drying and the like. It may also further 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, further preferably 40% by mass or more, and further preferably 50% by mass or more relative to the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 97% by mass or less, and further preferably 95% by mass or less relative to 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 containing two or more specific resins, the total amount is preferably within the above range.

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

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

When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more relative to the total solid content of the resin composition. Relative to the total solid content of the resin composition, the content of the other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. As a preferred embodiment of the resin composition of the present invention, it can also be set to an embodiment in which the content of other resins is low. In the above embodiment, relative to the total solid content of the resin composition, the content of other resins is preferably 20% by mass or less, 15% by mass or less is more preferred, 10% by mass or less is further preferred, 5% by mass or less is further preferred, and 1% by mass or less is further preferred. The lower limit of the above content is not particularly limited, and 0% by mass or more is sufficient. The resin composition of the present invention may contain only one other resin, or may contain two or more other resins. When containing two or more specific resins, it is preferred that the total amount is within the above range.

<Compound A> The resin composition of the present invention contains compound A. Compound A is a compound represented by the following formula (A-1) and the total number of carbon atoms in formula (A-1) is 3 to 30. [Chemical Formula 17] In formula (A-1), ^R1 represents a monovalent organic group, the bonding site of ^R1 to the nitrogen atom described in formula (A-1) is a carbon atom, ^R2 represents a hydrogen atom or a monovalent organic group, ^R3 represents a monovalent organic group, and ^R2 and ^R3 may bond to form a ring structure.

[Total carbon number] The total carbon number of formula (A-1) is 3 to 30. The total carbon number of formula (A-1) refers to the total number of all carbon atoms contained in the compound represented by formula (A-1). The chemical resistance of the obtained hardened material is excellent when the total carbon number is 30 or less. It is believed that the copper corrosion inhibitor that cannot be adsorbed on the substrate exists on the surface of the film or at a depth position in the middle. However, it is believed that if molecules with a total carbon number exceeding 30 exist on the surface of the film, etc. as described above, the plasticity of the film increases and the solubility of the film increases, thereby reducing the chemical resistance. The lower limit of the above carbon number is preferably 4 or more, more preferably 5 or more, and more preferably 6 or more. The upper limit of the above carbon number is preferably 25 or less, more preferably 22 or less, and more preferably 20 or less.

[R ¹ ] In the formula (A-1), R ¹ may be an aliphatic group or an aromatic group, and an aromatic group is preferred. Examples of the aliphatic group include an alkyl group and the like.

The aromatic group may be an aromatic alkyl group or an aromatic heterocyclic group. However, an aromatic heterocyclic group is preferred from the viewpoint of the adhesion of the cured product after exposure to heating conditions.

As the above-mentioned aromatic alkyl group, an aromatic alkyl group having 6 to 30 carbon atoms is preferred, a phenyl group or a naphthyl group is more preferred, and a phenyl group is further preferred. In addition, when R ¹ is an aromatic alkyl group, the aromatic alkyl group may further have a substituent. The substituent is not particularly limited, and alkyl, alkoxy, hydroxyl, dimethylphosphinoyl, etc. can be listed. Among them, as a substituent, it is preferred to have a substituent having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. When R ¹ is an aromatic alkyl group having a substituent, for the ring member in R ¹ that is bonded to the nitrogen atom in formula (A-1), it is preferred that the substituent is bonded to an adjacent ring member. For example, when ^R1 is a phenyl group having a hydroxyl group, it is preferred that the bonding site of the phenyl group to the nitrogen atom in formula (A-1) and the hydroxyl group are present at adjacent positions.

As the heteroatom in the above-mentioned aromatic heterocyclic group, nitrogen atom, sulfur atom, oxygen atom, etc. can be listed. It is preferred to contain at least one of nitrogen atom and sulfur atom, it is further preferred to contain nitrogen atom, and it is particularly preferred to contain 2 or more nitrogen atoms. In addition, the state containing nitrogen atom and sulfur atom is also one of the preferred states of the present invention. The number of heteroatoms in the aromatic heterocyclic group is not particularly limited, 1 to 8 is preferred, 1 to 6 is more preferred, and 2 to 4 is more preferred.

The aromatic heterocyclic group is preferably a group obtained by removing one hydrogen atom from a five-membered ring structure, a group obtained by removing one hydrogen atom from a six-membered ring structure, a ring structure formed by condensing a five-membered ring structure with a six-membered ring structure, or a ring structure formed by condensing a six-membered ring structure with a six-membered ring structure. As the five-membered ring structure in the group obtained by removing one hydrogen atom from a five-membered ring structure, there can be listed a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, a tetrazole ring, a thiazole ring, a thiophene ring, an oxadiazole ring, a furan ring, and the like. As the six-membered ring structure in the group obtained by removing one hydrogen atom from the six-membered ring structure, there can be listed a pyridine ring, a pyrimidine ring, a pyrimidine ring, a pyridine ring, a 1,2,4-trithion ring, a 1,3,5-trithion ring, etc. Examples of the ring structure formed by condensation of a 5-membered ring structure and a 6-membered ring structure in the base obtained by removing one hydrogen atom from the ring structure formed by condensation of a 5-membered ring structure and a 6-membered ring structure include indole ring, isoindole ring, indole ring, indazole ring, benzimidazole ring, 7-azaindole ring, 7-azaindazole ring, pyrazolo "1,5-a" pyrimidine ring, purine ring, benzothiophene ring, benzoisothiazole ring, etc. Examples of the ring structure formed by condensing a 5-membered ring structure and a 6-membered ring structure in the group obtained by removing one hydrogen atom from the ring structure formed by condensing a 5-membered ring structure and a 6-membered ring structure include a naphthyl ring, a quinoline ring, an isoquinoline ring, a quinoline ring, a pyridine ring, a quinazoline ring, an octidine ring, a naphthyridine ring, a pyrido[3,2-d]pyrimidine ring, a pyrido[4,3-d]pyrimidine ring, a pyrido[3,4-b]pyridine ring, a pyrido[2,3-b]pyridine ring, and a pteridine ring.

The above aromatic heterocyclic group may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, a hydroxyl group, and a cyano group. For example, from the viewpoint of increasing the solubility of compound A in a solvent, a substituent containing an alkyl group (for example, a straight-chain alkyl group such as a methyl group and an ethyl group, or a branched-chain alkyl group such as an isopropyl group and a 2-ethylhexyl group) may be present.

Preferred specific examples of R ¹ are described below. The present invention is not limited to the following structure. In the following structure, * represents the bonding site with the nitrogen atom in formula (A-1). [Chemical Formula 18]

[R ² ] In formula (A-1), R ² represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom. The monovalent organic group in R ² is not particularly limited, and includes alkyl groups, aryl groups, etc., and preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group.

[R ³ ] In the formula (A-1), R ³ represents a monovalent organic group, and may be either an aliphatic group or an aromatic group, but an aromatic group is preferred. Examples of the aliphatic group include an alkyl group and the like.

The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred from the viewpoint of the adhesion of the cured product after exposure to heating conditions.

As the above-mentioned aromatic alkyl group, an aromatic alkyl group having 6 to 30 carbon atoms is preferred, a phenyl group or a naphthyl group is more preferred, and a phenyl group is further preferred. In addition, when R ³ is an aromatic alkyl group, the aromatic alkyl group may further have a substituent. The substituent is not particularly limited, and an alkyl group, an alkoxy group, a hydroxyl group, etc. can be listed, and a hydroxyl group is preferred. When R ³ is an aromatic alkyl group having a substituent, for the ring member in R ¹ that is bonded to the nitrogen atom in formula (A-1), it is preferred that the substituent is bonded to an adjacent ring member. For example, when R ¹ is a phenyl group having a hydroxyl group, it is preferred that the bonding site in the above-mentioned phenyl group to the nitrogen atom in formula (A-1) and the above-mentioned hydroxyl group are present at adjacent positions.

When R ³ is an aromatic heterocyclic group, the preferred embodiment of the aromatic heterocyclic group is the same as the preferred embodiment when R ¹ is an aromatic heterocyclic group. In addition, the embodiment in which R ³ is an aromatic heterocyclic group having no nitrogen atom is also one of the preferred embodiments of the present invention. As the aromatic heterocyclic group in this embodiment, furanyl, thienyl, etc. can be listed.

Preferred specific examples of R ³ are described below. The present invention is not limited to the following structure. In the following structure, * represents the bonding site with the carbon atom in formula (A-1). [Chemical Formula 19]

Furthermore, ^R2 and ^R3 may bond to form a ring structure. The ring structure formed is preferably a ring structure condensed with the aromatic ring structure in the above ^R3 , more preferably an aliphatic ring structure condensed with the aromatic ring structure in the above ^R3 , and still more preferably an aliphatic 5-membered ring structure condensed with the aromatic ring structure in the above ^R3 . The following shows examples of structures when ^R2 and ^R3 bond to form a ring structure, but the present invention is not limited to them. In the following structure, * represents the bonding site with the nitrogen atom in formula (A-1). The carbon atom directly bonded to * in the following structure by a double bond is the carbon atom in formula (A-1). [Chemical Formula 20]

The resin composition of the present invention preferably contains a compound represented by the following formula (A-2) as the compound A. [Chemical Formula 21] In formula (A-2), ^Ar1 and ^Ar2 are each independently an aromatic group which may have a substituent and has at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom at at least one of the ring members of the aromatic group and the substituent, and ^R2 represents a hydrogen atom or a monovalent organic group.

In formula (A-2), the preferred embodiment of Ar ¹ is the same as the preferred embodiment when R ¹ in formula (A-1) is an aromatic group. In formula (A-2), the preferred embodiment of R ² is the same as the preferred embodiment when R ² in formula (A-1) is an aromatic group. In formula (A-2), the preferred embodiment of Ar ² is the same as the preferred embodiment when R ³ in formula (A-1) is an aromatic group.

It is preferred that at least one of Ar ¹ , Ar ² and R ² has a phenolic hydroxyl group. It is preferred that at least one of Ar ¹ and Ar ² has a phenolic hydroxyl group. Specifically, it is preferred that at least one of Ar ¹ and Ar ² is a 2-hydroxyphenyl group.

It is preferred that at least one of Ar ¹ , Ar ² and R ² has a heterocyclic structure. It is preferred that at least one of Ar ¹ and Ar ² has a heterocyclic structure. As the heterocyclic structure, an aromatic heterocyclic structure is preferred. The preferred embodiment of the aromatic heterocyclic structure is the same as the preferred embodiment when R ¹ or R ³ is an aromatic heterocyclic group.

[Molecular weight] The molecular weight of compound A is preferably 150 to 2,000, more preferably 160 to 1,000, and even more preferably 180 to 500.

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

[Specific example] As specific examples of compound A, there are no particular limitations, and F-1 to F-23 used in the examples can be cited.

[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 0.02 mass % or more, which is more preferred, 0.05 mass % or more, which is further preferred, and 0.10 mass % or more, which is particularly preferred. The upper limit is 8 mass % or less, which is more preferred, 5 mass % or less, which is further preferred, and 3 mass % or less, which is particularly preferred. Compound A can be used alone or in combination of two or more. When two or more are used in combination, the total amount is preferably within the above range. In addition, the content of compound A relative to 100 mass parts of the specific resin in the resin composition of the present invention is preferably 0.05 to 8 mass parts, and more preferably 0.10 to 5 mass parts.

<Organic metal complex> From the viewpoint of drug resistance, the resin composition of the present invention may contain an organic metal complex. The organic metal complex is not particularly limited as long as it is an organic complex compound containing a metal atom, but a complex compound containing a metal atom and an organic group is preferred, a compound in which an organic group and a metal atom are coordinated is more preferred, and a metallocene compound is further preferred. The metallocene compound refers to an organic metal complex having two cyclopentadienyl anion derivatives which may have substituents as η5-ligands. The above-mentioned organic group is not particularly limited, and a hydrocarbon group or a group composed of a combination of a hydrocarbon group and a heteroatom is preferred. As the heteroatom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferred. It is preferred that at least one of the above organic groups is a cyclic group, and it is more preferred that at least two of them are cyclic groups. The above cyclic group is preferably selected from a cyclic group with five members and a cyclic group with six members, and a cyclic group with five members is more preferred. The above cyclic group may be a hydrocarbon ring or a heterocyclic ring, but a hydrocarbon ring is preferred. As a cyclic group with five members, a cyclopentadienyl group is preferred. 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 a metal belonging to Group 4 is preferred, at least one metal selected from the group consisting of titanium, zirconium and einsteinium is more preferred, at least one metal selected from the group consisting of titanium and zirconium is further preferred, and titanium is particularly preferred.

The organometallic complex may contain two or more metal atoms, or may contain only one metal atom, but it is preferred to contain only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one metal atom, or may contain two or more metal atoms.

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

The aspect in which the organometallic complex has the ability to initiate photoradical polymerization is also preferred. In the present invention, the ability to initiate photoradical polymerization refers to the ability to generate free radicals that can initiate free radical polymerization by irradiation with light. For example, when a composition containing a free radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region where the organometallic complex absorbs light and the free radical crosslinking agent does not absorb light, the ability to initiate photoradical polymerization can be confirmed by confirming whether the free radical crosslinking agent disappears. In order to confirm whether it disappears, an appropriate method can be selected according to the type of free radical crosslinking agent, for example, it can be confirmed by IR measurement (infrared spectrometry) or HPLC measurement (high performance liquid chromatography). When the organic metal complex has the ability to initiate photo-free radical polymerization, the organic metal complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a bismuthocene compound, further preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound. When the organometallic complex does not have the ability to initiate photo-radical polymerization, the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxy titanium compounds, titanium acylate compounds, titanium chelates, zirconocene compounds and bezocene compounds, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds and bezocene compounds, further preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds, and particularly preferably titanocene compounds.

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

As the organometallic complex, preferably, there can be mentioned a compound represented by the following formula (P). [Chemical Formula 22] In formula (P), M is a metal atom, and R is independently a substituent. Preferably, R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

As the metal atom represented by M in formula (P), iron atom, titanium atom, zirconium atom or arsenic atom is preferred, titanium atom, zirconium atom or arsenic atom is more preferred, titanium atom or zirconium atom is further preferred, and titanium atom is particularly preferred. As the aromatic group in R in formula (P), aromatic groups having 6 to 20 carbon atoms can be listed, aromatic alkyl groups having 6 to 20 carbon atoms are preferred, and phenyl, 1-naphthyl or 2-naphthyl can be listed. As the alkyl group in R in formula (P), alkyl groups having 1 to 20 carbon atoms are preferred, and alkyl groups having 1 to 10 carbon atoms are more preferred, and methyl, ethyl, propyl, octyl, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl and the like can be listed. As the halogen atom in the above R, F, Cl, Br, and I can be listed. As the alkyl group constituting the alkylsulfonyloxy group in the above R, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred, and methyl, ethyl, propyl, octyl, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. can be listed. The above R can further have a substituent. As examples of substituents, halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, monoalkylamino, dialkylamino, monoarylamino, and diarylamino can be listed.

Specific examples of the organometallic complex are not particularly limited, and include titanium tetraisopropoxide, titanium tetra(2-ethylhexyloxy), titanium diisopropoxide bis(ethyl acetylacetate), titanium diisopropoxide bis(acetylacetone), titanium bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl), titanium pentamethylcyclopentadienyl trimethoxy, titanium bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl), and the following compounds. [Chemical Formula 23]

In addition, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be cited, and the contents are incorporated into this specification.

The content of the organometallic complex is preferably 0.1 to 30 mass % relative to the total solid content of the resin composition. The lower limit is more preferably 1.0 mass %, more preferably 1.5 mass %, and more preferably 3.0 mass %. The upper limit is more preferably 25 mass %. One or more organometallic complexes can be used. When two or more 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. Here, the resin composition of the present invention preferably contains a photopolymerization initiator and a polymerizable compound described later. As the polymerizable compound, free radical crosslinking agents or other crosslinking agents can be listed.

[Free radical crosslinking agent] The resin composition of the present invention preferably contains a free radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenic unsaturated bond is preferred. As the group containing the above-mentioned ethylenic unsaturated bond, there can be listed vinyl, allyl, vinylphenyl, (meth)acryl, butylene diimide, (meth)acrylamide, etc. Among them, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferred, and from the viewpoint of reactivity, (meth)acryl is more preferred.

The free radical crosslinking agent is preferably a compound having one or more ethylenic unsaturated bonds, and a compound having two or more ethylenic unsaturated bonds is more preferred. The free radical crosslinking agent may have three or more ethylenic unsaturated bonds. As the compound having two or more ethylenic unsaturated bonds, a compound having 2 to 15 ethylenic unsaturated bonds is preferred, a compound having 2 to 10 ethylenic unsaturated bonds is more preferred, and a compound having 2 to 6 ethylenic unsaturated bonds is further preferred. From the viewpoint of the film strength of the obtained pattern (cured product), the resin composition of the present invention preferably contains a compound having two ethylenic unsaturated bonds and a compound having three or more ethylenic 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 free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol 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 thiohydrides with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can also be preferably used. Moreover, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and the substitution reaction products of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Moreover, as another example, the above-mentioned unsaturated carboxylic acids can also be replaced by unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, and allyl ethers. As a specific example, the description of paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357 can be referred to, and the content is incorporated into this specification.

The radical crosslinking agent is preferably a compound having a boiling point of 100° C. or higher at normal pressure. Examples of compounds having a boiling point of 100° C. or higher at normal pressure include compounds described in paragraph 0203 of International Publication No. 2021/112189. This content is incorporated into this specification.

Preferred radical crosslinking agents other than those mentioned above include radical polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021/112189, and the contents are incorporated into this specification.

As the free radical crosslinking agent, dipentatriol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentatriol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.)), A-TMMT (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.)), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)), A-DPH (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.) and the structure in which the (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues is preferred. Oligomers of the above types can also be used.

As commercially available free radical crosslinking agents, for example, there can be mentioned tetrafunctional acrylate SR-494 having four vinyloxy chains, bifunctional methacrylate SR-209, 231, 239 having four vinyloxy chains (all manufactured by Sartomer Company, Inc.), hexafunctional acrylate DPCA-60 having six pentyloxy chains, trifunctional acrylate TPA-330 having three isobutyloxy chains (all manufactured by Nippon Kayaku Co., Ltd.), urethane oligomers 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, 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, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION.), etc.

As free radical crosslinking agents, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. As the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238 can also be used.

The free radical crosslinking agent can be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The free radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is more preferably a free radical crosslinking agent in which the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to give it an acid group. The following compound is particularly preferred: in the free radical crosslinking agent in which the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to give it an acid group, the aliphatic polyhydroxy compound is neopentyl triol or dipentyl triol. As commercially available products, for example, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO., LTD. can be cited.

The acid value of the free radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, and more preferably 1 to 100 mgKOH/g. As long as the acid value of the free radical crosslinking agent is within the above range, the operability in production is excellent and the developing property is excellent. In addition, the polymerizability is good. The above acid value is measured according to the description of JIS K 0070:1992.

From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate as the resin composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate can be used. Ester, 1,6-hexanediol dimethacrylate, dihydroxymethyl-tricyclodecane diacrylate, dihydroxymethyl-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid EO modified dimethacrylate, other bifunctional acrylates with urethane bonds, bifunctional methacrylates with urethane bonds. These can be used in combination of two or more as needed. Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200. From the viewpoint of suppressing the warping of the pattern (cured product), the resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as a 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-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and other (meth)acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl caprolactam and other N-vinyl compounds, allyl glycidyl ether and the like can be preferably used. As a monofunctional free radical crosslinking agent, in order to suppress volatility before exposure, a compound having a boiling point of 100°C or more at normal pressure is also preferred. In addition, as a bifunctional or higher-functional free radical crosslinking agent, allyl compounds such as diallyl phthalate and triallyl trimellitate can be listed.

When a free radical crosslinking agent is contained, the content of the free radical crosslinking agent is preferably more than 0 mass % and less than 60 mass % relative to 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 free radical crosslinking agent may be used alone or in combination of two or more. When two or more are used in combination, the total amount thereof is preferably within the above range.

[Other crosslinking agents] The resin composition of the present invention preferably contains other crosslinking agents different from the above-mentioned free radical crosslinking agents. Other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents. It is preferred that the compound has multiple groups in the molecule that are promoted by the photosensitization of the above-mentioned photoacid generator or photoalkali generator (forming covalent bonds with other compounds in the composition or their reaction products), and it is more preferred that the compound has multiple groups in the molecule that are promoted by the action of an acid or a base (forming covalent bonds with other compounds in the composition or their reaction products). It is preferred that the above-mentioned acid or base is an acid or base generated from the photoacid generator or photoalkali generator in the exposure step. As other crosslinking agents, the compounds described in paragraphs 0179 to 0207 of International Publication No. 2022/145355 can be cited. The above description is incorporated into this specification.

[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 preferred to contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet region to the visible region is preferred. In addition, it may be an activator that reacts with a photoexcited sensitizer and generates active radicals.

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

As the photoradical polymerization initiator, any known compound can be used. For example, alkyl halides derivatives (e.g., compounds having a trioxane skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic hydrocarbon complexes, etc. can be listed. For details of the above, please refer to paragraphs 0165 to 0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated into this specification. In addition, the compounds described in paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173 and Japanese Patent No. 6301489, MATERIAL STAGE 37～60p, vol.19, No.3, 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, the photopolymerization initiator described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiator described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiator described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated into this specification.

Examples of the ketone compound include compounds described in paragraph 0087 of Japanese Patent Application Laid-Open No. 2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and the contents are incorporated into this specification.

As the α-hydroxyketone-based initiator, 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, IRGACURE 127 (all manufactured by BASF) can be used.

As the α-aminoketone-based initiator, 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-based initiator, the acylphosphine oxide-based initiator, and the metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021/112189 can also be preferably used. The contents are incorporated into this specification.

As the photo-radical polymerization initiator, oxime compounds are more preferably cited. By using oxime compounds, the exposure tolerance can be further effectively improved. Oxime compounds have a wider exposure tolerance (exposure margin) and also function as a photohardening accelerator, so they are particularly preferred.

Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, compounds described in Japanese Patent Application Publication No. 2000-080068, compounds described in Japanese Patent Application Publication No. 2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. The compounds described in Japanese Unexamined Patent Application (1995, pp. 202-232), the compounds described in Japanese Unexamined Patent Application No. 2000-066385, the compounds described in Japanese Unexamined Patent Application No. 2004-534797, the compounds described in Japanese Unexamined Patent Application No. 2017-019766, the compounds described in Japanese Patent No. 6065596, the compounds described in International Publication No. 20 The compounds described in 15/152153, the compounds described in International Publication No. 2017/051680, the compounds described in Japanese Patent Publication No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, the compounds described in International Publication No. 2013/167515, etc., the contents of which are incorporated into this specification.

Preferred oxime compounds include, for example, compounds having the following structures: 3-(benzoyloxy(imino))butan-2-one, 3-(acetyloxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetyloxy(imino))pentan-3-one, 2-(acetyloxy(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, the oxime compound is preferably used as a photoradical polymerization initiator. The oxime compound used as a photoradical polymerization initiator has a linking group >C=N-O-C(=O)- in the molecule.

[Chemical formula 24]

Examples of commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in JP-A-2012-014052), TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemix Corporation), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). In addition, an oxime compound having the following structure can also be used. [Chemical Formula 25]

As a photoradical polymerization initiator, for example, an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of International Publication No. 2021/112189, an oxime compound having a carbazole ring in which at least one benzene ring is a naphthalene ring, and an oxime compound having a fluorine atom can also be used. In addition, an oxime compound having a nitro group described in paragraphs 0208 to 0210 of International Publication No. 2021/020359, an oxime compound having a benzofuran skeleton, and an oxime compound having a hydroxyl substituent bonded to the carbazole skeleton can also be used. These contents are incorporated into this specification.

As a photopolymerization initiator, an oxime compound having an aromatic ring group Ar ^OX1 with an electron-withdrawing group introduced into the aromatic ring (hereinafter, also referred to as an oxime compound OX) can also be used. As the electron-withdrawing group possessed by the above-mentioned aromatic ring group Ar ^OX1 , there can be listed 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. From the reason that a film with excellent light resistance can be easily formed, an acyl group is more preferred, and a benzoyl group is further preferred. The benzoyl group may have a substituent. As the substituent, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxygen group, an alkenyl group, an alkylthiohydrogen group, an arylthiohydrogen group, an acyl group or an amino group is preferred; an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxygen group, an alkylthiohydrogen group, an arylthiohydrogen group or an amino group is more preferred; an alkoxy group, an alkylthiohydrogen group or an amino group is further preferred.

The oxime compound OX is preferably at least one selected from the group consisting of a compound represented by the formula (OX1) and a compound represented by the formula (OX2), and more preferably a compound represented by the formula (OX2). [Chemical Formula 26] In the formula, ^RX1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylthio group, an arylthio 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, an aminoformyl group or an aminosulfonyl group, ^RX2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group or an amino group, and ^RX3 to ^RX14 each independently represent a hydrogen atom or a substituent. Among them, at least one of ^RX10 to ^RX14 is an electron-withdrawing group.

In the above formula, ^RX12 is an electron-withdrawing group, and ^RX10 , ^RX11 , ^RX13 , and ^RX14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated into the present specification.

As particularly preferred oxime compounds, there can be mentioned oxime compounds having specific substituents disclosed in Japanese Patent Application Laid-Open No. 2007-269779, oxime compounds having thioaryl groups disclosed in Japanese Patent Application Laid-Open No. 2009-191061, and the like, the contents of which are incorporated into the present specification.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyl trioxane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halogenated methyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

Furthermore, the photoradical polymerization initiator is a trihalogenmethyl trioxane compound, an α-amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. It is more preferred that the initiator be at least one compound selected from the group consisting of a trihalogenmethyl trioxane compound, an α-amino ketone compound, a metallocene compound, an oxime compound, a triaryl imidazole dimer, or a benzophenone compound, and it is further preferred that the metallocene compound or the oxime compound be further preferred.

As the photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of International Publication No. 2021/020359 and the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used, and the contents are incorporated into this specification.

As the photoradical polymerization initiator, a difunctional or trifunctional or higher photoradical polymerization initiator can be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thereby obtaining good sensitivity. In addition, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in a solvent or the like increases, and it becomes difficult to precipitate over time, thereby improving the temporal stability of the resin composition. Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015/004565, paragraphs 0407 to 0412 of JP-A-2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017/033680, and compounds (E) and compounds described in JP-A-2013-522445. (G), Cmpd1 to 7 described in International Publication No. 2016/034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Publication No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Patent Publication No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent No. 6469669, etc., the contents of which are incorporated into this specification.

When the resin composition contains a photopolymerization initiator, the content thereof is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, more preferably 0.5 to 15 mass %, and even more preferably 1.0 to 10 mass % relative to the total solid content of the resin composition. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range. Furthermore, since the photopolymerization initiator sometimes also acts as a thermal polymerization initiator, the crosslinking using the photopolymerization initiator is sometimes further promoted by heating with an oven, a heating plate, etc.

[Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal free radical polymerization initiator, a photo free radical polymerization initiator, etc., and produces electron transfer, energy transfer, heat, etc. As a result, the thermal free radical polymerization initiator and the photo free radical polymerization initiator cause chemical changes and decompose, and generate free radicals, acids or bases. As the sensitizers that can be used, compounds such as benzophenone series, michler's ketone series, coumarin series, pyrazole azo series, anilino azo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series, benzylidene series, oxycyanine series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenathiophene series, pyrrolopyrazole azo methine series, phthalocyanine series, benzopyran series, indigo series, etc. can be used. As the sensitizer, for example, michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidenedihydroindanone, p-dimethylaminophenylallylidenedihydroindanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethyl Oxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-ortho-benzophenone, isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate, 2-benzimidazole, 1-phenyl-5-benzyltetrazolyl, 2-benzthiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthalene (1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetylamide, benzanilide, N-methylacetylanilide, 3',4'-dimethylacetylanilide, etc. Other sensitizing dyes can also be used. For details of sensitizing dyes, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated into this specification.

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

[Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005), pages 683-684. As chain transfer agents, for example, a group of compounds having -SS-, -SO ₂ -S-, -NO-, SH, PH, SiH and GeH in the molecule, dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds having a thiocarbonylthio group used for RAFT (Reversible Addition Fragmentation chain Transfer) polymerization, etc. can be used. These generate free radicals by donating hydrogen to low-activity free radicals, or can generate free radicals by deprotonating after oxidation. In particular, thiol compounds can be preferably used.

In addition, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used as chain transfer agents, and the contents are incorporated into this specification.

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, relative to 100 parts by mass of the total solid content of the resin composition. The chain transfer agent may be only one or two or more. When there are two or more chain transfer agents, the total amount thereof is preferably within the above range.

<Base generator> The resin composition of the present invention may contain a base generator. Here, the base generator refers to a compound that can generate a base by physical action or chemical action. As preferred base generators, thermal base generators and photobase generators can be listed. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferred that the resin composition contains a base generator. By including a thermal alkali generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, so that the mechanical properties or chemical resistance of the cured product are good, and the performance of the interlayer insulating film for the redistribution layer contained in the semiconductor package is improved. The alkali generator may be an ionic alkali generator or a non-ionic alkali generator. As the alkali generated from the alkali generator, for example, diamines and tertiary amines can be listed. The alkali generator is not particularly limited, and a known alkali generator can be used. As known alkali generators, for example, there can be listed aminoformyl oxime compounds, aminoformylhydroxylamine compounds, aminoformic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, o-phthalimide derivative compounds, acyloxyimide compounds, etc. As specific examples of non-ionic base generators, the compounds described in paragraphs 0249 to 0275 of International Publication No. 2022/145355 can be cited. The above description is incorporated into this specification.

Examples of the base generator include the following compounds, but the base generator is not limited thereto.

[Chemical formula 27]

The molecular weight of the non-ionic base generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

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

As specific examples of ammonium salts, the following compounds can be cited, but are not limited to them. [Chemical Formula 28]

As specific examples of imine salts, the following compounds can be cited, but are not limited thereto. [Chemical Formula 29]

When the resin composition contains an alkali generator, the content of the alkali 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 preferably 0.3 parts by mass or more, and 0.5 parts by mass or more is further preferred. The upper limit is preferably 30 parts by mass or less, 20 parts by mass or less is further preferred, 10 parts by mass or less is further preferred, 5 parts by mass or less is further preferred, and 4 parts by mass or less is particularly preferred. Alkali generators can be used in one or more than two kinds. When two or more kinds are used, the total amount is preferably within the above range.

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

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc.) ethyl 2-methoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

As the ethers, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiourea acetate, ethyl thiourea 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, dipropylene glycol dimethyl ether and the like can be listed as preferred ones.

As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferably mentioned.

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

As the sulfoxides, for example, dimethyl sulfoxide can be cited as a preferred one.

As the amides, 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-formyl propionamide, N-acetyl propionamide and the like are preferably exemplified.

As the urea, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferred.

As alcohols, there may be mentioned 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, methylbenzyl alcohol, n-pentanol, methylpentanol and diacetone alcohol.

From the viewpoint of improving the properties of the coated surface, it is also preferable that the solvent is in the form of a mixture of two or more types.

In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celulose 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, levulose ketone and dihydrolevulose ketone or a mixed solvent consisting of two or more thereof is preferred. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone, dimethyl sulfoxide and γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide together, or N-methyl-2-pyrrolidone and ethyl lactate together. In addition, the embodiment in which 1 to 10% by mass of toluene is further added to the solvent used together relative to the total mass of the solvent is also one of the better embodiments of the present invention. In particular, from the perspective of the storage stability of the resin composition, the embodiment containing γ-valerolactone as a solvent is also one of the better embodiments of the present invention. In this embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50 mass% or more, more preferably 60 mass% or more, and even more preferably 70 mass% or more. In addition, the upper limit of the above content is not particularly limited and can be 100 mass%. The above content can be determined by considering the solubility of the specific resin and other components contained in the resin composition. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used together, relative to the total mass of the solvent, it is preferred that the solvent contains 60-90 mass% of γ-valerolactone and 10-40 mass% of dimethyl sulfoxide, more preferably 70-90 mass% of γ-valerolactone and 10-30 mass% of dimethyl sulfoxide, and even more preferably 75-85 mass% of γ-valerolactone and 15-25 mass% of dimethyl sulfoxide.

From the viewpoint of coating properties, the content of the solvent is preferably set to an amount where the total solid content concentration of the resin composition of the present invention reaches 5 to 80 mass %, more preferably 5 to 75 mass %, more preferably 10 to 70 mass %, and even more preferably 20 to 70 mass %. The solvent content can be adjusted according to the required thickness of the coating and the coating method. When two or more solvents are contained, it is preferably that the total is within the above range.

<Metal Adhesion Improver> From the viewpoint of improving adhesion to metal materials used in electrodes or wiring, it is preferred that the resin composition of the present invention contains a metal adhesion improver. Examples of metal adhesion improvers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds having sulfonamide structures and compounds having thiourea structures, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[Silane coupling agent] As a silane coupling agent, for example, the compound described in paragraph 0316 of International Publication No. 2021/112189 and the compound described in paragraphs 0067 to 0078 of Japanese Patent Publication No. 2018-173573 can be listed, and these contents are incorporated into this specification. In addition, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358, it is also preferred to use two or more different silane coupling agents. It is also preferred to use the following compounds as silane coupling agents. In the following formula, Me represents a methyl group and Et represents an ethyl group. In addition, the following R can list the structure of the blocking agent derived from the blocked isocyanate group. As the end-capping agent, it can be selected according to the desorption temperature, and alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, etc. can be listed. For example, from the perspective of setting the desorption temperature to 160 to 180°C, caprolactam is preferred. As a commercial product of such a compound, X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be listed.

[Chemical formula 30]

As other silane coupling agents, for example, vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxyhexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl Oxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-butylenepropylmethyldimethoxysilane, 3-butylenepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more. In addition, as a silane coupling agent, an oligomer-type compound having a plurality of alkoxysilyl groups can also be used. As such an oligomer-type compound, a compound containing a repeating unit represented by the following formula (S-1) can be cited. [Chemical Formula 31] In formula (S-1), ^RS1 represents a monovalent organic group, ^RS2 represents a hydrogen atom, a hydroxyl group or an alkoxy group, and n represents an integer of 0 to 2. ^RS1 preferably has a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxide group, an oxacyclobutane group, a benzoxazolyl group, a blocked isocyanate group, an amine group, and the like. As the group having an ethylenic unsaturated bond, there can be mentioned 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., vinylphenyl, etc.), a (meth)acrylamide group, a (meth)acryloxy group, etc., preferably a vinylphenyl group, a (meth)acrylamide group or a (meth)acryloxy group, more preferably a vinylphenyl group or a (meth)acryloxy group, and further preferably a (meth)acryloxy group. ^RS2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. n represents an integer of 0 to 2, preferably 1. Here, the structures of the plurality of repeating units represented by the 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, n is preferably 1 or 2 in at least one, more preferably 1 or 2 in at least two, and even more preferably 1 in at least two. As such an oligomer type compound, a commercially available product can be used, and as a commercially available product, for example, KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be cited.

[Aluminum-based bonding aid] Examples of aluminum-based bonding aids include tri(ethyl acetylacetate)aluminum, tri(acetylacetone)aluminum, and diisopropyl ethyl acetylacetate aluminum.

As other metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can also be used, and these contents are incorporated into this specification.

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 relative to 100 parts by mass of the specific resin. By setting it to above the lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it to below the upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver can be only one kind or two or more kinds. When two or more kinds are used, it is preferably 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 a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, it is possible to effectively inhibit metal ions originating from the metal layer (or metal wiring) from migrating into the film. Among them, the compound corresponding to the above-mentioned compound A does not correspond to the migration inhibitor.

Migration inhibitors are not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxadiazole ring, thiazole ring, pyrazole ring, isoxadiazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, pyrimidine ring, 2H-pyranyl ring, 6H-pyranyl ring, triazole ring), compounds having thiourea and thiohydrin, 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 capture agent that captures anions such as halogen ions can also be used.

As other migration inhibitors, the rustproofing agent described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used, and the contents are incorporated into this specification.

As specific examples of migration inhibitors, the following compounds can be cited.

[Chemical formula 32]

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 %, relative to the total solid content of the resin composition.

The number of migration inhibitors may be one or more. When there are two or more migration inhibitors, the total amount thereof is preferably within the above range.

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

Specific examples of the polymerization inhibitor include compounds described in paragraph 0310 of International Publication No. 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl radical, phenanthroline, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc. The contents are incorporated into this specification.

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 %, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %, relative to the total solid content of the resin composition.

The polymerization inhibitor may be one or more. When the polymerization inhibitor is two or more, the total amount thereof is preferably within the above range.

<Light absorber> The resin composition of the present invention preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases due to exposure.

Whether compound a contained in the resin composition corresponds to a light absorber (that is, whether its absorbance at the exposure wavelength decreases due to exposure) can be determined by the following method. First, prepare a solution of compound a at the same concentration as the concentration contained in the resin composition, and measure the molar absorbance of compound a at the wavelength of the exposure light (mol ^-1・L・cm ^-1 , also called "molar absorbance 1"). In order to reduce the influence of changes such as a decrease in the molar absorbance of compound a, the above measurement is performed quickly. Regarding the solvent in the above solution, when the resin composition contains a solvent, the solvent is used, and when the resin composition does not contain a solvent, N-methyl-2-pyrrolidone is used. Then, the solution of compound a is irradiated with exposure light. The cumulative exposure amount is set to 500mJ relative to 1 mol of compound a. Afterwards, the molar absorbance of compound a at the wavelength of the exposure light is measured using the solution of compound a after exposure (mol ^-1・L・cm ^-1 , also referred to as "molar absorbance 2"). The attenuation rate (%) is calculated from the molar absorbance 1 and the molar absorbance 2 according to the following formula. When the attenuation rate (%) is 5% or more, compound a is judged to be a compound whose absorbance at the exposure wavelength decreases due to exposure (i.e., a light absorber). Attenuation rate (%) = 1-molar absorbance 2/molar absorbance 1×100 The attenuation rate is preferably 10% or more, and more preferably 20% or more. In addition, the lower limit of the attenuation rate is not particularly limited, and 0% or more is sufficient. The wavelength of the exposure light mentioned above can be any wavelength to which the photosensitive film is exposed when the resin composition is used to form a photosensitive film. Furthermore, the wavelength of the exposure light mentioned above is preferably a wavelength to which the photopolymerization initiator contained in the resin composition has sensitivity. The photopolymerization initiator having sensitivity to a certain wavelength means that when the photopolymerization initiator is exposed at a certain wavelength, polymerization initiator species will be generated. As for the wavelength of the exposure light, in terms of its relationship with the light source, there are (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (3 wavelengths of g, h, and i rays), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser's second harmonic wave 532nm, third harmonic wave 355nm, etc. Regarding the wavelength of the exposure light, for example, it is sufficient to select a wavelength to which the photopolymerization initiator has sensitivity, but h rays (wavelength 405nm) or i rays (wavelength 365nm) are preferred, and i rays (wavelength 365nm) are more preferred.

The light absorber may be a compound that generates a radical polymerization initiator upon exposure, but from the viewpoint of resolution and chemical resistance, a compound that does not generate a radical polymerization initiator upon exposure is preferred. Whether the light absorber is a compound that generates a radical polymerization initiator upon exposure can be determined by the following method. A light absorber having the same concentration as that contained in the resin composition and a solution containing a radical crosslinking agent are prepared. When the resin composition contains a radical crosslinking agent, a compound that is the same as the radical crosslinking agent contained in the resin composition is used as the radical crosslinking agent in the above solution at the same concentration. When the resin composition does not contain a radical crosslinking agent, methyl methacrylate is used at a concentration 5 times that of the light absorber. Thereafter, exposure light is irradiated. The accumulated exposure amount is set to 500 mJ. After exposure, for example, the polymerization of the polymerizable compound is determined by high-speed liquid chromatography. When the ratio of the molar amount of the polymerizable compound to the total molar amount of the polymerizable compound is 10% or less, the light absorber is determined to be a compound that does not generate free radical polymerization initiators due to exposure. The above molar ratio is preferably 5% or less, and 3% or less is more preferably. In addition, the lower limit of the above molar ratio is not particularly limited and can be 0%. As the wavelength of the above exposure light, when the resin composition is used to form a photosensitive film, it only needs to be the wavelength to which the photosensitive film is exposed. In addition, as the wavelength of the above exposure light, it is preferably a wavelength to which the photopolymerization initiator contained in the resin composition has sensitivity.

As compounds that generate free radical polymerization initiators due to exposure, the same compounds as the above-mentioned photoradical polymerization initiators can be listed. When the composition contains a photoradical polymerization initiator as a light absorber, the one with the lowest polymerization initiation ability of the generated free radical species is used as the light absorber, and the others are used as photopolymerization initiators. As compounds that do not generate free radical polymerization initiators due to exposure, in addition to photoacid generators and photoalkali generators, pigments that change the absorption wavelength due to exposure can be listed. Among them, naphthoquinone diazide compounds or pigments that change the absorbance due to exposure are preferred as light absorbers, and naphthoquinone diazide compounds are more preferred. Furthermore, as a light absorber, for example, it is also possible to consider using a photoacid generator or a photobase generator in combination with a compound whose absorbance decreases depending on the exposure wavelength of pH.

[Naphthoquinone diazide compound] Examples of naphthoquinone diazide compounds include compounds that generate indene carboxylic acid upon exposure and reduce the absorbance at the exposure wavelength, and compounds having a 1,2-naphthoquinone diazide structure are preferred. Examples of naphthoquinone diazide compounds include naphthoquinone diazide sulfonates of hydroxyl compounds. Examples of the hydroxyl compounds include compounds represented by any one of the following formulae (H1) to (H6). [Chemical Formula 33] In formula (H1), ^R1 and ^R2 each independently represent a monovalent organic group, ^R3 and ^R4 each independently represent a hydrogen atom or a monovalent organic group, n1, n2, m1 and m2 each independently represent an integer of 0 to 5, and at least one of m1 and m2 is an integer of 1 to 5. In formula (H2), Z represents a tetravalent organic group, ^L1 , ^L2 , ^L3 and ^L4 each independently represent a single bond or a divalent organic group, ^R5 , ^R6 , ^R7 and ^R8 each independently represent a monovalent organic group, n3, n4, n5 and n6 each independently represent an integer of 0 to 3, m3, m4, m5 and m6 each independently represent an integer of 0 to 2, and at least one of m3, m4, m5 and m6 is 1 or 2. In formula (H3), ^R9 and ^R10 each independently represent a hydrogen atom or a monovalent organic group, ^L5 each independently represents a divalent organic group, and n7 represents an integer of 3 to 8. In formula (H4), ^L6 represents a divalent organic group, and ^L7 and ^L8 each independently represent a divalent organic group containing a tertiary or quaternary carbon of an aliphatic group. In formula (H5), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, L ⁹ , L ¹⁰ and L ¹¹ each independently represent a single bond or a divalent organic group, m7, m8, m9 and m10 each independently represent an integer of 0 to 2, and at least one of m7, m8, m9 and m10 is 1 or 2. In formula (H6), R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ each independently represent a hydrogen atom or a monovalent organic group, R ⁴⁶ and R ⁴⁷ each independently represent a monovalent organic group, n16 and n17 each independently represent an integer of 0 to 4, m11 and m12 each independently represent an integer of 0 to 4, and at least one of m11 and m12 is an integer of 1 to 4.

In formula (H1), ^R1 and ^R2 are each independently a monovalent organic group having 1 to 60 carbon atoms, preferably a monovalent organic group having 1 to 30 carbon atoms. Examples of the monovalent organic group in ^R1 and ^R2 include a alkyl group which may have a substituent, for example, an aromatic alkyl group which may have a substituent such as a hydroxyl group. In formula (H1), ^R3 and ^R4 are each independently a monovalent organic group having 1 to 60 carbon atoms, preferably a monovalent organic group having 1 to 30 carbon atoms. Examples of the monovalent organic group in ^R3 and ^R4 include a alkyl group which may have a substituent, for example, an alkyl group which may have a substituent such as a hydroxyl group. In formula (H1), n1 and n2 are each independently 0 or 1, preferably 0. In formula (H1), it is preferred that m1 and m2 are both 1.

The compound represented by formula (H1) is preferably a compound represented by any one of formula (H1-1) to formula (H1-5). [Chemical Formula 34] In formula (H1-1), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or a group represented by the following formula (R-1). [Chemical Formula 35] In formula (R-1), ^R29 represents a hydrogen atom, an alkyl group or an alkoxy group, n13 represents an integer of 0 to 2, and * represents a bonding site with other structures. In formula (H1-1), n8, n9 and n10 each independently represent an integer of 0 to 2, preferably 0 or 1.

In formula (H1-2), ^R24 represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. n14, n15, and n16 each independently represent an integer of 0 to 2. ^R30 represents a hydrogen atom or an alkyl group.

In formula (H1-3), ^R25 , ^R26 , ^R27 and ^R28 each independently represent a monovalent organic group, preferably a hydrogen atom, an alkyl group or a group represented by the above formula (R-1). In formula (H1-3), n11, n12 and n13 each independently represent an integer of 0 to 2, preferably 0 or 1.

As the compound represented by formula (H1-1), a compound represented by any one of the following formulas (H1-1-1) to (H1-1-4) is preferred. As the compound represented by formula (H1-2), a compound represented by the following formula (H1-2-1) or (H1-2-2) is preferred. As the compound represented by formula (H1-3), a compound represented by the following formulas (H1-3-1) to (H1-3-3) is preferred. [Chemical Formula 36]

In formula (H2), Z is preferably a tetravalent group having 1 to 20 carbon atoms, and more preferably a group represented by any one of the following formulas (Z-1) to (Z-4). In the following formulas (Z-1) to (Z-4), * represents a bonding site with other structures. [Chemical Formula 37] In formula (H2), L ¹ , L ² , L ³ and L ⁴ are each independently a single bond or a methylene group. In formula (H2), R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an organic group having 1 to 30 carbon atoms. In formula (H2), n3, n4, n5 and n6 are each independently an integer of 0 to 2, preferably 0 or 1. In formula (H2), m3, m4, m5 and m6 are each independently 1 or 2, preferably 1. Examples of the compound represented by formula (H2) include compounds having the following structures. [Chemical Formula 38]

In formula (H3), ^R9 and ^R10 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. In formula (H3), ^L5 are each independently a group represented by the following formula (L-1). [Chemical Formula 39] In formula (L-1), R ³⁰ represents a monovalent organic group having 1 to 20 carbon atoms, n14 represents an integer of 1 to 5, and * represents a bonding site with other structures. In formula (H3), n7 is preferably an integer of 4 to 6. The following compounds can be cited as compounds represented by formula (H3). In the following formula, n each independently represents an integer of 0 to 9. [Chemical Formula 40]

In formula (H4), L ⁶ is preferably -C(CF ₃ ) ₂ -, -S(=O) ₂ - or -C(=O)-. In formula (H4), L ⁷ and L ⁸ are preferably independently a divalent organic group having 2 to 20 carbon atoms. Examples of the compound represented by formula (H4) include the following compounds. [Chemical Formula 41]

In formula (H5), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group or an acyl group. In formula (H5), L ⁹ , L ¹⁰ and L ¹¹ are each independently a single bond, -O-, -S-, -S(=O) ₂ -, -C(=O)-, -C(=O)O-, a cyclopentylene group, a cyclohexylene group, a phenylene group or a divalent organic group having 1 to 20 carbon atoms. A group represented by any one of the following formulas (L-2) to (L-4) is more preferred. [Chemical Formula 42] In formula (L-2) to formula (L-4), R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ each independently represent a hydrogen atom or an alkyl group, n15 is an integer from 1 to 5, R ³⁸ , R ³⁹ , R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom or an alkyl group, and * represents a bonding site with other structures. As the compound represented by formula (H5), the following compounds can be listed. [Chemical Formula 43]

In formula (H6), R ⁴² , R ⁴³ , R ⁴⁴ and R ⁴⁵ each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. In formula (H6), R ⁴⁶ and R ⁴⁷ each independently represent an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group. In formula (H6), n16 and n17 each independently represent an integer of 0 to 2, preferably 0 or 1. In formula (H6), n16 and n17 each independently represent an integer of 1 to 3, more preferably 2 or 3. As the compound represented by formula (H6), the following compounds can be listed. [Chemical Formula 44]

In addition, as the hydroxyl compound, there can be mentioned 2,3,4-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2′-methylbenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2 ,4,6,3′,4′-pentahydroxybenzophenone, 2,3,4,2′,4′-pentahydroxybenzophenone, 2,3,4,2′,5′-pentahydroxybenzophenone, 2,4,6,3′,4′,5′-hexahydroxybenzophenone, 2,3,4,3′,4′,5′-hexahydroxybenzophenone and other polyhydroxybenzophenones, 2,3,4-Trihydroxyacetophenone, 2,3,4-trihydroxyphenylpentanone, 2,3,4-trihydroxyphenylhexanone and other polyhydroxyphenyl alkyl ketones, Bis(2,4-dihydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)propane-1, bis(2,3,4-trihydroxyphenyl)propane-1, nordihydroretinic acid, 1,1-bis(4-hydroxyphenyl)cyclohexane and other bis((poly)hydroxyphenyl)alkanes, Polyhydroxybenzoic acid esters such as 3,4,5-trihydroxybenzoic acid propyl ester, 2,3,4-trihydroxybenzoic acid phenyl ester, 3,4,5-trihydroxybenzoic acid phenyl ester, Bis(2,3,4-trihydroxybenzoyl)methane, bis(3-acetyl-4,5,6-trihydroxyphenyl)-methane, bis(2,3,4-trihydroxybenzoyl)benzene, bis(2,4,6-trihydroxybenzoyl)benzene and other bis(polyhydroxybenzoyl)alkanes or bis(polyhydroxybenzoyl)aryls, Ethylene glycol-bis(3,5-dihydroxybenzoate), ethylene glycol-bis(3,4,5-trihydroxybenzoate) and other alkyl-bis(polyhydroxybenzoate), 2,3,4-biphenyltriol, 3,4,5-biphenyltriol, 3,5,3′,5′-biphenyltetraol, 2,4,2′,4′-biphenyltetraol, 2,4,6,3′,5′-biphenylpentaol, 2,4,6,2′,4′,6′-biphenylhexanol, 2,3,4,2′,3′,4′-biphenylhexanol and other polyhydroxy biphenyls, 4,4′-thiobis(1,3-dihydroxy)benzene and other di(polyhydroxy) sulfides, 2,2′,4,4′-tetrahydroxydiphenyl ether and other bis(polyhydroxyphenyl) ethers, 2,2′,4,4′-tetrahydroxydiphenyl sulfone and other bis(polyhydroxyphenyl) sulfones, 2,2′,4,4′-diphenyl sulfone and other bis(polyhydroxyphenyl) sulfones, Tris(4-hydroxyphenyl)methane, 4,4′,4″-trihydroxy-3,5,3′,5′-tetramethyltriphenylmethane, 4,4′,3″,4″-tetrahydroxy-3,5,3′,5′-tetramethyltriphenylmethane, 4-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-2-methoxy-phenol, 4,4′-(3,4-diol-benzylidene)bis[2,6-dimethylphenol], 4,4′-[(2-hydroxy-phenyl)methylene]bis[2-cyclohexyl-5-methylphenol, 4,4′,2″,3″,4″-pentahydroxy-3,5,3′, 5'-tetramethyltriphenylmethane, 2,3,4,2',3',4'-hexahydroxy-5,5'-diethyltriphenylmethane, 2,3,4,2',3',4',3",4"-octahydroxy-5,5'-diethyltriphenylmethane, 2,4,6,2',4',6'-hexahydroxy-5,5'-dipropionyltriphenylmethane and other polyhydroxytriphenylmethanes, 4,4'-(phenylmethylene)bisphenol, 4,4'-(1-phenyl-ethylidene)bis[2-methylphenol], 4,4',4"-ethylidene-triphenol and other polyhydroxytriphenylethanes, 3,3,3′,3′-tetramethyl-1,1′-spirobi-indane-5,6,5′,6′-tetraol, 3,3,3′,3′-tetramethyl-1,1′-spirobi-indane-5,6,7,5′,6′,7′-hexanol, 3,3,3′,3′-tetramethyl-1,1′-spirobi-indane-4,5,6,4′,5′,6′-hexanol, 3,3,3′,3′-tetramethyl-1,1′-spirobi-indane-4,5,6,5′,6′,7′-hexanol and other polyhydroxyspirobi-indanes, 2,4,4-trimethyl-2′,4′,7′-trihydroxyflavanes and other polyhydroxyflavanes, 3,3-Bis(3,4-dihydroxyphenyl)phthalolide, 3,3-bis(2,3,4-trihydroxyphenyl)phthalolide, 3′,4′,5′,6′-tetrahydroxybis[phthalolide-3,9′-oroyama-koshi] and other polyhydroxyphthalolides, morin, quercetin, rutin and other flavonoid pigments, α,α’,α’’-tri(4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α’,α’’-tri(3,5-dimethyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α’,α’’-tri(3,5-diethyl-4-hydroxyphenyl)1,3,5-triisopropylbenzene, α,α’,α’’-tri(3, 5-di-n-propyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α,α’,α’’-tris(3,5-diisopropyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α,α’,α’’-tris(3,5-di-n-butyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α,α’,α’’-tris(3-methyl -4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α,α’,α’’-tris(3-methoxy-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α,α’,α’’-tris(2,4-dihydroxyphenyl) 1,3,5-triisopropylbenzene, 1,3,5-tris(3,5-dimethyl-4-hydroxyphenyl)benzene, 1,3,5-tris(5-methyl-2-hydroxyphenyl)benzene, 2,4,6-tris(3,5-dimethyl-4-hydroxyphenylthiomethyl) symmetric trimethylbenzene, 1-[α-methyl-α-(4’-hydroxyphenyl)ethyl]-4-[α,α’-bis(4’’-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(4’-hydroxyphenyl)ethyl]-3-[α ,α'-bis(4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3',5'-dimethyl-4''-hydroxyphenyl)ethyl]-4-[α,α'-bis(3'',5''-dimethyl-4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(3'-methyl-4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(3''-methyl-4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(3'-methoxy-4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(3''-methoxy-4''-hydroxyphenyl)ethyl]benzene, 1-[α-methyl-α-(2',4'-dihydroxyphenyl)ethyl]-4- [α’,α’-bis(4’’-hydroxyphenyl)ethyl]benzene, 1-[α-methyl(2’,4’-dihydroxyphenyl)ethyl]-3-[α’,α’-bis(4’’-hydroxyphenyl)ethyl]benzene and other polyhydroxy compounds described in Japanese Patent Laid-Open No. 4-253058, α,α,α’,α’,α’’,α’’-hexa-(4-hydroxyphenyl)-1,3,5-triethylbenzene and other polyhydroxy compounds described in Japanese Patent Laid-Open No. 5-224410, 1,2,2,3-tetra(p-hydroxyphenyl)propane, 1,3,3,5-tetra(p-hydroxyphenyl)pentane and other poly(hydroxyphenyl)alkanes described in Japanese Patent Laid-Open No. 5-303200, EP-530148, p-Bis(2,3,4-trihydroxybenzyl)benzene, p-Bis(2,4,6-trihydroxybenzyl)benzene, m-Bis(2,3,4-trihydroxybenzyl)benzene, m-Bis(2,4,6-trihydroxybenzyl)benzene, p-Bis(2,5-dihydroxy-3-bromobenzyl)benzene, p-Bis(2,3,4-trihydroxy-5-methylbenzyl)benzene, p-Bis(2,3,4-trihydroxy-5-methoxybenzyl)benzene, p-Bis(2,3,4-trihydroxy-5-nitrobenzyl)benzene, p-Bis(2,3,4-trihydroxy-5- 1,3,5-tris(2,5-dihydroxybenzyl)benzene, 1,3,5-tris(2,3,4-trihydroxybenzyl)benzene, 1,2,3-tris(2,3,4-trihydroxybenzyl)benzene, 1,2,4-tris(2,3,4-trihydroxybenzyl)benzene, 1,2,4,5-tetrakis(2,3,4-trihydroxybenzyl)benzene, α,α’-bis(2,3,4-trihydroxybenzyl)p-xylene, α,α’,α’-tris(2,3,4-trihydroxybenzyl)symmetric trimethylbenzene, 2,6-Bis-(2-hydroxy-3,5-dimethylbenzyl)-p-cresol, 2,6-Bis-(2-hydroxy-5′-methylbenzyl)-p-cresol, 2,6-Bis-(2,4,6-trihydroxybenzyl)-p-cresol, 2,6-Bis-(2,3,4-trihydroxybenzyl)-p-cresol, 2,6-Bis-(2,3,4-trihydroxybenzyl)-3,5-dimethyl-phenol, 4,6-Bis-(4-hydroxy-3,5-dimethylbenzyl)-gallate, 2,6-Bis-(4 -Hydroxy-3,5-dimethylbenzyl)-1,3,4-trihydroxy-phenol, 4,6-bis-(2,4,6-trihydroxybenzyl)-2,4-dimethyl-phenol, 4,6-bis-(2,3,4-trihydroxybenzyl)-2,5-dimethyl-phenol, 2,6-bis-(4-hydroxybenzyl)-p-cresol, 2,6-bis(4-hydroxybenzyl)-4-cyclohexylphenol, 2,6-bis(4-hydroxy-3-methylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-3,5 -dimethylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-2,5-dimethylbenzyl)-p-cresol, 2,6-bis(4-hydroxy-3-methylbenzyl)-4-phenyl-phenol, 2,2′,6,6′-tetrakis[(4-hydroxyphenyl)methyl]-4,4′-methylenediphenol, 2,2′,6,6′-tetrakis[(4-hydroxy-3,5-dimethylphenyl)methyl]-4,4′-methylenediphenol, 2,2′,6,6′-tetrakis[(4-hydroxy-3 -methylphenyl)methyl]-4,4′-methylenediphenol, 2,2′-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]6,6′-dimethyl-4,4′-methylenediphenol, 2,2’,3,3’-tetrahydro-3,3,3’,3’-tetramethyl-1,1’-spirobis(1H-indene)-5,5’,6,6’,7,7’hexanol, bis(4-hydroxy-3,5-dimethylphenyl)-(4-hydroxy-3-methoxyphenyl)methane, etc. In addition, low-nucleus forms of phenolic resins such as novolac resins can also be used.

Examples of the naphthoquinonediazidesulfonic acid include 6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonic acid and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid, and these may be used in combination.

The method for producing naphthoquinone diazide sulfonic acid ester of a hydroxy compound is not particularly limited. For example, it can be obtained by sulfonyl chlorinating naphthoquinone diazide sulfonic acid with chlorosulfonic acid or thionyl chloride, and subjecting the obtained naphthoquinone diazide sulfonyl chloride to a condensation reaction with a hydroxy compound. For example, it can be obtained by subjecting a hydroxy compound to a predetermined amount of naphthoquinone diazide sulfonyl chloride in a solvent such as dioxane, acetone or tetrahydrofuran in the presence of an alkaline catalyst such as triethylamine to esterification, and then washing and drying the obtained product.

The esterification rate in naphthoquinone diazide sulfonic acid ester is not particularly limited, but is preferably 10% or more, and more preferably 20% or more. The upper limit of the esterification rate is not particularly limited, and may be 100%. The esterification rate can be confirmed by ¹ H-NMR or the like as the ratio of esterified groups in the hydroxyl groups of the hydroxyl compound.

In addition, as the light absorber, the compounds described in paragraphs 0088 to 0108 of JP-A-2019-206689 can also be used.

<Other additives> The resin composition of the present invention may contain various additives as needed within the scope of obtaining the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers and other additives (e.g., defoamers, flame retardants, etc.). In addition, the resin composition of the present invention may also contain urea compounds, carbodiimide compounds or isourea compounds. By appropriately containing these components, the properties of the film such as physical properties can be adjusted. For these components, for example, reference can be made to paragraphs 0183 and thereafter of Japanese Patent Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013/0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Publication No. 2008-250074, and the contents are incorporated into this specification. When these additives are blended, it is preferred that their total content is set to 3% by mass or less of the solid content of the resin composition of the present invention. As other additives, the compounds described in paragraphs 0316 to 00358 of International Publication No. 2022/145355 can be cited. The above description is incorporated into this manual.

<Characteristics of the resin composition> The viscosity of the resin composition of the present invention can be adjusted according to the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm ² /s to 12,000 mm ² /s is preferred, 2,000 mm ² /s to 10,000 mm ² /s is more preferred, and 2,500 mm ² /s to 8,000 mm ² /s is further preferred. Within the above range, a highly uniform coating film can be easily obtained. For example, if it is 1,000 mm ² /s or more, it is easy to apply the film with the required film thickness as a redistribution insulation film, and if it is 12,000 mm ² /s or less, a coating film with excellent coating surface appearance can be obtained.

<Restrictions on substances contained in the resin composition> The resin composition of the present invention preferably has a water content of less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. As a method for maintaining the water content, it is possible to cite such methods as adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. 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, the total of the metals is preferably within the above range.

Furthermore, as a method for reducing the metal impurities accidentally contained in the resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as a raw material constituting the resin composition of the present invention, filtering the raw material constituting the resin composition of the present invention through a filter, lining the inside of the device with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.

Regarding the resin composition of the present invention, if the use as a semiconductor material is considered, from the perspective of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm. Among them, the content of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be listed. It is preferred that the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions are respectively within the above range. As a method for adjusting the content of halogen atoms, ion exchange treatment, etc. can be preferably listed.

As a container for the resin composition of the present invention, a conventionally known container can be used. As a container, in order to suppress the mixing of impurities into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle having an inner wall composed of six types of six layers of resins or a bottle having a seven-layer structure formed of six types of resins. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

<Cured resin composition> By curing the resin composition of the present invention, a cured resin composition can be obtained. The cured resin composition of the present invention is a cured resin composition. The curing of the resin composition is preferably performed by heating, and the heating temperature is preferably 120°C to 400°C, more preferably 140°C to 380°C, and even more preferably 170°C to 350°C. The shape of the cured resin composition is not particularly limited, and can be selected from a film, rod, spherical, granular, etc. according to the application. In the present invention, the cured product is preferably a film. By patterning the resin composition, the shape of the cured product can be selected according to the purpose of forming a protective film on the wall, forming a conductive through hole, adjusting impedance, electrostatic capacitance or internal stress, and providing a heat dissipation function. The film thickness of the cured product (film composed of the cured product) is preferably 0.5μm or more and 150μm or less. The shrinkage rate when curing the resin composition of the present invention is preferably 50% or less, 45% or less is more preferably, and 40% or less is further preferably. Here, the shrinkage rate refers to the percentage of the volume change of the resin composition before and after curing, and can be calculated by the following formula. Shrinkage rate [%] = 100-(volume after curing ÷ volume before curing) × 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, it may become a cured product with 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 more, more preferably 210°C or more, and even more preferably 230°C or more.

<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 performed by a conventionally known method. As the mixing method, mixing using a stirring blade, mixing using a ball mill, mixing by rotating a tank, etc. can be listed. The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

For the purpose of removing foreign matter such as dust or particles in the resin composition of the present invention, it is preferred to perform filtering using a filter. Regarding the pore size of the filter, for example, 5 μm or less is preferred, 1 μm or less is more preferred, 0.5 μm or less is further preferred, and 0.1 μm or less is further preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be pre-cleaned with an organic solvent. In the filtering step of the filter, a plurality of filters can be connected in series or in parallel for use. When a plurality of filters are used, filters with different pore sizes or materials can be used in combination. As a connection example, for example, the following example can be cited: a HDPE filter with a pore size of 1 μm is used as the first section, and a HDPE filter with a pore size of 0.2 μm is used as the second section, and the two are connected in series. In addition, various materials can be filtered multiple times. When filtering is repeated multiple times, it can be a cycle filtration. In addition, pressurized filtration can be performed. When filtering is performed by pressurization, the pressure applied is preferably 0.01 MPa or more and 1.0 MPa or less, 0.03 MPa or more and 0.9 MPa or less, 0.05 MPa or more and 0.7 MPa or less is further preferred, and 0.05 MPa or more and 0.5 MPa or less is further preferred. In addition to filtering using a filter, impurity removal using an adsorbent can also be performed. Filtering using a filter and impurity removal using an adsorbent can also be combined. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be listed. After filtering using a filter, the resin composition filled in the bottle can be placed under reduced pressure for degassing.

(Method for producing a cured product) The method for producing a cured product of the present invention preferably includes a film forming step of applying a resin composition to a substrate to form a film. The method for producing a cured product preferably includes the film forming step, an exposure step of selectively exposing the film formed by the film forming step, and a developing step of developing the film exposed by the exposure step with a developer to form a pattern. The method for producing a cured product preferably includes at least one of the film forming step, the exposure step, the developing step, a heating step of heating the pattern obtained by the developing step, and a post-development exposure step of exposing the pattern obtained by the developing step. Furthermore, it is also preferred that the method for producing a cured product includes the above-mentioned film forming step and the step of heating the above-mentioned film. The details of each step are described below.

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

[Substrate] The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of the substrate include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, any of a substrate formed of metal and a substrate having a metal layer formed by plating, deposition, etc.), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrate, molded substrate, and electrode plates of a plasma display panel (PDP). The substrate is preferably a semiconductor substrate, and a silicon substrate, a Cu substrate, and a molded substrate are more preferably. A bonding layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided on the surface of the substrate. The shape of the substrate is not particularly limited, and may be circular or rectangular. Regarding the size of the substrate, if it is circular, for example, the diameter is preferably 100 to 450 mm, and 200 to 450 mm is more preferred. If it is rectangular, for example, the length of the short side is preferably 100 to 1000 mm, and 200 to 700 mm is more preferred. As the substrate, for example, a plate-shaped substrate may be used, and a panel-shaped substrate (substrate) is preferably used.

When a resin composition is applied to the surface of a resin layer (for example, a layer composed of a hardened material) or the surface of a metal layer to form a film, the resin layer or the metal layer becomes a base material.

As a method for applying the resin composition to the substrate, coating is preferred. As the applicable method, specifically, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating and inkjet coating can be listed. From the perspective of uniformity of film thickness, spin coating, slit coating, spray coating or inkjet coating is preferred, and from the perspective of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition or the coating conditions according to the method to be applied, a film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected according to the shape of the substrate. If it is a circular substrate such as a wafer, spin coating, spray coating, inkjet method, etc. are preferred. If it is a rectangular substrate, slit coating, spray coating, inkjet method, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. In addition, a method of transferring the coating film previously applied by the above-mentioned applying method and formed on the temporary support to the substrate can also be applied. Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Publication No. 2006-047592 can also be preferably used. In addition, a step of removing excess film at the end of the substrate can also be performed. Examples of such a step include edge bead rinse (EBR) and back rinse. The following pre-wetting step can also be adopted: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate and then the resin composition is applied.

<Drying step> After the film forming step (layer forming step), the film may be subjected to a step of drying the formed film (layer) in order to remove the solvent (drying step). That is, the method for producing a hardened product of the present invention may include a drying step of drying the film formed by the film forming step. The drying step is preferably performed 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. In addition, drying may be performed by reducing the pressure. The drying time may be 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

<Exposure step> The above-mentioned film can be provided for an exposure step of selectively exposing the film. The method for manufacturing a cured product may include an exposure step of selectively exposing the film formed by the film forming step. Selective exposure refers to exposing a portion of the film. In addition, by selective exposure, an exposed area (exposed portion) and an unexposed area (non-exposed portion) are formed on the film. The exposure amount is not particularly limited as long as it can cure the resin composition of the present invention. For example, when converted to exposure energy at a wavelength of 365nm, 50 to 10,000mJ/ ^cm2 is preferred, and 200 to 8,000mJ/ ^cm2 is more preferred.

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

Regarding exposure wavelength, in terms of its relationship with the light source, we can cite (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide wavelengths (3 wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F ₂ Excimer laser (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beam, (7) secondary harmonic 532nm, third harmonic 355nm of YAG laser, etc. With regard to the resin composition of the present invention, exposure using a high-pressure mercury lamp is particularly preferred, and from the perspective of exposure sensitivity, exposure using i-rays is more preferred. The exposure method is not particularly limited as long as at least a portion of the film composed of the resin composition of the present invention is exposed, and examples thereof include exposure using a mask, exposure using a laser direct imaging method, etc.

<Post-exposure heating step> The above-mentioned film can be provided for a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably 1 to 12°C/minute from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/minute, and even more preferably 3 to 10°C/minute. In addition, the heating rate can be appropriately changed during the heating process. There is no particular limitation on the heating method in the post-exposure heating step, and a known heating plate, oven, infrared heater, etc. can be used. In addition, when heating, it is also preferred to conduct the heating in an environment with low oxygen concentration by circulating an inert gas such as nitrogen, helium, and argon.

<Developing step> The film after exposure can be subjected to a developing step of forming a pattern by developing with a developer. That is, the method for producing a hardened product of the present invention may include a developing step of forming a pattern by developing the film exposed by the exposure step with a developer. By developing, one of the exposed portion and the non-exposed portion of the film is removed to form a pattern. Here, the development of removing the non-exposed portion of the film by the developing step is referred to as negative development, and the development of removing the exposed portion of the film by the developing step is referred to as positive development.

[Developer] As the developer used in the developing step, there can be cited an alkaline aqueous solution or a developer containing an organic solvent.

When the developer is an alkaline aqueous solution, the alkaline compound that can be contained in the alkaline aqueous solution includes inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, preferably 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, tetraethyl hydroxide ammonium, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, piperidine, and more preferably TMAH. The content of the alkaline 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 International Publication No. 2021/112189 can be used as the organic solvent. The contents are incorporated into this specification. In addition, as alcohols, preferably methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc. can also be listed, and as amides, preferably N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc. can also be listed.

Furthermore, when the developer contains an organic solvent, the organic solvent can 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, dimethyl sulfoxide, N-methyl-2-pyrrolidone and cyclohexanone is preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is 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 mass % or more, more preferably 70 mass % or more, further preferably 80 mass % or more, and particularly preferably 90 mass % or more. Furthermore, the above content may also be 100 mass %.

When the developer contains an organic solvent, the developer may further contain at least one of an alkaline compound and an alkali generator. When at least one of the alkaline compound and the alkali generator in the developer permeates into the pattern, the properties such as the elongation at break of the pattern may be improved.

As alkaline compounds, organic bases are preferred from the viewpoint of reliability when remaining in the cured film (adhesion to the substrate when the cured product is further heated). As alkaline compounds, alkaline compounds having an amine group are preferred, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc. are preferred. In order to promote the imidization reaction, primary amines, secondary amines, tertiary amines or ammonium salts are preferred, secondary amines, tertiary amines or ammonium salts are more preferred, secondary amines or tertiary amines are further preferred, and tertiary amines are particularly preferred. As an alkaline compound, it is preferred that it is not easy to remain in the cured film (the obtained cured product) from the viewpoint of the mechanical properties (elongation at break) of the cured product, and it is preferred that the residual amount is not easy to be reduced by gasification before heating from the viewpoint of promoting cyclization. Therefore, the boiling point of the alkaline compound is preferably 30℃～350℃ at normal pressure (101,325Pa), more preferably 80℃～270℃, and even more preferably 100℃～230℃. The boiling point of the alkaline compound is preferably higher than the temperature obtained by subtracting 20℃ from the boiling point of the organic solvent contained in the developer, and it is even more preferred that it is 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 boiling point of the alkaline compound used is preferably 80°C or higher, and more preferably 100°C or higher. The developer may contain only one alkaline compound, or may contain two or more.

Specific examples of the alkaline compound 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-diaminopentane, N-methylhexylamine, N -Methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N’,N’-tetrabutyl-1,6-hexanediamine, fine triamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, dimethylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-diphenylamineethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, N,N,N,N-tetramethylethylenediamine, N,N,N,N-tetramethyl-1,3-propylenediamine, etc.

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

When the developer contains at least one of an alkaline compound and an alkali generator, the content of the alkaline compound or the alkali generator is preferably 10% by mass or less, and more preferably 5% by mass or less relative to the total mass of the developer. The lower limit of the above content is not particularly limited, for example, 0.1% by mass or more is preferred. When the alkaline compound or the alkali generator is solid in the environment in which the developer is used, the content of the alkaline compound or the alkali generator is also preferably 70 to 100% by mass relative to the total solid content of the developer. The developer may contain only one alkaline compound and at least one of the alkali generators, or may contain at least one of two or more alkaline compounds and alkali generators. When at least one of the alkaline compound and the alkali generator is two or more, it is preferred that the total amount is within the above range.

The developer may further contain other components. As other components, for example, a known surfactant or a known defoaming agent can be listed.

[Developer supply method] As long as the desired pattern can be formed, the developer supply method is not particularly limited, and there are the following methods: a method of immersing the substrate formed with a film in the developer, a method of using a nozzle to supply the developer to the film formed on the substrate by immersion development, or a method of continuously supplying the developer. The type of nozzle is not particularly limited, and can be a straight nozzle, a shower nozzle, a spray nozzle, etc. From the perspective of the permeability of the developer, the removability of the non-image part, and the efficiency in manufacturing, the method of supplying the developer with a straight nozzle or the method of continuously supplying with a spray nozzle is preferred, and from the perspective of the permeability of the developer to the image part, the method of supplying with a spray nozzle is more preferred. In addition, the following steps may be adopted: after continuously supplying the developer with a direct nozzle, the substrate is rotated to remove the developer from the substrate, and after rotating and drying, the developer is continuously supplied with the direct nozzle again, and the substrate is rotated to remove the developer from the substrate. This step may also be repeated several times. As a method for supplying the developer in the developing step, there can be listed: a step of continuously supplying the developer to the substrate, a step of keeping the developer on the substrate in a substantially static state, a step of vibrating the developer on the substrate using ultrasound or the like, and a step of combining these steps, etc.

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

In the developing step, the pattern may be cleaned (rinsed) with a rinse solution after being treated with a developer. Alternatively, a rinse solution may be supplied before the developer in contact with the pattern is completely dried.

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

As the organic solvent when the rinse liquid contains an organic solvent, the same organic solvent as the one exemplified when the developer contains an organic solvent can be cited. It is preferable that the organic solvent contained in the rinse liquid is different from the organic solvent contained in the developer, and it is more preferable that the organic solvent has a lower solubility in the pattern than the organic solvent contained in the developer.

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

When the rinse liquid contains an organic solvent, the organic solvent is preferably 50 mass % or more, more preferably 70 mass % or more, and even more preferably 90 mass % or more relative to the total mass of the rinse liquid. Alternatively, the organic solvent may be 100 mass % relative to the total mass of the rinse liquid.

The rinse solution may contain at least one of an alkaline compound and an alkali generator. Although not particularly limited, when the developer contains an organic solvent, the embodiment in which the rinse solution contains at least one of the organic solvent, the alkaline compound and the alkali generator is also one of the preferred embodiments of the present invention. As the alkaline compound and the alkali generator contained in the rinse solution, the alkaline compound that can be contained when the developer contains an organic solvent and the compound exemplified as the alkali generator can be listed, and the preferred embodiments are also the same. With regard to the alkaline compound and the alkali generator contained in the rinse solution, it is sufficient to select them in consideration of the solubility in the solvent in the rinse solution, etc.

When the rinse liquid contains at least one of an alkaline compound and an alkali generator, the content of the alkaline compound or the alkali generator is preferably 10% by mass or less, and more preferably 5% by mass or less relative to the total mass of the rinse liquid. The lower limit of the above content is not particularly limited, for example, 0.1% by mass or more is preferred. When the alkaline compound or the alkali generator is solid in the environment where the rinse liquid is used, the content of the alkaline compound or the alkali generator is also preferably 70-100% by mass relative to the total solid content of the rinse liquid. When the rinse liquid contains at least one of an alkaline compound and an alkali generator, the rinse liquid may contain only one alkaline compound and at least one of an alkali generator, or may contain two or more alkaline compounds and at least one of an alkali generator. When at least one of the alkaline compound and the alkali generator is two or more, it is preferred that the total amount is within the above range.

The rinse solution may further contain other components. As other components, for example, a known surfactant or a known defoaming agent can be listed.

[Method for supplying the rinse liquid] As long as the desired pattern can be formed, there is no particular limitation on the method for supplying the rinse liquid. The following methods are available: a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by a liquid pile, a method of supplying the rinse liquid to the substrate by spraying, and a method of continuously supplying the rinse liquid to the substrate by means of a straight nozzle or the like. From the perspective of the permeability of the rinse liquid, the removability of the non-image portion, and the efficiency in manufacturing, there are methods for supplying the rinse liquid by using a shower nozzle, a straight nozzle, a spray nozzle, etc. The method of continuously supplying by using a spray nozzle is preferred. From the perspective of the permeability of the rinse liquid to the image portion, the method of supplying by 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, and the like. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the film after exposure using a straight nozzle, and more preferably a step of supplying the rinsing liquid using a spray nozzle. As a method of supplying the rinsing liquid in the rinsing step, there can be adopted a step of continuously supplying the rinsing liquid to the substrate, a step of keeping the rinsing liquid in a substantially stationary state on the substrate, a step of vibrating the rinsing liquid on the substrate using ultrasound or the like, and a step of combining them, and the like.

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

In the developing step, after the pattern is treated with a developer or after the pattern is washed with a rinse solution, a step of bringing the treatment solution into contact with the pattern may be included. Alternatively, a method of supplying the treatment solution before the developer or rinse solution in contact with the pattern is completely dried may be adopted.

As the above-mentioned treatment liquid, a treatment liquid containing at least one of water and an organic solvent and at least one of an alkaline compound and an alkali generator can be listed. The preferred embodiment of the above-mentioned organic solvent and at least one of the alkaline compound and the alkali generator is the same as the preferred embodiment of the organic solvent and at least one of the alkaline compound and the alkali generator used in the above-mentioned rinse liquid. The method of supplying the treatment liquid to the pattern can use the same method as the method of supplying the above-mentioned rinse liquid, and the preferred embodiment is also the same.

The content of the alkaline compound or alkali generator in the treatment liquid is preferably 10% by mass or less, and more preferably 5% by mass or less relative to the total mass of the treatment liquid. The lower limit of the above content is not particularly limited, for example, 0.1% by mass or more is preferred. In addition, when the alkaline compound or alkali generator is solid in the environment in which the treatment liquid is used, the content of the alkaline compound or alkali generator is 70 to 100% by mass relative to the total solid component of the treatment liquid. When the treatment liquid contains at least one of the alkaline compound and the alkali generator, the treatment liquid may contain only one alkaline compound and at least one of the alkali generator, or may contain at least one of two or more alkaline compounds and alkali generators. When at least one of the alkaline compound and the alkali generator is two or more, it is preferred that the total amount is within the above range.

<Heating step> The pattern obtained by the developing step (the pattern after washing in the case of the washing step) can be subjected to a heating step of heating the pattern obtained by the above-mentioned development. That is, the method for producing a hardened product of the present invention may include a heating step of heating the pattern obtained by the developing step. Furthermore, the method for producing a hardened product of the present invention may also include a heating step of heating a pattern obtained by other methods without the developing step or a film obtained by the film forming step. In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as a polyimide. In addition, crosslinking of unreacted crosslinking groups in the specific resin or the crosslinking agent other than the specific resin is also performed. As the heating temperature (maximum heating temperature) in the heating step, 50 to 450°C is preferred, 150 to 350°C is more preferred, 150 to 250°C is further preferred, 160 to 250°C is further preferred, and 160 to 230°C is particularly preferred.

The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by heating and utilizing the action of the base generated by the base generator.

The heating in the heating step is preferably performed at a heating rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature. The above heating rate is preferably 2 to 10°C/min, and 3 to 10°C/min is further preferred. By setting the heating rate to 1°C/min or more, productivity can be ensured and excessive volatilization of acid or solvent can be prevented. By setting the heating rate to 12°C/min or less, the residual stress of the hardened material can be alleviated. In addition, in the case of an oven capable of rapid heating, it is preferably performed at a heating rate of 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, 2 to 7°C/sec is further preferred, and 3 to 6°C/sec is further preferred.

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 the start of the step of heating to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, it is the temperature of the dried film (layer). For example, it is preferred to start heating 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 highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and further preferably 15 to 240 minutes.

In particular, when forming a multi-layer laminate, from the perspective of inter-layer adhesion, the heating temperature is preferably 30°C or higher, 80°C or higher, 100°C or higher, and 120°C or higher. The upper limit of the above heating temperature is preferably 350°C or lower, 250°C or lower, and 240°C or lower.

Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at 3°C/min and maintaining at 120°C for 60 minutes, heating from 120°C to 180°C at 2°C/min and maintaining at 180°C for 120 minutes. In addition, as described in the specification of U.S. Patent No. 9159547, it is also preferred to perform the treatment while irradiating with ultraviolet rays. This pretreatment step can improve the properties of the membrane. The pretreatment step can be performed in a short time of about 10 seconds to 2 hours, and 15 seconds to 30 minutes is more preferred. The pretreatment step can be set as a step of two or more stages. For example, the first stage pretreatment step can be carried out in the range of 100 to 150°C, and then the second stage pretreatment step can be carried out in the range of 150 to 200°C. Furthermore, cooling can be carried out after heating, and the cooling speed at this time is preferably 1 to 5°C/minute.

Regarding the heating step, from the viewpoint of preventing the decomposition of the specific resin, it is preferable to conduct the heating step in a low oxygen concentration environment by flowing an inert gas such as nitrogen, helium, or argon, or by conducting the heating step under reduced pressure. 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, and examples thereof include a heating plate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven, and the like.

<Post-development exposure step> The pattern obtained by the development step (the pattern after washing in the case of washing step) may be subjected to a post-development exposure step for exposing the pattern after the development step, instead of or in addition to the above-mentioned heating step. That is, the method for producing a hardened product of the present invention may include a post-development exposure step for exposing the pattern obtained by the development step. The method for producing a hardened product of the present invention may include a heating step and a post-development exposure step, or may include either a heating step or a post-development exposure step. In the post-development exposure step, for example, the cyclization reaction of the polyimide precursor etc. by the photosensitization of the photobase generator, the removal reaction of the acid-degradable group by the photosensitization of the photoacid generator, etc. can be promoted. In the post-development exposure step, at least a part of the pattern obtained in the development step is sufficient to be exposed, but it is preferred that the entire pattern is exposed. The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/ ^cm2 , and more preferably 100 to 15,000 mJ/ ^cm2 , calculated as exposure energy at a wavelength at which the photosensitive compound has sensitivity. Regarding the post-development exposure step, for example, it can be performed using the light source in the above-mentioned exposure step, and it is preferred to use broadband light.

<Metal layer forming step> The pattern obtained by the developing step (preferably the pattern provided for at least one of the heating step and the post-development exposure step) can also be provided for the metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a hardened product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably the pattern provided for at least one of the heating step and the post-development exposure step).

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

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

The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, based on the thickest portion.

<Application> As the manufacturing method of the cured product or the field of the cured product to which the present invention can be applied, insulating films for electronic devices, interlayer insulating films for redistribution layers, stress buffer films, etc. can be listed. In addition, sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films) or the formation of patterns by etching on insulating films for mounting purposes such as the above can be listed. For such uses, for example, you can refer to Science & Technology Co., Ltd. "High-functionalization and application technology of polyimide" April 2008, Kakimoto Masaaki/supervised, CMC Technical Library "Basics and development of polyimide materials" November 2011, Japan Polyimide and Aromatic Polymer Research Association/ed. "Latest Polyimide Fundamentals and Applications" NTS, August 2010, etc.

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 offset printing plates or screen printing plates, etching of formed parts, and producing protective varnishes and dielectric layers in electronics, especially microelectronics.

(Laminar body and method for manufacturing the laminated body) The laminated body of the present invention refers to a structure having a plurality of layers composed of the hardened material of the present invention. The laminated body is a laminated body including two or more layers composed of hardened materials, and may also be a laminated body including three or more layers. Among the two or more layers composed of the hardened materials contained in the laminated body, at least one layer is a layer composed of the hardened material of the present invention. From the viewpoint of suppressing the shrinkage of the hardened material or the deformation of the hardened material accompanying the shrinkage, it is also preferable that all the layers composed of hardened materials contained in the laminated body are layers composed of the hardened material of the present invention.

That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the hardened object of the present invention, and more preferably includes repeating the steps of the method for manufacturing the hardened object of the present invention several times.

The laminate of the present invention preferably includes two or more layers consisting of a hardened material, and preferably includes a metal layer between any of the layers consisting of the hardened material. The metal layer is preferably formed by the metal layer forming step. That is, the method for manufacturing the laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on the layer consisting of a hardened material between multiple hardened material manufacturing methods. The preferred embodiment of the metal layer forming step is as described above. As the above-mentioned laminate, for example, a laminate having a layer structure including at least three layers, namely, a layer composed of a first hardened material, a metal layer, and a layer composed of a second hardened material, can be cited as a preferred one. It is preferred that both the layer composed of the first hardened material and the layer composed of the second hardened material are layers composed of the hardened material of the present invention. The resin composition of the present invention used to form the layer composed of the first hardened material and the resin composition of the present invention used to form the layer composed of the second hardened material may be a composition of the same composition or a composition of different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a redistribution layer.

<Lamination step> The method for manufacturing a laminated body of the present invention preferably includes a lamination step. The lamination step is a series of steps including performing (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, (d) a heating step, and at least one of a post-development exposure step on the surface of a pattern (resin layer) or a metal layer in sequence again. Among them, it can be a state in which at least one of (a) a film forming step, (d) a heating step, and a post-development exposure step is repeated. In addition, it can include (e) a metal layer forming step after at least one of (d) a heating step and a post-development exposure step. The layering step may of course further include the above-mentioned drying step, etc. as appropriate.

When a further layering step is performed after the layering step, a surface activation treatment step may be performed after the exposure step and after the heating step or after the metal layer forming step. As the surface activation treatment, plasma treatment may be exemplified. The details of the surface activation treatment will be described later.

The above-mentioned lamination step is preferably performed 2 to 20 times, and more preferably 2 to 9 times. For example, in the case of resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, it is preferred to set the resin layer to a structure of more than 2 layers and less than 20 layers, and it is further preferred to set the resin layer to a structure of more than 2 layers and less than 9 layers. The composition, shape, film thickness, etc. of the above-mentioned layers may be the same or different.

In the present invention, after the metal layer is provided, it is preferred that a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer. Specifically, there can be cited an embodiment in which the following sequence of (a) film forming step, (b) exposure step, (c) development step, (d) heating step and at least one of the post-development exposure step, and (e) metal layer forming step is repeated, or an embodiment in which the following sequence of (a) film forming step, (d) heating step and at least one of the post-development exposure step, and (e) metal layer forming step is repeated. By alternately performing the step of laminating the resin composition layer (resin layer) of the present invention and the step of forming the metal layer, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

(Surface activation treatment step) The method for manufacturing a laminate of the present invention preferably includes a surface activation treatment step of performing surface activation treatment on at least a portion of the above-mentioned metal layer and the resin composition layer. The surface activation treatment step is usually performed after the metal layer forming step, but the metal layer forming step can also be performed after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) and after performing the surface activation treatment step on the resin composition layer. The surface activation treatment can be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or can be performed on at least a portion of both the metal layer and the resin composition layer after exposure. It is preferred that the surface activation treatment be performed on at least a portion of the metal layer, and it is preferred that the surface activation treatment be performed on a portion or all of the area of the metal layer where 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) disposed on the surface thereof can be improved. It is also preferred that the surface activation treatment be performed on a portion or all of the resin composition layer (resin layer) after exposure. In this way, by performing a surface activation treatment on the surface of the resin composition layer, the adhesion with the metal layer and the resin layer provided on the surface after the surface activation treatment can be improved. In particular, when the resin composition layer is hardened, such as when negative development is performed, it is not easy to be damaged by the surface treatment, so that the adhesion is easily improved. The surface activation treatment can be implemented, for example, by the method described in paragraph 0415 of International Publication No. 2021/112189. This content is incorporated into this specification.

(Semiconductor device and method for manufacturing the same) The present invention also discloses a semiconductor device including the cured product or laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing the cured product or laminate of the present invention. As a specific example of a semiconductor device in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Publication No. 2016-027357, which are incorporated into this specification. [Example]

The present invention is further specifically described below by way of examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the main purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

<Method for producing a precursor of a cyclized resin> [Synthesis Example 1: Synthesis of a precursor of a cyclized resin (Resin 1)] 23.48 g of 4,4'-oxydiphthalic anhydride (ODPA) and 22.27 g of diphthalic anhydride (BPDA) were added to a separation flask, and 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of tetrahydrofuran were added, and stirred at room temperature (25°C). While stirring, 24.66 g of pyridine was added to obtain a reaction mixture. After the heat generated by the reaction subsided, the mixture was naturally cooled 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, and then 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.73 g of tetrahydrofuran was added to the reaction mixture over 60 minutes while stirring. After stirring at room temperature for 2 hours, 7.17 g of ethanol was added and stirred for 1 hour, and then 136.83 g of tetrahydrofuran was added. The precipitate generated in the reaction mixture was removed by filtration, thereby obtaining a reaction solution. The obtained reaction solution was added to 716.21 g of ethanol to generate a precipitate consisting of a crude polymer. The generated crude polymer was filtered and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the obtained 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 conversion), and the weight average molecular weight (Mw) was 20,000. The structure of resin 1 was confirmed by ¹ H-NMR to be a structure represented by the following formula (P-1).

[Synthesis Example 2: Synthesis of a precursor of a cyclized resin (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 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Then, the reaction mixture was cooled to -10°C, and 17.0 g of sulfinyl chloride was added over 60 minutes while the temperature was maintained at -10±5°C. After diluting with 50 mL of N-methylpyrrolidone, a solution obtained by dissolving 12.6 g of 4,4'-diaminodiphenyl ether 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. Thereafter, 10.0 g of ethanol was added, and the mixture was stirred at room temperature for 1 hour. Next, 6000 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid of the polyimide precursor) was filtered 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 stirred precipitate (solid of the polyimide precursor) was filtered again and dried at 45°C under reduced pressure for 3 days. 46.6 g of the dried powder was dissolved in 419.6 g of tetrahydrofuran, and 2.3 g of triethylamine was added and stirred at room temperature for 35 minutes. Thereafter, 3000 g of ethanol was added and the precipitate was filtered. 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 Ambertech Limited) were added thereto, and the mixture was stirred for 4 hours. Thereafter, 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 filtered and dried at 45°C under reduced pressure for 24 hours to obtain 45.1 g of resin 2. The structure of resin 2 was confirmed to be a structure represented by the following formula (P-2) by ¹ H-NMR. The molecular weight of resin 2 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000. Furthermore, by appropriately adjusting the equivalent weight of 4,4'-diaminodiphenyl ether, resin 2 having a Mw of 5,000, resin 2 having a Mw of 10,000, and resin 2 having a Mw of 30,000 were synthesized.

[Synthesis Examples 3 to 9: Synthesis of Cyclic Resin Promotors (Resins 3 to 9)] Resins 3 to 9 having a structure represented by any of the following formulas (P-3) to (P-9) were synthesized by the same method as Synthesis Example 2 except that the compounds used were appropriately changed. The Mw of Resin 3 was 20,000, the Mw of Resin 4 was 20,000, the Mw of Resin 5 was 20,000, the Mw of Resin 6 was 20,000, the Mw of Resin 7 was 20,000, the Mw of Resin 8 was 20,000, and the Mw of Resin 9 was 20,000.

[Synthesis Example 10: Synthesis of a cyclized resin precursor (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 water. 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. Next, 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 stirred at 80°C for 3 hours, and 50 g of N-methylpyrrolidone (NMP) was added for dilution. The reaction solution was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was obtained by filtration, and was 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 1 day to obtain Resin 10. The molecular weight of the resin 10 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000. The structure of the resin 10 was confirmed by ¹ H-NMR to be a structure represented by the following formula (P-10).

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

[Chemical formula 45] [Chemical formula 46]

<Examples and Comparative Examples> In each example, the components listed in the following table were mixed to obtain each resin composition. In the comparative example, the components listed in the following table were mixed to obtain a comparative composition. Specifically, the content (blending amount) of each component other than the solvent listed in the table is set to the amount (mass part) listed in the "mass part" column of each column of the table. The content (blending amount) of the solvent is set to the value (mass %) at which the solid content concentration of the composition becomes the "solid content concentration" in the table, and the ratio (mass ratio) of the content of each solvent relative to the total mass of the solvent is set to the ratio listed in the "ratio" column in the table. The obtained resin composition and the comparative composition were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.8 μm. In addition, in the table, the entry "-" indicates that the composition does not contain the corresponding component.

[Table 1] Embodiment Comparison Example Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Composition Resin Type Resin 1 Resin 1 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 M 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 Single Type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator Type I-2 I-2 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Alkali generator Type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 Quality 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Polymerization inhibitor Type B-2 B-2 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent Type C-2 C-2 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Migration inhibitors Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Additives Type E-1 E-1 - - - - - - - - - - - - - - Quality 2.4 2.4 - - - - - - - - - - - - - - Type E-2 E-2 - - - - - - - - - - - - - - Quality 0.9 0.9 - - - - - - - - - - - - - - Compound A Type F-1 FR-1 F-1 F-2 F-3 F-4 F-5 F-6 F-7 F-8 F-9 F-10 F-11 F-12 F-13 F-14 Quality 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Solvent Type NMP NMP GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 45 45 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Type EL EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Type - - - - - - - - - - - - - - - - ratio - - - - - - - - - - - - - - - - Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 Reviews Adhesion after heat resistance test B D B C C B B A A B B B B C C B Composition stability A E A A A D B C C C C C A A A A

[Table 2] Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 16 17 18 19 20 twenty one twenty two twenty three twenty four 25 26 27 28 29 30 31 Composition Resin Type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 M 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 Single Type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator Type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Alkali generator Type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 Quality 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Polymerization inhibitor Type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent Type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Migration inhibitors Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Additives Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Compound A Type F-15 F-16 F-17 F-18 F-19 F-20 F-21 F-22 F-23 F-1 F-1 F-1 F-1 F-1 F-1 F-1 Quality 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.6 1.5 0.1 0.03 0.15 0.15 0.15 Type - - - - - - - - - - - - - F-7 F-16 FR-1 Quality - - - - - - - - - - - - - 0.15 0.15 0.15 Solvent Type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Type - - - - - - - - - - - - - - - - ratio - - - - - - - - - - - - - - - - Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 Reviews Adhesion after heat resistance test B A B C B B C C C A B B C A A C Composition stability A A A B A A A B C A A A A A A B

[table 3] Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 Composition Resin Type Resin 3 Resin 4 Resin 5 Resin 6 Resin 7 Resin 8 Resin 9 Resin 10 Resin 11 Resin 11 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2/Resin 3 M 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 30000 10000 5000 20000 20000 20000/20000 Quality 35 35 35 35 35 35 35 35 35 35 35 35 35 25 45 17/17 Single Type M-1 M-1 M-2 M-1 M-2 M-1 M-2 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 3 3 6 3 3 3 3 3 3 3 6 6 6 6 6 6 Polymerization initiator or photoacid generator Type I-1 I-1 I-3 I-1 I-4 I-1 I-4 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1.1 1.1 3 1.1 3 1.1 3 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Alkali generator Type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 Quality 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Polymerization inhibitor Type B-1 B-1 - B-1 - B-1 - B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 0.1 0.1 - 0.1 - 0.1 - 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent Type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Migration inhibitors Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Additives Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Compound A Type F-1 F-1 F-1 F-1 F-1 F1 F-1 F4 F-1 F-7 F-1 F-1 F-1 F-1 F-1 F-1 Quality 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Solvent Type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Type - - - - - - - - - - - - - - - - ratio - - - - - - - - - - - - - - - - Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone TMAH aqueous solution Cyclopentanone TMAH aqueous solution Cyclopentanone TMAH aqueous solution Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions Negative Negative just Negative just Negative just Negative Negative Negative Negative Negative Negative Negative Negative Negative Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 Reviews Adhesion after heat resistance test B B C B C B C B B A A B B B B B Composition stability A A A A A A A A A A B A A A A A

[Table 4] Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 Composition Resin Type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 M 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 Single Type DPHA M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator Type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-2 I-5 I-1/I-2 I-6 I-7 I-1 I-1 I-1 I-1 Quality 1.1 1.1 1.1 1.1 1.1 0.5 3 2 2 0.6/0.6 1.1 1.1 1.1 1.1 1.1 1.1 Alkali generator Type A-1 A-2 A-3 A-4 A-5 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 Quality 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Polymerization inhibitor Type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-2 B-3 Quality 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.05 0.5 0.1 0.1 Silane coupling agent Type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Migration inhibitors Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Additives Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Compound A Type F-1 F-1 F-1 F-1 F-1 F-1 F1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 Quality 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 03 0.3 0.3 0.3 0.3 0.3 Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Solvent Type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Type - - - - - - - - - - - - - - - - ratio - - - - - - - - - - - - - - - - Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 405 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M D M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 Reviews Adhesion after heat resistance test C B C C C C B B B B B B B B B B Composition stability B A B B B A A A A A A A A A A A

[table 5] Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 Composition Resin Type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 M 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 Single Type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 Quality 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Polymerization initiator or photoacid generator Type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Alkali generator Type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 Quality 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Polymerization inhibitor Type B-4 Bl/B-2 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 0.1 0.05/0.05 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent Type C-1 C-1 C-1 C-1 C-2 C-3 C-1/C-2 C-4 C-5 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1 1 0.5 3 1 1 0.5/0.5 1 1 1 1 1 1 1 1 1 Migration inhibitors Type - - - - - - - - - D-1 D-2 D-3 D-4 - - - Quality - - - - - - - - - 0.1 0.1 0.1 0.1 - - - Additives Type - - - - - - - - - - - - - E-3 E-4 E-5 Quality - - - - - - - - - - - - - 2 2 2 Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Compound A Type F-1 F-1 F-1 F-1 F4 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 Quality 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Type - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - Solvent Type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 Type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Type - - - - - - - - - - - - - - - - ratio - - - - - - - - - - - - - - - - Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 Reviews Adhesion after heat resistance test B B B B B B B B B B B B B B B B Composition stability A A A A A A A A A A A A A A A A

[Table 6] Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 Composition Resin Type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 1 M 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Quality 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 29 50 Single Type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 DPHA M-1 Quality 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 4.5 5 Polymerization initiator or photoacid generator Type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 0.8 1.5 Alkali generator Type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-2 A-2 A-2 A-1 A-1 - Quality 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 - Polymerization inhibitor Type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 - B-1 B-1 B-1 B-1 B-1 B-1 B-1 - Quality 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - Silane coupling agent Type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 - - C-1 C-1 C-1 C-1 C-1 C-1 C-1 - Quality 1 1 1 1 1 1 1 1 - - 1 1 1 1 1 1 0.6 - Migration inhibitors Type - - - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - - - Additives Type E-6 - - - - - - - - - - - - - - - E-7 E-8 Quality 0.1 - - - - - - - - - - - - - - - 0.8 5 Type - - - - - - - - - - - - - - - - - E-9 Quality - - - - - - - - - - - - - - - - - 0.02 Compound A Type F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 Quality 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Type - - - - - - - - - - - - - - - - - - Quality - - - - - - - - - - - - - - - - - - Solvent Type GBL GBL GBL NMP GBL GVL MDMPA GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL NMP ratio 40 30 10 20 30 40 45 38 40 40 40 40 40 40 40 40 40 40 Type DMSO DMSO DMSO EL DMSO DMSO EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO EL ratio 10 20 40 35 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Type - - - - NMP - - Toluene - - - - - - - - - - ratio - - - - 10 - - 2 - - - - - - - - - - Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 37 55 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 30 10 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M M M M M M M M Developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Negative Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 200 180 160 IR 230 230 Hardening time (minutes) 180 180 180 180 180 180 180 180 180 180 180 180 120 120 120 180 180 180 Reviews Adhesion after heat resistance test B B B B B B B B B B B B B B C B B B Composition stability A A A A A A A A A A A A A A A A A A

The details of each ingredient listed in the table are as follows.

[Resin] ・Resin 1 to Resin 11: Resin 1 to Resin 11 obtained by the above-mentioned synthesis example

[Monomer (polymerizable compound)] M-1 to M-2: Compounds of the following structures. The subscript in parentheses indicates the number of repetitions. [Chemical Formula 47] DPHA: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[Polymerization initiator or photoacid generator] ・I-1 to I-5: Compounds with the following structures ・I-6: Omnirad 1312 (manufactured by IGM Resins BV) ・I-7: Omnirad TPO H (manufactured by IGM Resins BV) [Chemical formula 48]

[Alkali generator] A-1 to A-5: Compounds having the following structures [Chemical formula 49]

[Polymerization inhibitor] ・B-1 to B-4: Compounds having the following structure [Chemical formula 50]

[Silane coupling agent (metal adhesion improver)] ・C-1 to C-3: Compounds of the following structures. In the following formula, Et represents an ethyl group. ・C-4: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd., a silane coupling agent for protecting isocyanate groups) ・C-5: KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd., a silane coupling agent for oligomers containing acrylic groups) [Chemical formula 51]

[Migration inhibitor] ・D-1 to D-4: Compounds with the following structure [Chemical formula 52]

[Additives] E-1 to E-7, E-9: Compound E-8 having the following structure was synthesized by the method described in paragraph 0184 of Japanese Patent Application Laid-Open No. 2019-206689. Specifically, 30 g (0.0707 mol) of 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylene)bisphenol (trade name Tris-PA manufactured by Honshu Chemical Industry Co., Ltd.) and 47.49 g (0.177 mol) of 1,2-naphthoquinonediazide-5-sulfonyl chloride in an amount corresponding to 83.3 mol% of the OH group were stirred and dissolved in 300 g of acetone in a separation flask equipped with a stirrer, a dropping funnel, and a thermometer, and the flask was adjusted to 30°C in a thermostat. Next, 17.9 g of triethylamine was dissolved in 18 g of acetone and placed in a dropping funnel, and then it was dripped into the flask over 30 minutes. After the dripping was completed, stirring was continued for 30 minutes, and then hydrochloric acid was dripped, and stirring was continued for another 30 minutes to terminate the reaction. After that, the reaction product was filtered to remove triethylamine hydrochloride. 1640 g of pure water and 30 g of hydrochloric acid were mixed and stirred in a flask, and the filtrate was dripped into the mixture while stirring to obtain a precipitate. After washing and filtering the precipitate, it was dried at 40°C under reduced pressure for 48 hours to obtain E-8. [Chemical formula 53]

[Compound A] ・F-1 to F-23: Compounds with the following structures. F-1 to F-23 are compounds corresponding to the above-mentioned compound A. FR-1: Compounds with the following structure. FR-1 is a compound that does not correspond to the above-mentioned compound A. [Chemical formula 54]

-Synthesis of F-1- 10.00 g of 2-aminophenol and 170 mL of ethanol were stirred in a flask, and 11.18 g of 2-hydroxybenzaldehyde was added. After adding 0.08 g of formic acid, the temperature was raised to 90°C and stirred for 2 hours. Solids were precipitated by air cooling to room temperature, so the solids were recovered by reduced pressure filtration and washed by suspension washing with 85 mL of ethanol. The solids were vacuum dried to obtain 18.53 g of F-1 (yield 95%). 1H NMR (400 MHz, DMSO-d6): δ 13.82 (br s, 1H), 9.75 (br s, 1H), 8.97 (s, 1H), 7.62 (dd, 1H), 7.40-7.35 (m, 2H), 7.14 (dt, 1H), 6.99 (d, 1H), 6.96-6.94 (m, 2H), 6.89 (dt, 1H). F-2 to F-23 were synthesized by the same method as F-1 except that the raw materials were appropriately changed.

[Solvent] ・NMP: N-methyl-2-pyrrolidone ・EL: Ethyl lactate ・DMSO: Dimethyl sulfoxide ・GBL: γ-butyrolactone ・GVL: γ-valerolactone ・MDMPA: 3-methoxy-N,N-dimethylpropionamide ・toluen: Toluene

<Evaluation> [Evaluation of Adhesion after Heat Resistance Test] The resin composition or comparison composition prepared in each embodiment and comparative example was applied in a layer on an 8-inch Si wafer with Cu wiring pattern (L/S 10μm (thickness 5μm) (comb-shaped) Si wafer with Cu wiring pattern) that had not been pretreated by a spin coating method to form a resin composition layer or a comparison 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, thereby forming a resin composition layer or comparative composition layer having a uniform thickness as described in the "Film Thickness (μm)" column of the table on the copper substrate. In the example where "Negative" is recorded in the "Development Conditions" column of the table, a photomask with a square non-mask portion of 100 μm square is used, and in the example where "Positive" is recorded in the "Development Conditions" column of the table, a photomask with a square mask portion of 100 μm square is used. The resin composition layer or the comparative composition layer on the copper substrate is exposed with light of the exposure wavelength (nm) recorded in the "Exposure Wavelength (nm)" column of the table at an exposure energy of 500 mJ/ ^cm2 . In the example where "M" is recorded in the "Exposure Conditions" column, exposure is performed using a stepper as a light source. In the example where "D" is recorded in the "Exposure Conditions" column, a direct exposure device (ADTEC DE-6UH III) is used as a light source, and laser direct imaging exposure is performed in a range of 100 μm square without using a photomask. Thereafter, the resin layer was developed for 60 seconds using the developer described in the table to obtain a 100 μm square resin layer. The "TMAH aqueous solution" in the table refers to a 2.38 mass % aqueous solution of tetramethylammonium hydroxide. In the case where a numerical value is described in the "hardening temperature" column, the resin composition layer after exposure was heated at a heating rate of 10°C/min in a nitrogen environment using a heating plate, and after reaching the temperature described in the "hardening temperature (°C)" column in the table, the temperature was maintained for the "hardening time (min)" in the table to obtain a hardened material. In the example where "IR" is written in the "Curing temperature (°C)" column, the resin film obtained in each embodiment was heated at a heating rate of 10°C/min in a nitrogen environment using an infrared lamp heating device (manufactured by ADVANCE RIKO, Inc., RTP-6). After reaching 230°C, the above temperature was maintained for the time of "Curing time (min)" in the table to obtain a cured product. The copper substrate with the obtained cured product was placed in a tank at a temperature of 175°C in the atmosphere for 192 hours. A cross-sectional SEM (scanning microscope) measurement was performed, and the void area ratio between the Cu wiring pattern and the cured product was evaluated. The void area ratio was calculated by the following formula. Void area ratio (%) = (area of voids observed by SEM measurement) / (total area of hardened product) × 100 Based on the obtained void area ratio value, the evaluation was performed according to the following evaluation criteria. The evaluation results are recorded in the "Adhesion after heat resistance test" column of the table. It can be said that the smaller the void area ratio, the better the adhesion of the cured film after the heat resistance test, and it can be said that even after a long time, voids are unlikely to occur between the metal layer and the hardened product. -Evaluation criteria- A: The void area ratio is 0.5% or less. B: The void area ratio exceeds 0.5% and is 1% or less. C: The void area ratio exceeds 1% and is 2% or less. D: The void area ratio exceeds 2%.

[Composition stability] The resin composition or comparative composition prepared in each embodiment or comparative example was left to stand for 3 days under light-shielding conditions and at 38°C. After the standing, the viscosity was measured using a viscometer (Toki Sangyo Co., Ltd RE-85L), compared with the initial state (before the standing), and the viscosity change rate after the standing was calculated according to the following formula, and evaluated according to the following evaluation criteria. The evaluation results are recorded in the "Composition stability" column of the table. It can be said that the smaller the viscosity change rate, the better the composition stability of the composition. Viscosity change rate (%) = | (viscosity after the above-mentioned static state - viscosity before the above-mentioned static state) | / (viscosity before the above-mentioned static state) × 100 -Evaluation criteria- A: The absolute value of the above-mentioned viscosity change rate is 3% or less. B: The absolute value of the above-mentioned viscosity change rate exceeds 3% and is 5% or less. C: The absolute value of the above-mentioned viscosity change rate exceeds 5% and is 8% or less. D: The absolute value of the above-mentioned viscosity change rate exceeds 8% and is 10% or less. E: The absolute value of the above-mentioned viscosity change rate exceeds 10%.

From the above results, it can be seen that the cured product formed by the resin composition of the present invention has excellent adhesion even after the heat resistance test. The comparative composition of Comparative Example 1 does not contain compound A. It can be seen that for this comparative composition, the cured product after the heat resistance test has poor adhesion.

<Example 101> The resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by spin coating, and after drying at 100°C for 5 minutes to form a photosensitive film with a film thickness of 20μm, it was exposed using a stepper (manufactured by Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365nm through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10μm). After the above exposure, the layer pattern was obtained by developing with cyclopentanone for 2 minutes and rinsing with PGMEA for 30 seconds. Then, in a nitrogen environment, the temperature was raised at a rate of 10°C/min to 230°C, and then maintained at 230°C for 180 minutes to form an interlayer insulating film for the redistribution layer. The interlayer insulating film for the redistribution layer has excellent insulation properties. In addition, the results of using the interlayer insulating film for the redistribution layer to manufacture semiconductor devices confirmed that they were operating normally.

without.

Claims (15)

A resin composition comprising: at least one resin selected from the group consisting of cyclized resins and precursors thereof; and a compound A represented by the following formula (A-1) having a total carbon number of 3 to 30, [Chemical Formula 1] In formula (A-1), ^R1 represents a monovalent organic group, the bonding site of ^R1 to the nitrogen atom described in formula (A-1) is a carbon atom, ^R2 represents a hydrogen atom or a monovalent organic group, ^R3 represents a monovalent organic group, and ^R2 and ^R3 may bond to form a ring structure. The resin composition as claimed in claim 1, comprising a compound represented by the following formula (A-2) as the compound A, [Chemical Formula 2] In formula (A-2), ^Ar1 and ^Ar2 are each independently an aromatic group which may have a substituent and has at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom at at least one of the ring members of the aromatic group and the substituent, and ^R2 represents a hydrogen atom or a monovalent organic group. The resin composition as described in claim 2, wherein at least one of the Ar ¹ , Ar ² and R ² has a phenolic hydroxyl group. The resin composition as described in claim 2, wherein at least one of the aforementioned Ar ¹ , the aforementioned Ar ² and the aforementioned R ² has a heterocyclic structure. A resin composition as described in any one of claim 1 to claim 4, wherein the resin is polyimide or a polyimide precursor. The resin composition as described in any one of claims 1 to 4, further comprising a photopolymerization initiator and a polymerizable compound. The resin composition as described in any one of claims 1 to 4 is used to form an interlayer insulating film for a redistribution layer. A cured product obtained by curing the resin composition described in any one of claims 1 to 7. A laminate comprising two or more layers consisting of the hardened material as defined in claim 8, and comprising a metal layer between any of the layers consisting of the hardened material. A method for producing a cured product, comprising a film forming step of applying the resin composition described in any one of claims 1 to 7 to a substrate to form a film. The method for manufacturing a hardened product as described in claim 10 comprises: an exposure step of selectively exposing the aforementioned film; and a developing step of developing the aforementioned film using a developer to form a pattern. The method for manufacturing a cured product as described in claim 10 includes a heating step of heating the aforementioned film at 50 to 450°C. A method for manufacturing a laminate, comprising the method for manufacturing a hardened object as described in claim 10. A method for manufacturing a semiconductor device, comprising the method for manufacturing a hardened material as described in claim 10. A semiconductor device comprising the hardener described in claim 8.