TWI890841B - Curable resin composition, cured product, laminate, method for producing cured product, semiconductor device, polyimide precursor and method for producing the same - Google Patents

Abstract

The present invention provides a curable resin composition containing a polyimide precursor having a group containing an ethylenically unsaturated bond or a polar conversion group, a total content of cyclic imide structures and cyclic isoimide structures of 0 to 0.29 mmol/g, and an amine value of 0.0040 to 1.1100 mmol/g; a cured product formed by curing the curable resin composition; a laminate containing the cured product; a method for producing the cured product; a semiconductor device containing the cured product or the laminate; and the polyimide precursor and its method for producing the same.

Description

Curable resin composition, cured product, laminate, method for producing cured product, semiconductor device, polyimide precursor and method for producing the same

The present invention relates to a curable resin composition, a cured product, a laminate, a method for manufacturing the cured product, a semiconductor device, a polyimide precursor, and a method for manufacturing the same.

Polyimide's excellent heat resistance and insulation properties make it suitable for a variety of applications. While these applications are not particularly limited, examples include its use as insulating films, sealing materials, and protective films for semiconductor devices. Furthermore, it can be used as a base film or cover film for flexible substrates.

For example, in the aforementioned applications, polyimide is used in the form of a curable resin composition containing a polyimide precursor. This curable resin composition is applied to a substrate, for example, by coating, to form a photosensitive film. The film is then exposed, developed, and heated as needed to form a cured product on the substrate. The polyimide precursor is cyclized, for example, by heating, to form a polyimide in the cured product. Because the curable resin composition can be applied using known coating methods, it offers excellent manufacturing flexibility, allowing for a high degree of design freedom in terms of the shape, size, and application location of the curable resin composition. Considering the excellent manufacturing adaptability in addition to the high performance of polyimide, the industrial application development of these curable resin compositions is increasingly anticipated.

For example, Patent Document 1 describes a photosensitive resin composition comprising a heterocyclic polymer precursor selected from polyimide precursors and polybenzoxazole precursors and a solvent. The amine value of the solid component of the photosensitive resin composition is 0.0002 to 0.0200 mmol/g.

[Patent Document 1] International Publication No. 2018/151195

Curable resin compositions are required to have a high tolerance for variations in exposure during exposure. In the present invention, a high tolerance for variations in exposure during exposure of a curable resin composition is also referred to as having excellent exposure tolerance. Furthermore, cured products made from curable resin compositions are required to have improved chemical resistance.

The present invention aims to provide a curable resin composition having excellent exposure latitude and a cured product having excellent chemical resistance, a cured product formed by curing the curable resin composition, a laminate containing the cured product, a method for producing the cured product, and a semiconductor device containing the cured product or the laminate. Another object of the present invention is to provide a novel polyimide precursor and a method for producing the same.

Representative embodiments of the present invention are shown below. <1> A curable resin composition comprising a polyimide precursor having a group containing an ethylenically unsaturated bond or a polar conversion group, a total content of cyclic imide structures and cyclic isoimide structures of 0 to 0.29 mmol/g, and an amine value of 0.0040 to 1.1100 mmol/g. <2> The curable resin composition according to <1>, further comprising a photopolymerization initiator. <3> The curable resin composition according to <2>, wherein the photopolymerization initiator is an oxime compound. <4> The hardening resin composition according to any one of <1> to <3>, further comprising a polymerizable compound. <5> The hardening resin composition according to any one of <1> to <4>, further comprising an organometallic complex. <6> The hardening resin composition according to <5>, wherein the organometallic complex is a metallocene compound. <7> The hardening resin composition according to <5> or <6>, wherein the metal contained in the organometallic complex is at least one metal selected from the group consisting of titanium, zirconium, and einsteinium. <8> The hardening resin composition according to any one of <1> to <7>, used to form a photosensitive film for negative tone development. <9> The curable resin composition according to any one of <1> to <8>, which is used to form an interlayer insulating film for a redistribution layer. <10> A cured product obtained by curing the curable resin composition according to any one of <1> to <9>. <11> A laminate comprising two or more layers comprising the cured product according to <10>, wherein a metal layer is provided between any of the layers comprising the cured product. <12> A method for producing a cured product, comprising a film forming step of applying the curable resin composition according to any one of <1> to <9> to a substrate to form a film. <13> The method for producing a cured product according to <12>, comprising an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern. <14> The method for producing a cured product according to <13>, wherein the exposure light used in the exposure comprises light having a wavelength of 405 nm. <15> The method for producing a cured product according to <13> or <14>, wherein the exposure is performed by a laser direct imaging method. <16> The method for producing a cured product according to any one of <12> to <15>, comprising a heating step of heating the film at 50 to 450°C. <17> A semiconductor device comprising the cured product according to <10> or the laminate according to <11>. <18> A polyimide precursor having a group containing an ethylenically unsaturated bond or a polar conversion group, a total content of cyclic imide structures and cyclic isoimide structures of 0 to 0.29 mmol/g, and an amine value of 0.0040 to 1.1100 mmol/g. <19> A method for producing a polyimide precursor, comprising: an amidation step of reacting a dicarboxylic acid compound with a diamine compound to obtain an amide compound; and an end-capping step of reacting the amide compound with an end-capping agent having an amino group. <20> A method for producing a polyimide precursor, comprising: an amidation step of reacting a dicarboxylic acid compound with a diamine compound in the presence of an alkaline catalyst to obtain an amide compound; and an acidic compound addition step of adding an acid to the amide compound. [Effects of the Invention]

The present invention provides a curable resin composition having excellent exposure latitude and a cured product having excellent chemical resistance, a cured product formed by curing the curable resin composition, a laminate containing the cured product, a method for producing the cured product, and a semiconductor device containing the cured product or the laminate. Furthermore, the present invention provides a novel polyimide precursor and a method for producing the same.

The following describes the main embodiments of the present invention. However, the present invention is not limited to the embodiments described. In this specification, numerical ranges indicated by the symbol "～" include the numerical values before and after the symbol "～" as the lower and upper limits, respectively. In this specification, the term "step" refers not only to independent steps but also to steps that cannot be clearly distinguished from other steps, as long as the intended effect of the step is achieved. With regard to the description of groups (atomic groups) in this specification, the description of "unsubstituted" and "unsubstituted" includes both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure with light but also exposure with particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and actinic radiation such as electron beams or radiation. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate," "(meth)acrylic acid" means either or both of "acrylic acid" and "methacrylic acid," and "(meth)acryl" means either or both of "acryl" and "methacryl." 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 solids content refers to the total mass of all components of the composition excluding the solvent. Furthermore, the solids concentration in this specification is the mass percentage of the components excluding the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) and are defined as polystyrene-equivalent values. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined using, for example, an HLC-8220GPC (manufactured by Tosoh Corporation) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, in cases where THF is unsuitable as an eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can be used. Unless otherwise specified, GPC measurements utilize UV (ultraviolet) light with a wavelength of 254 nm. In this specification, when the positional relationship of layers constituting a laminate is described as "upper" or "lower," it suffices to state that other layers exist above or below the reference layer in question. In other words, a third layer or third element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked with respect to a substrate is referred to as "upper." Alternatively, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." This up-down orientation is for the sake of convenience in this specification; in practice, the "upper" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, each component included in a composition may include two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in a composition represents the total content of all compounds corresponding to that component. Unless otherwise specified, this specification assumes a temperature of 23°C, an air pressure of 101,325 Pa (1 atm), and a relative humidity of 50% RH. In this specification, the preferred combination is considered the preferred combination.

(Curing Resin Composition) The curable resin composition of the present invention (hereinafter also referred to as the "resin composition") contains a polyimide precursor (hereinafter also referred to as the "specific resin"). The polyimide precursor has a group containing an ethylenically unsaturated bond or a polar conversion group, a total content of cyclic imide structures and cyclic isoimide structures of 0 to 0.29 mmol/g, and an amine value of 0.0040 to 1.1100 mmol/g.

The curable 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. Furthermore, the curable resin composition of the present invention is preferably used to form a photosensitive film for negative-tone development. In the present invention, negative-tone development refers to development in which unexposed areas are removed by development during exposure and development, while positive-tone development refers to development in which exposed areas are removed by development. For example, the exposure method, developer, and developing method described in the exposure step and the developer and developing method described in the developing step in the description of the method for producing a cured product described below can be used as the exposure method, developer, and developing method.

The curable resin composition of the present invention exhibits excellent exposure sensitivity and chemical resistance of the resulting patterns. While the mechanism for achieving these effects is not yet clear, it is speculated as follows.

The polyimide precursor used in the present invention has a combined content of cyclic imide and cyclic isoimide structures of 0 to 0.29 mmol/g and an amine value of 0.0040 to 1.1100 mmol/g. By maintaining the combined content of cyclic imide and cyclic isoimide structures within the above range, the amount of ethylenically unsaturated bond-bearing groups or polar conversion groups contained in the specific resin increases, thereby improving the reactivity of the ethylenically unsaturated bond-bearing groups or polar conversion groups during exposure. This enables pattern hardening based on sufficient crosslinking over a wide range of exposure doses, and enhances exposure latitude (tolerance to exposure dose variations). On the other hand, keeping the amine value within the above range increases the alkalinity of the photosensitive film, facilitating imidization during curing. This is expected to improve the chemical resistance of the cured product. Originally, when the combined content of cyclic imide and cyclic isoimide structures is below 0.29 mmol/g, the imidization rate after curing is reduced, leading to decreased chemical resistance and elongation at break. However, in the present invention, by keeping the amine value in the specific resin within the above range, it is expected that the imidization rate in the cured product can be effectively increased, thereby achieving excellent chemical resistance. The excellent chemical resistance of the cured product is believed to inhibit dissolution of the cured product even when it comes into contact with a developer or other curable resin composition, for example, when applying another curable resin composition containing a solvent to the cured product obtained by curing the curable resin composition of the present invention and curing the cured product to form a laminate. According to the present invention, it is believed that a cured product with excellent chemical resistance can be obtained, for example, with suppressed solubility in polar solvents such as dimethylsulfoxide (DMSO) and N-methylpyrrolidone (NMP), aqueous alkaline solutions such as aqueous tetramethylammonium hydroxide (TMAH), or mixtures of such polar solvents and aqueous alkaline solutions.

Furthermore, it is speculated that the ease of imidization in the cured product, as described above, also contributes to an improvement in the elongation at break of the cured product. Furthermore, it is speculated that by keeping the total content of the cyclic imide structure and the cyclic isoimide structure within the above range, the resin's light transmittance is increased, resulting in a significantly improved exposure latitude (tolerance to variations in exposure).

Patent Document 1 does not describe a curable resin composition containing a polyimide precursor having a total content of cyclic imide structures and cyclic isoimide structures within the aforementioned range and an amine value within the aforementioned range.

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

<Specified Resin> The curable resin composition of the present invention contains a polyimide precursor (specified resin) having a total content of cyclic imide and cyclic isoimide structures of 0 to 0.29 mmol/g and an amine value of 0.0040 to 1.1100 mmol/g.

[Total Content of Cyclic Imine Structures and Cyclic Isoimide Structures] The total content of cyclic imide structures and cyclic isoimide structures in the specific resin is 0 to 0.29 mmol/g. When the specific resin has at least one of a cyclic imide structure and a cyclic isoimide structure, the at least one of the cyclic imide structure and the cyclic isoimide structure may be present in a side chain, but preferably in the main chain. In this specification, the main chain of a resin refers to the relatively longest molecular chain in the molecule. The lower limit of the total content is preferably 0.01 mmol/g or greater, and more preferably 0.02 mmol/g or greater. The upper limit of the total content is preferably 0.28 mmol/g or less, and more preferably 0.27 mmol/g or less. The total content can be calculated, for example, by the method described in the Examples.

[Amine Value] The specific resin has an amine value of 0.0040 to 1.1100 mmol/g. The lower limit of the amine value is preferably 0.0045 mmol/g or greater, and more preferably 0.0050 mmol/g or greater. The upper limit of the amine value is preferably 1.1050 mmol/g or less, and more preferably 1.1000 mmol/g or less. The amine value can be calculated, for example, by the method described in the Examples.

Furthermore, the specific resin has a group containing an ethylenically unsaturated bond or a polar conversion group. Preferred groups containing an ethylenically unsaturated bond include vinyl, allyl, vinylphenyl, and (meth)acryloyl. From the perspective of reactivity, (meth)acryloyl is more preferred, and (meth)acryloyloxy is even more preferred. The molar content of the group containing an ethylenically unsaturated bond per gram of the specific resin is preferably 2.10 to 2.80 mmol/g, more preferably 2.15 to 2.75 mmol/g, and even more preferably 2.20 to 2.70 mmol/g.

Examples of polarity-converting groups include acid-degradable groups. Acid-degradable groups are not particularly limited as long as they decompose under the action of acid to generate alkali-soluble groups such as phenolic hydroxyl groups and carboxyl groups. However, acetal groups, ketal groups, silyl groups, silyl ether groups, and tertiary alkyl ester groups are preferred. From the perspective of exposure sensitivity, acetal groups or ketal groups are more preferred. Specific examples of acid-degradable groups include tertiary butoxycarbonyl groups, isopropoxycarbonyl groups, tetrahydropyranyl groups, tetrahydrofuranyl groups, ethoxyethyl groups, methoxyethyl groups, ethoxymethyl groups, trimethylsilyl groups, tertiary butoxycarbonylmethyl groups, and trimethylsilyl ether groups. From the perspective of exposure sensitivity, ethoxyethyl or tetrahydrofuryl groups are preferred. The molar content of the polarity-converting group per gram of the specific resin is preferably 2.10 to 2.80 mmol/g, more preferably 2.15 to 2.75 mmol/g, and even more preferably 2.20 to 2.70 mmol/g. When the specific resin has an acid-degradable group, the curable resin composition preferably includes a photoacid generator, described below, as a photosensitizer. For example, a chemically amplified positive-working photosensitive film or a negative-working photosensitive film can be formed from this curable resin composition.

[Repeating unit represented by formula (2)] In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

In formula (2), ^A1 and ^A2 independently represent an oxygen atom or -NH-, preferably an oxygen atom. In formula (2), ^R111 represents a divalent organic group. Examples of the divalent organic group include groups comprising linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Groups comprising 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 combinations thereof are preferred. Groups comprising aromatic groups having 6 to 20 carbon atoms are even more preferred. The aforementioned linear or branched aliphatic groups may be substituted with groups containing heteroatoms in the chain's alkyl groups, and the aforementioned cyclic aliphatic and aromatic groups may be substituted with groups containing heteroatoms in the ring member's alkyl groups. Preferred embodiments of the present invention include groups represented by -Ar- and -Ar-L-Ar-, with groups represented by -Ar-L-Ar- being particularly preferred. Ar is independently an aromatic group, and L is a group comprising a single bond, an aliphatic alkyl group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, _-SO2- , or -NHCO-, or a combination of two or more of the foregoing. These 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, a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof is preferred, and a diamine containing an aromatic group having 6 to 20 carbon atoms is even more preferred. The linear or branched aliphatic group may be substituted with a group containing a heteroatom in the alkyl group in the chain, and the cyclic aliphatic and aromatic groups may be substituted with a group containing a heteroatom in the alkyl group of a ring member. As examples of the group containing an aromatic group, the following can be cited.

[Chemical formula 1] In the formula, A represents a single bond or a divalent linking group. A single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -C(=O)-, -S-, _-SO2- , -NHCO-, or a combination thereof is preferred. A single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted with fluorine atoms, -O-, -C(=O)-, -S-, or _-SO2- is more preferred. _-CH2- , -O-, -S-, _-SO2- , -C( _CF3 ) _2- , or -C( _CH3 ) _2- is even more preferred. In the formula, * represents a bonding site to another structure.

Specifically, the diamine includes 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyl Cyclohexylmethane and isophoronediamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfonium and 3,3-diaminodiphenylsulfonium, 4,4'-diaminodiphenyl ether and 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzophenone 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'-diaminoterphenyl, 4,4'-bis(4-aminophenyl) Bis[4-(4-aminophenoxy)phenyl]sulfone, Bis[4-(3-aminophenoxy)phenyl]sulfone, Bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane , 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]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-Diaminocumene and 2,5-Diaminocumene, 2,5-Dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-Tetramethyl-p-phenylenediamine, 2,4,6-Trimethyl-m-phenylenediamine, Bis(3-aminopropyl)tetramethyldisiloxane, Bis(p-aminophenyl)octamethylpentasiloxane, 2,7-Diaminofluorene, 2,5-Diaminopyridine, 1,2-Bis(4-aminophenyl)ethane, Diaminobenzanilide, Esters of diaminobenzoic acid, 1,5-Diaminonaphthalene, Diaminotrifluorotoluene, 1,3-Bis(4-aminophenyl)hexafluoropropane, 1,4-Bis(4-aminophenyl)hexafluoropropane (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-trifluoromethyl) at least one diamine selected from the group consisting of 2,4’-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4’-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4’-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3’,5,5’-tetramethyl-4,4’-diaminobiphenyl, 4,4’-diamino-2,2’-bis(trifluoromethyl)biphenyl, 2,2’,5,5’,6,6’-hexafluorotolidine, and 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 described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 in the main chain can also be preferably used.

From the perspective of the flexibility of the resulting organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Ar is independently an aromatic group, and L is an aliphatic alkyl group having 1 to 10 carbon atoms that may be substituted with fluorine atoms, -O-, -CO-, -S-, -SO ₂ -, or -NHCO-, or a combination of two or more of these. Ar is preferably a phenylene group, and L is preferably an aliphatic alkyl group having 1 or 2 carbon atoms that may be substituted with fluorine atoms, -O-, -CO-, -S-, or -SO ₂ -. The aliphatic alkyl group 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 2] In formula (51), ^R50 to ^R57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, at least one of ^R50 to ^R57 is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in formula (2). Examples of the monovalent organic group represented by ^R50 to ^R57 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 3] In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in formula (2). Examples of diamines that provide the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These can be used alone or in combination of two or more.

In formula (2), R ¹¹⁵ represents a tetravalent organic group. A tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * independently represents a bonding site with another structure. [Chemical Formula 4] 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, 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 even 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 includes the tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride. The polyimide precursor may contain only one tetracarboxylic dianhydride residue or two or more tetracarboxylic dianhydride residues as a structure corresponding to R ^115. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 5] In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ has the same meaning as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane Dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-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.

Furthermore, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can be cited as preferred examples.

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

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

[Chemical formula 6]

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group, or a hydroxymethyl group, preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site to another structure. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, a cycloalkylene group, or a polyalkyleneoxy group. 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 polyalkoxylene groups. More preferred are alkylene groups such as ethylene and propylene, -CH ₂ CH (OH) CH ₂ -, cyclohexyl, and polyalkoxylene groups. Even more preferred are alkylene groups such as ethylene and propylene, or polyalkoxylene groups. In the present invention, a polyalkoxylene group refers to a group formed by directly bonding two or more alkoxylene groups. The alkylene groups in the multiple alkoxylene groups contained in the polyalkoxylene group may be the same or different. When a polyalkoxyl group contains multiple alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be random, blocky, or alternating. The carbon number of the alkoxyl group (including the carbon number of the substituent, if the alkylene group has a substituent) is preferably 2 or greater, more preferably 2-10, more preferably 2-6, even more preferably 2-5, even more preferably 2-4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. Furthermore, the number of alkoxyl groups in the polyalkoxyl group (the number of repetitions of the polyalkoxyl group) is preferably 2-20, more preferably 2-10, and even more preferably 2-6. From the perspective of solvent solubility and solvent resistance, polyalkyleneoxy groups are preferably polyethyleneoxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethyleneoxy, or groups formed by bonding multiple polyethyleneoxy groups to multiple propoxy groups. Polyethyleneoxy or polypropyleneoxy groups are more preferred, and polyethyleneoxy is even more preferred. In the aforementioned groups formed by bonding multiple polyethyleneoxy groups to multiple propoxy groups, the polyethyleneoxy and propoxy groups may be arranged randomly, in blocks, or in an alternating pattern. Preferred aspects of the number of repetitions of polyethyleneoxy groups in these groups are as described above.

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

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polarity-converting group such as an acid-decomposable group. Examples of the polarity-converting group include the acid-decomposable groups described above.

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

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

The repeating units represented by formula (2) are preferably repeating units represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having repeating units represented by formula (2-A). By containing repeating units represented by formula (2-A) in the polyimide precursor, the exposure latitude can be further increased. Formula (2-A) [Chemical Formula 7] 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, and at least one of ^R113 and ^R114 is a group containing a polymerizable group, and preferably both contain 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 type of repeating unit represented by formula (2), or may contain two or more types. Furthermore, it may contain structural isomers of the repeating unit represented by formula (2). Furthermore, it goes without saying that the polyimide precursor may contain other types of repeating units in addition to the repeating unit represented by formula (2).

As one embodiment of the polyimide precursor of the present invention, the content of the repeating units represented by formula (2) is 50 mol% or more of all repeating units. A total content of 70 mol% or more is more preferred, 90 mol% or more is even more preferred, and more than 90 mol% is particularly preferred. There is no particular upper limit to the total content, except that all repeating units in the terminal polyimide precursor may be repeating units represented by formula (2).

When the specific resin contains a repeating unit having at least one of a cyclic imide structure and a cyclic isoimide structure, it preferably contains at least one repeating unit selected from the group consisting of repeating units represented by any one of the following formulae (2-1) to (2-4), and more preferably contains at least one repeating unit selected from the group consisting of repeating units represented by any one of the following formulae (2-1) to (2-2). [Chemical Formula 8] In formulae (2-1) to (2-4), R ¹¹¹ , R ¹¹⁴ , R ¹¹⁵ and A ¹ have the same meanings as R ¹¹¹ , R ¹¹⁴ , R ¹¹⁵ and A ¹ in formula (2), and preferred embodiments thereof are also the same.

The total content of the repeating units represented by any one of Formulas (2-1) to (2-4) may be such that the total content of the cyclic imide structure and the cyclic isoimide structure in the specific resin is within the above range.

As an embodiment of the specific resin of the present invention, the total content of the repeating unit represented by formula (2) and the repeating unit represented by any one of formulas (2-1) to (2-4) is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, except that all the repeating units in the terminal specific resin can be any one of the repeating units represented by formula (2) and the repeating units represented by any one of formulas (2-1) to (2-4). Furthermore, as an embodiment of the specific resin of the present invention, the total content of the repeating unit represented by formula (3) and the repeating unit represented by any one of formulas (2-1) to (2-4) is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, except that all the repeating units in the terminal specific resin can be any one of the repeating units represented by formula (3) and the repeating units represented by any one of formulas (2-1) to (2-4).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. Furthermore, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of the polyimide precursor is preferably 1.5 or greater, more preferably 1.8 or greater, and even more preferably 2.0 or greater. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly specified; for example, a value of 7.0 or less is preferred, 6.5 or less is more preferred, and 6.0 or less is even more preferred. In this specification, the molecular weight dispersion is calculated as weight-average molecular weight/number-average molecular weight. Furthermore, when the resin composition includes multiple polyimide precursors as the specific resin, it is preferred that the weight-average molecular weight, number-average molecular weight, and dispersion of at least one polyimide precursor be within the above-mentioned ranges. Furthermore, it is also preferred that the weight-average molecular weight, number-average molecular weight, and dispersion of the multiple polyimide precursors as a single resin are each within the above-mentioned ranges.

[Method for Producing a Specific Resin] A preferred first aspect of the method for producing a specific resin includes an amidation step of reacting a dicarboxylic acid compound with a diamine compound to obtain an amide compound, and a capping step of reacting the amide compound with a capping agent having an amino group.

The amidation step can be carried out by known methods, for example, preferably by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting it with a diamine. Examples of such halogenating agents include sulfinyl chloride and phosphinoyl chloride. Also, the synthesis can be carried out using a non-halogenated catalyst instead of the halogenating agent. Known amidation catalysts that do not contain a halogen atom can be used without particular limitation as such non-halogenated catalysts, such as boroxine compounds, N-hydroxy compounds, tertiary amines, phosphates, amine salts, urea compounds, and carbodiimide compounds. Examples of the carbodiimide compound include N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methyl iodide. It is also preferred to conduct the amidation step at a temperature below -10°C.

In the first aspect described above, the amidation step can be carried out in an organic solvent. The organic solvent can be appropriately determined depending on the starting materials, and examples thereof include pyridine, γ-butyrolactone, diethylene glycol dimethyl ether (DGE), N-methylpyrrolidone, and N-ethylpyrrolidone.

The capping step involves reacting a capping agent having an amino group with the amide compound. Preferably, the amide compound is one having a carboxyl group at the end. Preferable capping agents include compounds having an amino group and a hydroxyl group. Examples of compounds having an amino group and a hydroxyl group include ethanolamine, 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, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, and 4-aminophenol. Two or more of these may be used, and multiple different terminal groups may be introduced by reacting multiple end-capping agents.

The method for producing a specific resin may include a dicarboxylic acid compound synthesis step in which tetracarboxylic acid dianhydride is reacted with an alcohol compound to obtain a dicarboxylic acid compound (a diester compound of tetracarboxylic acid dianhydride). This reaction can be carried out with reference to a known esterification reaction. The dicarboxylic acid compound obtained in the dicarboxylic acid compound synthesis step can be used as the dicarboxylic acid compound in the amidation step.

The first aspect of the method for producing the specific resin may include a chilling step of adding water or an alcohol compound to the reaction solution containing the amide compound after the amidation step.

The method for producing the specific resin may further include a reprecipitation step. Specific examples of the reprecipitation step include adding the reaction mixture after the shock cooling step to water or alcohol to precipitate the polyimide precursor. The reprecipitation step may be performed after the shock cooling step.

The method for producing the specific resin may include a redissolution step after the reprecipitation step. Specific examples of the redissolution step include obtaining the precipitated resin after the reprecipitation step by filtration or the like, and dissolving the obtained resin in a solvent such as tetrahydrofuran, in which the specific resin is soluble, to prepare a solution. The reprecipitation and redissolution steps may be repeated multiple times. For example, a redissolution step may be performed after the reprecipitation step, and the obtained solution may be subjected to a further reprecipitation step after the redissolution step.

The first aspect described above may further include a drying step. The drying step is preferably a step of collecting the precipitated resin after the reprecipitation step by filtering or the like and drying the resulting product. The drying method is not particularly limited and may be performed by a known method. For example, drying in a known reduced pressure dryer is an example. The drying conditions are not particularly limited; for example, drying at 20°C to 60°C under reduced pressure is an example.

Furthermore, the first aspect described above may further include a purification step for purifying the specific resin. This purification step can, for example, remove residual catalyst residues such as the aforementioned slurry. The purification method is not particularly limited, and known methods can be used, such as contacting the ion-exchange resin with a solution containing the specific resin.

A preferred second aspect of the method for producing a specific resin includes an amidation step of reacting a dicarboxylic acid compound with a diamine compound in the presence of an alkaline catalyst to obtain an amide compound, and an acidic compound addition step of adding an acid to the amide compound. Examples of the alkaline catalyst include tertiary amines, amine salts, and carbodiimide compounds, with carbodiimide compounds being preferred. Examples of the carbodiimide compound include N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methyl iodide.

In the second aspect, the amidation step can be carried out in an organic solvent. The organic solvent can be appropriately determined depending on the raw materials, and the same solvents as those used in the first aspect can be used. In addition, in the second aspect, carrying out the amidation step at a temperature of 10°C or less, for the purpose of reducing the total content of cyclic imide structures and cyclic isoimide structures, is also a preferred aspect of the present invention.

Examples of the acidic compound used in the acidic compound addition step include carboxylic acid compounds, phosphoric acid compounds, phosphonic acid compounds, or sulfonic acid compounds. Carboxylic acid compounds or sulfonic acid compounds are preferred, sulfonic acid compounds are more preferred, and p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, or 10-camphorsulfonic acid or hydrates thereof are even more preferred. The amount of the acidic compound added is preferably 0.05 to 0.5 mol%, and more preferably 0.10 to 0.30 mol%, relative to the molar amount of the amide compound. In the second aspect, performing the acidic compound addition step can yield a specific resin having a combined content of cyclic imide structures and cyclic isoimide structures within the aforementioned range. The acidic compound addition step can be performed, for example, after the amidation step and before the chilling step.

The second aspect may further include the dicarboxylic acid compound synthesis step, the quenching step, the reprecipitation step, the re-dissolution step, the drying step, the purification step, and the like.

[Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or greater, more preferably 30% by mass or greater, even more preferably 40% by mass or greater, and even more preferably 50% by mass or greater, relative to the total solids content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solids content of the resin composition. The resin composition of the present invention may contain only one specific resin or two or more. When more than two types are included, it is best if the total amount is within the above range.

Furthermore, 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, may contain two or more specific resins, and preferably contains two or more specific resins. When the curable resin composition of the present invention contains two or more polyimide precursors, the total content of the cyclic imide structure and the cyclic isoimide structure contained in at least one polyimide precursor and the amine value are within the above ranges, which is equivalent to the total amount of all polyimide precursors being 1g. Some polyimide precursors preferably have a total content of cyclic imide structures and cyclic isoimide structures and an amine value within the above ranges. Regarding the polyimide precursors contained in each curable resin composition, it is more preferred that the total content of cyclic imide structures and cyclic isoimide structures and an amine value within the above ranges. When the resin composition of the present invention contains two or more specific resins, it is preferred to contain two or more polyimide precursors having different structures (R ¹¹⁵ in the above formula (2)) derived from dianhydrate.

<Other Resins> The resin composition of the present invention may contain the specific resins described above and other resins different from the specific resins (hereinafter referred to as "other resins"). Examples of such other resins include phenolic resins, polyamides, epoxy resins, resins containing polysiloxane or siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, by adding a (meth)acrylic resin having a weight-average molecular weight of 20,000 or less and a high polymerizable group value (e.g., a polymerizable group content of 1× ^10-3 mol/g or more per gram of resin) to the resin composition, instead of or in addition to the polymerizable compound described below, the coatability of the resin composition and the solvent resistance of the pattern (cured product) can be improved.

When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or greater, more preferably 0.05% by mass or greater, even more preferably 1% by mass or greater, even more preferably 2% by mass or greater, even more preferably 5% by mass or greater, and even more preferably 10% by mass or greater, relative to the total solids content of the resin composition. Furthermore, 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, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solids content of the resin composition. In a preferred embodiment of the resin composition of the present invention, the content of other resins can be low. In this embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, relative to the total solids content of the resin composition. The lower limit of this content is not particularly limited, as long as it is 0% by mass or greater. The resin composition of the present invention may contain only one other resin or two or more. When containing two or more other resins, the total content is preferably within the above range.

<Organometallic Complex> From the perspective of chemical resistance, the curable resin composition of the present invention preferably contains an organometallic complex. It is speculated that when a specific resin and an organometallic complex are included, the interaction between the organometallic complex and at least one of the cyclic imide structure and cyclic isoimide structure contained in the specific resin can suppress aggregation of the organometallic complex in the photosensitive film and the cured product. Therefore, chemical resistance is further improved compared to the use of a conventional polyimide precursor separate from the specific resin and an organometallic complex.

The organometallic complex may be any organic complex compound containing a metal atom, preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated with a metal atom, and even more preferably a metallocene compound. In the present invention, a metallocene compound refers to an organometallic complex compound having two optionally substituted cyclopentadienyl anion derivatives as η5-ligands. The organic group is not particularly limited; however, a alkyl group or a group composed of a alkyl group and a heteroatom is preferred. Heteroatoms include oxygen, sulfur, and nitrogen atoms. In the present invention, it is preferred that at least one of the organic groups be a cyclic group, and it is even more preferred that at least two of the organic groups be cyclic groups. The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, with a 5-membered cyclic group being even more preferred. The cyclic group may be alkyl or heterocyclic, with alkyl being preferred. A cyclopentadienyl group is preferred as the 5-membered cyclic group. Furthermore, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups per molecule.

The metal contained in the organometallic complex is not particularly limited, but is preferably a metal corresponding to a Group 4 element, more preferably at least one metal selected from the group consisting of titanium, zirconium, and einsteinium, further preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

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

One preferred aspect of the present invention is that the organometallic complex has the ability to initiate photoradical polymerization. In the present invention, having photoradical polymerization initiation ability means the ability to generate free radicals capable of initiating free radical polymerization upon exposure to light. For example, when a composition containing a free radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region absorbed by the organometallic complex and not absorbed by the free radical crosslinking agent, the presence or absence of photoradical polymerization initiation ability can be confirmed by confirming the disappearance of the free radical crosslinking agent. The confirmation of disappearance can be determined by selecting an appropriate method depending on the type of free radical crosslinking agent, such as IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography). When the organometallic complex has the ability to initiate photoradical polymerization, the organometallic 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 photoradical polymerization, the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds, and bezocene compounds. It is more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds, and bezocene compounds. It is even more preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds. Titanocene compounds are particularly preferred.

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

As the organometallic complex, a compound represented by the following formula (P) can be preferably exemplified. [Chemical Formula 9] 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.

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

Specific examples of the organometallic complex are not particularly limited, but include titanium tetraisopropoxide, titanium tetra(2-ethylhexyloxy), titanium diisopropoxide bis(ethylacetoxyacetate), titanium diisopropoxide bis(acetylacetonate), titanium bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl), titanium pentamethylcyclopentadienyl trimethoxide, titanium bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl), and the following compounds. [Chemical Formula 10]

In addition, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but are not limited thereto.

The organometallic complex content is preferably 0.1 to 30 mass% relative to the total solids content of the curable resin composition of the present invention. The lower limit is more preferably 1.0 mass% or greater, even more preferably 1.5 mass% or greater, and particularly preferably 3.0 mass% or greater. The upper limit is even more preferably 25 mass% or less. One or more organometallic complexes may be used. When two or more 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. An organic solvent is preferably used. 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, 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, ethyl 3-ethoxypropionate), etc. esters, etc.)), alkyl 2-alkoxypropionates (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, 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 (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

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

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

Preferred examples of 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 preferably mentioned.

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

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

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

Regarding solvents, mixing two or more solvents is also preferred from the perspective of improving the properties of the coated surface.

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

From the perspective of coating properties, the solvent content is preferably set so that the total solids concentration of the resin composition of the present invention is 5-80 mass%, more preferably 5-75 mass%, even more preferably 10-70 mass%, and even more preferably 20-70 mass%. The solvent content can be adjusted based on the desired coating thickness and coating method.

The resin composition of the present invention may contain only one solvent or two or more solvents. When containing two or more solvents, it is preferred that the total amount of the solvents be within the above range.

[Polymerization Initiator] The resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. A photopolymerization initiator is particularly preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from among known photoradical polymerization initiators. For example, photoradical polymerization initiators that are sensitive to light in the ultraviolet to visible range are preferred. Alternatively, an activator that generates active radicals by interacting with a photoexcited sensitizer may be used.

The photoradical polymerization initiator preferably contains at least one compound having a molar absorbance of at least about 50 L·mol ^-1 ·cm ^-1 within a wavelength range of approximately 240 to 800 nm (preferably 330 to 500 nm). The molar absorbance of the compound can be measured using known methods. For example, it is preferably measured using a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Medical Systems, Inc.) using an ethyl acetate solvent at a concentration of 0.01 g/L.

Any known compound can be used as a photoradical polymerization initiator. Examples include alkyl halides (e.g., compounds having a trioxane skeleton, compounds having a oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazoles and 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, organoboron compounds, and iron aromatic complexes. For details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application 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 Application Publication No. 2014-130173 and Japanese Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the peroxide-based 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 Application Publication No. 2019-043864, the photopolymerization initiator described in Japanese Patent Application Publication No. 2019-044030, and the peroxide-based initiator described in Japanese Patent Application Publication No. 2019-167313 are also incorporated into this specification.

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

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

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

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

As aminoacetophenone-based initiators, compounds described in Japanese Patent Application Laid-Open No. 2009-191179, whose maximum absorption wavelength matches a light source having a wavelength of 365 nm or 405 nm, can also be used, and the contents of such compounds are incorporated into this specification.

Examples of acylphosphine oxide-based initiators include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. In addition, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins B.V.), IRGACURE-819, or IRGACURE-TPO (all manufactured by BASF) can be used.

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

Oxime compounds are more effective as photoradical polymerization initiators. Using oxime compounds effectively increases exposure latitude. Oxime compounds are particularly advantageous because they offer a wider exposure latitude (exposure margin) and also function as photohardening accelerators.

Specific examples of oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, compounds described in Japanese Patent Application Laid-Open 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 Technology (1995, pp. 202-232), the compounds described in Japanese Patent Application Publication No. 2000-066385, the compounds described in Japanese Patent Application Publication No. 2004-534797, the compounds described in Japanese Patent Application Publication No. 2017-019766, the compounds described in Japanese Patent No. 6065596, the compounds described in International Publication No. 2 The compounds described in 015/152153, the compounds described in International Publication No. 2017/051680, the compounds described in JP-A-2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, and the compounds described in International Publication No. 2013/167515 are incorporated into this specification.

Preferred oxime compounds include, for example, compounds having the following structures: 3-benzyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a linking group of >C=N-O-C(=O)- in the molecule.

[Chemical formula 11]

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF) and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, a photoradical polymerization initiator 2 described in JP-A-2012-014052) are also preferably used. 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) can also be used. Alternatively, DFI-091 (manufactured by Daito Chemix Co., Ltd.) or SpeedCure PDO (manufactured by Sartomer Arkema) can be used. Furthermore, an oxime compound having the following structure can also be used. [Chemical Formula 12]

Oxime compounds having a fluorene ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a fluorene ring include compounds described in Japanese Patent Application Laid-Open No. 2014-137466 and Japanese Patent No. 06636081, the contents of which are incorporated into this specification.

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

Oxime compounds containing fluorine atoms can also be used. Specific examples of such oxime compounds include the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471, all of which are incorporated herein.

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

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

Oxime compounds having a hydroxyl substituent bonded to a carbazole backbone can also be used as photoradical polymerization initiators. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019/088055, the contents of which are incorporated herein.

As a photopolymerization initiator, an oxime compound having an aromatic ring group ^ArOX1 (hereinafter also referred to as the oxime compound OX) with an electron-withdrawing group introduced into an aromatic ring can also be used. Examples of the electron-withdrawing group possessed by the aromatic ring group ^ArOX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl and nitro groups are preferred. From the perspective of easily forming a film with excellent light resistance, acyl groups are more preferred, and benzoyl groups are even more 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 heterocyclooxy group, an alkenyl group, an alkylthio group, an arylthio group, an acyl group, or an amino group is preferred; an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, an alkylthio group, an arylthio group, or an amino group is more preferred; and an alkoxy group, an alkylthio 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 formula (OX1) and a compound represented by formula (OX2), and more preferably a compound represented by formula (OX2). [Chemical Formula 13] In the formula, ^RX1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy 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, a carbamoyl group, or a sulfonamyl group; ^RX2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy 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; ^RX3 - ^RX14 each independently represent a hydrogen atom or a substituent. At least one of ^RX10 - ^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 the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.

Preferred oxime compounds include oxime compounds having specific substituents disclosed in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having a thioaryl group disclosed in Japanese Patent Application Laid-Open No. 2009-191061, and the contents thereof are incorporated into the present specification.

From the perspective of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyl triphosphine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine 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.

Further preferred photoradical polymerization initiators are trihalogenomethyl triphosphine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. It is further preferred to use at least one compound selected from the group consisting of trihalogenomethyl triphosphine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds. It is even more preferred to use metallocene compounds or oxime compounds.

Furthermore, photoradical polymerization initiators that can be used include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, quinones formed by condensation of alkyl anthraquinones with aromatic rings, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoins, and benzyl derivatives such as benzyl dimethyl ketal. Compounds represented by the following formula (I) can also be used.

[Chemical formula 14]

In formula (I), R ¹⁰⁰ is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group or biphenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms; R ¹⁰¹ is a group represented by formula (II) or the same group as R ¹⁰⁰ ; and R ¹⁰² to R ¹⁰⁴ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[Chemical formula 15]

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

Furthermore, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used as the photoradical polymerization initiator, and the contents thereof are incorporated into this specification.

Bifunctional, trifunctional, or higher-functional photoradical polymerization initiators can also be used. Using such initiators generates two or more free radicals per molecule, thereby achieving excellent sensitivity. Furthermore, using asymmetric compounds reduces crystallinity and improves solubility in solvents, making precipitation less likely over time and thereby improving the stability of the resin composition over time. Specific examples of bifunctional or trifunctional or higher-functional photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015/004565, paragraphs 0407 to 0412 of JP-A-2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017/033680, and compounds (E) and ( G), Cmpd 1 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 Application Laid-Open No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, and the oxime ester photoinitiator described in Japanese Patent No. 6469669, the contents of which are incorporated into this specification.

When a photopolymerization initiator is included, its content is preferably 0.1-30 mass%, more preferably 0.1-20 mass%, even more preferably 0.5-15 mass%, and even more preferably 1.0-10 mass%, relative to the total solids content of the resin composition of the present invention. A single photopolymerization initiator may be included, or two or more may be included. When two or more photopolymerization initiators are included, the total amount is preferably within the above range. Since a photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further promoted by heating in an oven or on a hot plate.

[Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. When the electronically excited sensitizer comes into contact with a thermal radical polymerization initiator or a photoradical polymerization initiator, electron transfer, energy transfer, and heat generation occur. This chemically decomposes the thermal radical polymerization initiator or the photoradical polymerization initiator, generating free radicals, acids, or bases. As sensitizers, compounds that can be used include benzophenone, michler's ketone, oxonaphthol, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxocyanine, pyrazolotriazole azo, pyridone azo, cyanine, phenathiophene, pyrrolopyrazolyl methine azo, phthalocyanine, benzopyran, and indigo. Examples of the sensitizer include 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-dimethylaminobenzylidene Benzylidene dihydroindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxy Carbonyl-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-tolyldiethanolamine, N-phenylethanolamine, 4-benzoylbenzophenone, isoamyl dimethylaminobenzoate, diethylamine isoamyl benzoate, 2-benzylbenzimidazole, 1-phenyl-5-benzyltetrazolyl, 2-benzylbenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. Other sensitizing dyes may also be used. For details on sensitizing dyes, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, which is incorporated herein by reference.

When the resin composition includes 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 solids content of the resin composition. Sensitizers may be used singly or in combination.

[Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds containing -SS-, _-SO2 -S-, -NO-, SH, PH, SiH, and GeH within their molecules, and dithiobenzoic acids, trithiocarbonates, dithiocarbamates, and xanthate compounds containing thiocarbonylthio groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds generate free radicals by donating hydrogen to low-activity free radicals or by deprotonating after oxidation to generate free radicals. In particular, thiol compounds can be preferably used.

Furthermore, 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 thereof are incorporated into this specification.

When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solids content of the resin composition of the present invention. The chain transfer agent may be a single type or two or more types. When two or more types of chain transfer agents are used, their total content is preferably within the above range.

[Photoacid Generator] The resin composition of the present invention preferably contains a photoacid generator. A photoacid generator refers to a compound that generates at least one of a Brünster acid and a Lewis acid upon irradiation with light of 200 nm to 900 nm. The irradiated light preferably has a wavelength of 300 nm to 450 nm, more preferably 330 nm to 420 nm. When used alone or in combination with a sensitizer, a photoacid generator that generates an acid upon exposure is preferred. Preferred examples of the acid generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

Examples of photoacid generators used in the resin composition of the present invention include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfonate compounds, and onium salt compounds. From the perspectives of sensitivity and storage stability, organic halogenated compounds, oxime sulfonate compounds, and onium salt compounds are preferred. From the perspectives of mechanical properties of the resulting film, oxime esters are preferred.

Examples of quinonediazide compounds include those obtained by forming a sulfonate bond of quinonediazide with a monovalent or polyvalent hydroxyl compound, those obtained by forming a sulfonate-sulfonamide bond of quinonediazide with a monovalent or polyvalent amine compound, and those obtained by forming a sulfonate bond and/or a sulfonamide bond of quinonediazide with a polyhydroxypolyamine compound. All functional groups in these polyhydroxy compounds, polyamine compounds, and polyhydroxypolyamine compounds may not be substituted with quinonediazide, but preferably, at least 40 mol% of the total functional groups are substituted with quinonediazide on average. By containing this quinone diazide compound, a resin composition can be obtained that is sensitive to i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) of mercury lamps, which are common ultraviolet rays.

Specifically, the hydroxyl compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropyl alcohol, octanol, tert-butyl alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS- 26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are product names, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (these are product names, manufactured by Asahi Yukizai Corporation), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (product name, manufactured by Honshu Chemical Industry Co., Ltd.), novolac resin, etc., but are not limited to these.

Specific examples of the amino compound include, but are not limited to, aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 4,4'-diaminodiphenyl ether.

Specific examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine.

Among these, phenol compounds and esters with 4-naphthoquinonediazidesulfonyl groups are preferred as quinonediazide compounds. This allows for higher sensitivity and resolution to i-ray exposure.

The content of the quinonediazide compound used in the resin composition of the present invention is preferably 1 to 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of the resin. Setting the quinonediazide compound content within this range is preferred because it improves the contrast between exposed and unexposed areas, thereby achieving higher sensitivity. Furthermore, a sensitizer or the like may be added as needed.

The photoacid generator is preferably a compound containing an oximesulfonate group (hereinafter referred to as an "oximesulfonate compound"). The oximesulfonate compound is not particularly limited as long as it contains an oximesulfonate group, but oximesulfonate compounds represented by the following formula (OS-1), the later-described formula (OS-103), the formula (OS-104), or the formula (OS-105) are preferred.

[Chemical formula 16]

In formula (OS-1), ^X₃ represents an alkyl group, an alkoxy group, or a halogen atom. When multiple ^X₃ groups are present, they may be the same or different. The alkyl and alkoxy groups in ^X₃ may have substituents. The alkyl group in ^X₃ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group in ^X₃ is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in ^X₃ is preferably a chlorine atom or a fluorine atom. In formula (OS-1), m₃ represents an integer from 0 to 3, preferably 0 or 1. When m₃ is 2 or 3, the multiple ^X₃ groups may be the same or different. In formula (OS-1), ^R represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthracenyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

In formula (OS-1), the compound wherein m3 is 3, ^X3 is methyl, the substitution position of ^X3 is an ortho position, and ^R34 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorkanylmethyl, or p-tolyl is particularly preferred.

Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of JP-A-2011-209692 and paragraphs 0158 to 0167 of JP-A-2015-194674, the contents of which are incorporated herein.

[Chemical formula 17]

In Formulas (OS-103) to (OS-105), ^Rs1 represents an alkyl group, an aryl group, or a heteroaryl group. Plural ^Rs2 groups may be present and each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. Plural ^Rs6 groups may be present and each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group. Xs represents O or S, ns represents 1 or 2, and ms represents an integer from 0 to 6. In Formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by ^Rs1 may have known substituents as long as the effects of the present invention can be achieved.

In formulas (OS-103) to (OS-105), ^Rs2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), or an aryl group (preferably having 6 to 30 carbon atoms), more preferably a hydrogen atom or an alkyl group. In compounds where two or more ^Rs2 exist, one or two are preferably alkyl groups, aryl groups, or halogen atoms, more preferably one is an alkyl group, aryl group, or halogen atom, and particularly preferably one is an alkyl group and the rest are hydrogen atoms. The alkyl or aryl group represented by ^Rs2 may have known substituents as long as the effects of the present invention are achieved. In formulas (OS-103), (OS-104), or (OS-105), Xs represents O or S, preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1. When Xs is S, ns is preferably 2. In formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by ^Rs6 may have a substituent. In formulas (OS-103) to (OS-105), ms represents an integer from 0 to 6, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Furthermore, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110), or formula (OS-111), the compound represented by the above formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109). [Chemical Formula 18]

In Formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group, or a heteroaryl group; R ^t7 represents a hydrogen atom or a bromine atom; R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group; R ^t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group; and R ^t2 represents a hydrogen atom or a methyl group. In Formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, with a hydrogen atom being preferred.

In formulas (OS-106) to (OS-111), ^Rt8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group. An alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group is preferred. An alkyl group having 1 to 8 carbon atoms is more preferred. An alkyl group having 1 to 6 carbon atoms is even more preferred. A methyl group is particularly preferred.

In Formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, preferably a hydrogen atom. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Furthermore, in the above-mentioned oxime sulfonate compounds, the oxime stereostructure (E, Z) may be either one or a mixture. Specific examples of the oxime sulfonate compounds represented by Formulas (OS-103) to (OS-105) include the compounds described in paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs 0168 to 0194 of JP-A-2015-194674, the contents of which are incorporated herein.

As other preferred aspects of the oxime sulfonate compound containing at least one oxime sulfonate group, compounds represented by the following formula (OS-101) and formula (OS-102) can be cited.

[Chemical formula 19]

In Formula (OS-101) or (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. More preferably, R ^u9 is a cyano group or an aryl group, and even more preferably, R ^u9 is a cyano group, a phenyl group, or a naphthyl group. In Formula (OS-101) or (OS-102), R ^u2a represents an alkyl group or an aryl group. In Formula (OS-101) or (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, -CR ^u6 H-, or CR ^u6 R ^u7 -, and R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfonyl group, a cyano group, or an aryl group. Two of R ^u1 to R ^u4 may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring with a benzene ring. R ^u1 to R ^u4 are preferably a hydrogen atom, a halogen atom, or an alkyl group. It is also preferred that at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group. It is particularly preferred that all of R ^u1 to R ^u4 are hydrogen atoms. Each of the above substituents may further have a substituent.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102). Furthermore, in the above oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be any one or a mixture. Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Publication No. 2015-194674, the contents of which are incorporated into this specification. Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferred. [Chemical Formula 20] Commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

Furthermore, the compound represented by the following structural formula can be cited as a preferred example. [Chemical Formula 21]

Specific examples of organic halogenated compounds include Wakabayashi et al., Bull Chem. Soc Japan, 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Application Laid-Open No. 48-36281, Japanese Patent Application Laid-Open No. 55-32070, Japanese Patent Application Laid-Open No. 60-239736, Japanese Patent Application Laid-Open No. 61-169835, Japanese Patent Application Laid-Open No. 61-169837, Japanese Patent Application Laid-Open No. 62-58241, Japanese Patent Application Laid-Open No. 62-212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, and M.P. Hutt, "Journal of Heterocyclic The compounds described in "Chemistry" 1 (No. 3), (1970) and the like are incorporated into this specification. In particular, trihalomethyl-substituted azole compounds: symmetrical triazole compounds can be cited as preferred examples. More preferably, symmetrical triazole derivatives formed by bonding at least one mono-, di-, or trihalomethyl substituted methyl group to a symmetrical triazole ring can be cited. Specifically, for example, 2,4,6-tris(monochloromethyl)symmetrical triazole, 2,4,6-tris(dichloromethyl)symmetrical triazole, 2,4,6-tris(trichloromethyl)symmetrical triazole, 2-methyl-4,6-bis(trichloromethyl)symmetrical triazole, 2-n-propyl-4,6-bis(trichloromethyl)symmetrical triazole, trisinium, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl) symmetrical trisinium, 2-phenyl-4,6-bis(trichloromethyl) symmetrical trisinium, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl) symmetrical trisinium, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl) symmetrical trisinium, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl) symmetrical trisinium, 2-[1-(p-methoxyphenyl)] phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl) symmetrical trisinol, 2-phenylvinyl-4,6-bis(trichloromethyl) symmetrical trisinol, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl) symmetrical trisinol, 2-(p-isopropoxyphenyl)-4,6-bis(trichloromethyl) symmetrical trisinol, 2-(p-tolyl)-4,6-bis(trichloromethyl) symmetrical trisinol, 2-(4-naphthyloxyphenyl)- 2-Benzylthio-4,6-bis(trichloromethyl) symmetric trithione, 2-phenylthio-4,6-bis(trichloromethyl) symmetric trithione, 2-benzylthio-4,6-bis(trichloromethyl) symmetric trithione, 2,4,6-tris(dibromomethyl) symmetric trithione, 2,4,6-tris(tribromomethyl) symmetric trithione, 2-methyl-4,6-bis(tribromomethyl) symmetric trithione, 2-methoxy-4,6-bis(tribromomethyl) symmetric trithione, etc.

Examples of the organic borate compounds include Japanese Patent Application Laid-Open No. 62-143044, Japanese Patent Application Laid-Open No. 62-150242, Japanese Patent Application Laid-Open No. 9-188685, Japanese Patent Application Laid-Open No. 9-188686, Japanese Patent Application Laid-Open No. 9-188710, Japanese Patent Application Laid-Open No. 2000-131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, and Kunz, Martin "Rad Tech '98. Proceeding April Organic borates described in "Chicago" et al., 19-22, 1998, organic borate salts described in Japanese Patent Application Laid-Open No. 6-157623, Japanese Patent Application Laid-Open No. 6-175564, Japanese Patent Application Laid-Open No. 6-175561, organic boron-zinc complexes or organic boron-oxygen-zinc complexes described in Japanese Patent Application Laid-Open No. 6-175554, Japanese Patent Application Laid-Open No. 6-175553 Specific examples include organoboron transition metal complexes such as those described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014, and the like, and the contents thereof are incorporated into this specification.

Examples of the disulfide compounds include compounds described in Japanese Patent Application Laid-Open No. 61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfide compounds.

Examples of the above-mentioned onium salt compounds include S.I.Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S.Bal et al. Diazo salts described in al, Polymer, 21,423 (1980), ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Application Laid-Open No. 4-365049, etc., phosphonium salts described in U.S. Patent No. 4,069,055, U.S. Patent No. 4,069,056, European Patent No. 104,143, U.S. Patent No. 339,049, U.S. Patent No. 410,201, iodine salts described in Japanese Patent Application Laid-Open No. 2-150848, Japanese Patent Application Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 39 0,214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, J.V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J.V. Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), and onium salts such as arsenic salts and pyridinium salts described in C.S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), are incorporated into this specification.

Examples of onium salts include those represented by the following general formulas (RI-I) to (RI-III). [Chemical Formula 22]

In formula (RI-I), _Ar11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having 1 to 12 carbon atoms, an arylamide group having 6 to 20 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. From the perspective of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, and sulfinic acid ions are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms in an alkyl group, an alkylamide group or an arylamide group having 1 to 12 carbon atoms in an alkyl group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. From the perspective of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, and carboxylic acid ions are preferred. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each independently represent an aryl group having 6 to 20 carbon atoms, which may have 1 to 6 substituents, or an alkyl group, an alkenyl group, or an alkynyl group. Preferably, an aryl group is preferred from the viewpoint of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group in which the alkyl group independently has 1 to 12 carbon atoms, an alkylamide group or an arylamide group in which the alkyl group has 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. From the perspective of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, and carboxylic acid ions are preferred.

Specific examples of preferred photoacid generators include the following.

[Chemical formula 23] [Chemical formula 24] [Chemical formula 25] [Chemical formula 26]

The photoacid generator is preferably used in an amount of 0.1-20 mass%, more preferably 0.5-18 mass%, even more preferably 0.5-10 mass%, even more preferably 0.5-3 mass%, and even more preferably 0.5-1.2 mass%, relative to the total solids content of the resin composition. A single photoacid generator may be used alone, or multiple types may be used in combination. When multiple types are used in combination, the total amount is preferably within the above range. In addition, to impart photosensitivity to the desired light source, it is also preferably used in combination with a sensitizer.

<Thermal Acid Generator> The composition of the present invention may contain a thermal acid generator. The thermal acid generator has the effect of generating an acid upon heating, thereby promoting the crosslinking reaction of at least one compound selected from compounds having hydroxymethyl, alkoxymethyl, or acyloxymethyl groups, epoxy compounds, cyclohexane compounds, and benzophenone compounds.

The thermal decomposition starting temperature of the thermal acid generator is preferably between 50°C and 270°C, more preferably between 50°C and 250°C. Furthermore, it is preferable to select a thermal acid generator that does not generate acid during drying (pre-bake: approximately 70°C to 140°C) after the composition is applied to the substrate, but generates acid during the final heating (vulcanization: approximately 100°C to 400°C) after patterning during subsequent exposure and development. This can suppress sensitivity degradation during development and is therefore preferable. The thermal decomposition starting temperature is determined as the peak temperature of the lowest thermal peak when the thermal acid generator is heated at 5°C/minute to 500°C in a pressure-resistant capsule. Examples of equipment used to measure the thermal decomposition onset temperature include the Q2000 (manufactured by TA Instruments).

The acid generated by the thermal acid generator is preferably a strong acid, such as aromatic sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkanesulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or halogenated alkanesulfonic acids such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of Japanese Patent Application Laid-Open No. 2013-072935.

Among them, from the viewpoint of less residue in the organic membrane and less deterioration of the physical properties of the organic membrane, the one that generates an alkanesulfonic acid having 1 to 4 carbon atoms or a halogen alkanesulfonic acid having 1 to 4 carbon atoms is more preferred. As the thermal acid generator, (4-hydroxyphenyl)dimethylcoppersulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylcoppersulfonate, (4-hydroxyphenyl)methylcoppersulfonate, (4-((methoxycarbonyl)oxy)phenyl)methylcoppersulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)coppersulfonate), (4-hydroxyphenyl)trifluoromethanesulfonate Preferred are trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethylcopperium salt, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)methylcopperium salt, trifluoromethanesulfonic acid (benzyl(4-hydroxyphenyl)methylcopperium salt, trifluoromethanesulfonic acid (benzyl(4-((methoxycarbonyl)oxy)phenyl)methylcopperium salt, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copperium salt, trifluoromethanesulfonic acid (3-(5-((propanesulfonyl)oxy)imino)thiophen-2(5H)-ylidene)-2-(o-tolyl)propionitrile, and 2,2-bis(3-(methylsulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

Furthermore, as the thermal acid generator, the compound described in paragraph 0059 of Japanese Patent Application Laid-Open No. 2013-167742 is also preferred.

The content of the thermal acid generator is preferably 0.01 parts by mass or greater, and more preferably 0.1 parts by mass or greater, per 100 parts by mass of the specific resin. The inclusion of 0.01 parts by mass or greater promotes crosslinking reactions, thereby further improving the mechanical properties and solvent resistance of the organic film. Furthermore, from the perspective of the electrical insulation of the organic film, the content is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

<Base Generator> The resin composition of the present invention may contain a base generator. A base generator is a compound capable of generating a base through physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, it is particularly preferred that the resin composition contain a base generator. By including a thermal base generator in the resin composition, the cyclization reaction of the precursor can be accelerated, for example, by heating, resulting in a cured product with excellent mechanical properties and chemical resistance, such as interlayer insulation films for redistribution layers included in semiconductor packages. The base generator can be either ionic or non-ionic. Examples of bases generated from the base generator include diamines and tertiary amines. The base generator of the present invention is not particularly limited, and known base generators can be used. Examples of known base generators include aminoformyl oxime compounds, aminoformylhydroxylamine compounds, carbamic 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-xylylenediamine derivative compounds, and acyloxyimino compounds. Specific examples of non-ionic base generators include compounds represented by Formula (B1), Formula (B2), or Formula (B3). [Chemical Formula 27]

In formulas (B1) and (B2), ^Rb1 , ^Rb2 , and ^Rb3 are each independently an organic group, a halogen atom, or a hydrogen atom that does not have a tertiary amine structure. However, ^Rb1 and ^Rb2 cannot simultaneously be hydrogen atoms. Furthermore, ^Rb1 , ^Rb2 , and ^Rb3 do not have a carboxyl group. Furthermore, in this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, even when the carbon atom to which the bond is formed is a carbonyl group, that is, when it forms an amide group together with a nitrogen atom, the structure is not limited thereto.

In formula (B1) and formula (B2), at least one of ^Rb1 , ^Rb2 , and ^Rb3 preferably comprises a cyclic structure, and at least two of them more preferably comprise a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, with a monocyclic ring or a condensed ring formed by condensing two monocyclic rings being preferred. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, with a 6-membered ring being more preferred. The monocyclic ring is preferably a cyclohexyl ring or a benzene ring, with a cyclohexyl ring being more preferred.

More specifically, ^Rb1 and ^Rb2 are preferably hydrogen atoms, alkyl groups (preferably having 1-24 carbon atoms, more preferably 2-18 carbon atoms, and even more preferably 3-12 carbon atoms), alkenyl groups (preferably having 2-24 carbon atoms, more preferably 2-18 carbon atoms, and even more preferably 3-12 carbon atoms), aryl groups (preferably having 6-22 carbon atoms, more preferably 6-18 carbon atoms, and even more preferably 6-10 carbon atoms), or aralkyl groups (preferably having 7-25 carbon atoms, more preferably 7-19 carbon atoms, and even more preferably 7-12 carbon atoms). These groups may have substituents within the scope of the present invention. ^Rb1 and ^Rb2 may bond to each other to form a ring. The formed ring is preferably a 4-7 membered nitrogen-containing heterocyclic ring. In particular, ^Rb1 and ^Rb2 are preferably linear, branched, or cyclic alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms) which may have a substituent, more preferably cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms) which may have a substituent, and even more preferably cyclohexyl groups which may have a substituent.

Examples of Rb ³ include alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms), An aralkenyl group (preferably having 8-24 carbon atoms, more preferably 8-20, and even more preferably 8-16 carbon atoms), an alkoxy group (preferably having 1-24 carbon atoms, more preferably 2-18 carbon atoms, and even more preferably 3-12 carbon atoms), an aryloxy group (preferably having 6-22 carbon atoms, more preferably 6-18 carbon atoms, and even more preferably 6-12 carbon atoms), or an aralkyloxy group (preferably having 7-23 carbon atoms, more preferably 7-19 carbon atoms, and even more preferably 7-12 carbon atoms). Among these, cycloalkyl groups (preferably having 3-24 carbon atoms, more preferably 3-18 carbon atoms, and even more preferably 3-12 carbon atoms), aralkenyl groups, and aralkyloxy groups are preferred. ^Rb3 may further have a substituent as long as the effects of the present invention are exhibited.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical Formula 28]

In the formula, ^Rb11 and ^Rb12 and ^Rb31 and ^Rb32 have the same meanings as ^Rb1 and ^Rb2 in formula (B1), respectively. ^Rb13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms), and may have a substituent within the scope of exerting the effects of the present invention. Among them, ^Rb13 is preferably an aralkyl group.

^Rb33 and ^Rb34 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms), preferably a hydrogen atom.

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

Furthermore, the compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a). [Chemical Formula 29]

^Rb11 and ^Rb12 have the same meanings as ^Rb11 and ^Rb12 in formula (B1-1). ^Rb15 and ^Rb16 are hydrogen atom, alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms), aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms), preferably hydrogen atom or methyl group. Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms), wherein the aryl group is preferred.

[Chemical formula 30]

In formula (B3), L represents an alkyl group, which is a divalent alkyl group having a saturated alkyl group along the linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms along the linking chain is 3 or more. Furthermore, R ^N1 and R ^N2 each independently represent a monovalent organic group.

In this specification, "connecting chain" refers to the shortest (smallest number of atoms) atomic chain connecting two atoms or groups of atoms in the connecting chain. For example, in the compound represented by the following formula, L is composed of a phenylene ethylene group, and has an ethylene group as a saturated alkyl group. The connecting chain is composed of four carbon atoms, and the number of atoms in the connecting chain path (i.e., the number of atoms constituting the connecting chain, hereinafter also referred to as "connecting chain length" or "chain length") is 4. [Chemical Formula 31]

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

Furthermore, the base generator preferably includes a compound represented by the following formula (N1). [Chemical Formula 32]

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

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

In formula (N1), ^RN1 and ^RN2 each independently represent a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), preferably a alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 10 carbon atoms). Specifically, an aliphatic alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 10 carbon atoms) or an aromatic alkyl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms) can be exemplified. An aliphatic alkyl group is preferred. Using an aliphatic alkyl group as ^RN1 and ^RN2 is preferred because the resulting base has a high basicity. Furthermore, the aliphatic alkyl group and the aromatic alkyl group may have a substituent, and the aliphatic alkyl group and the aromatic alkyl group may have an oxygen atom in the aliphatic alkyl chain or in the aromatic ring or in the substituent. In particular, an embodiment in which the aliphatic alkyl group has an oxygen atom in the alkyl chain can be exemplified.

Examples of the aliphatic alkyl group constituting ^RN1 and ^RN2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of linear and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, dibutyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, and isohexyl. Cyclic alkyl groups preferably have 3 to 12 carbon atoms, more preferably 3 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. Groups associated with combinations of chain alkyl and cyclic alkyl groups preferably have 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Examples of groups associated with combinations of chain alkyl and cyclic alkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl. Alkyl groups having an oxygen atom in the chain preferably have 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The alkyl group containing an oxygen atom in the chain may be chain or cyclic, and may be linear or branched. From the perspective of increasing the boiling point of the base generated by decomposition described later, ^RN1 and ^RN2 are preferably alkyl groups having 5 to 12 carbon atoms. In formulations where adhesion to metals (e.g., copper) during layer-by-layer bonding is important, cyclic alkyl groups or alkyl groups having 1 to 8 carbon atoms are preferred.

^RN1 and ^RN2 may be linked to form a ring structure. When forming a ring structure, an oxygen atom or the like may be present in the chain. The ring structure formed by ^RN1 and ^RN2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. As the cyclic structure formed, a 5-membered or 6-membered ring containing a nitrogen atom in formula (N1) is preferred. Examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidinyl ring, an imidazolidinyl ring, a pyrazolidinyl ring, a piperidine ring, a piperonyl ring, and a morpholine ring. Preferred examples include a pyrroline ring, a pyrrolidinyl ring, a piperidine ring, a piperonyl ring, and a morpholine ring.

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

As the protecting group, a protecting group that is decomposed by the action of an acid or a base is preferred, and a protecting group that is decomposed by an acid can be preferably exemplified.

Specific examples of protecting groups include chain or cyclic alkyl groups or chain or cyclic alkyl groups containing an oxygen atom in the chain. Examples of chain or cyclic alkyl groups include methyl, ethyl, isopropyl, tertiary butyl, and cyclohexyl groups. Specifically, examples of chain alkyl groups containing an oxygen atom in the chain include alkyloxyalkyl groups, and more specifically, methoxymethyl (MOM) and ethoxyethyl (EE) groups. Examples of cyclic alkyl groups containing an oxygen atom in the chain include epoxy groups, glycidyl groups, cyclobutyloxy groups, tetrahydrofuryl groups, and tetrahydropyranyl (THP) groups.

The divalent linking group constituting L is not particularly limited, but a alkyl group is preferred, and an aliphatic alkyl group is more preferred. The alkyl group may have a substituent and may have atoms other than carbon atoms in the alkyl chain. More specifically, a divalent alkyl linking group that may have an oxygen atom in the chain is preferred, a divalent aliphatic alkyl group that may have an oxygen atom in the chain, a divalent aromatic alkyl group, or a group related to a combination of a divalent aliphatic alkyl group that may have an oxygen atom in the chain and a divalent aromatic alkyl group that may have an oxygen atom in the chain is more preferred, and a divalent aliphatic alkyl group that may have an oxygen atom in the chain is even more preferred. These groups preferably do not have an oxygen atom. The divalent alkyl linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic alkyl group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic alkyl group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. The group associated with the combination of a divalent aliphatic alkyl group and a divalent aromatic alkyl group (e.g., an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and even more preferably 7 to 10 carbon atoms.

Specifically, preferred linking groups include linear or branched chain alkylene groups, cyclic alkylene groups, groups related to combinations of chain and cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylene groups, and arylene alkylene groups. Linear or branched chain alkylene groups preferably have 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. Cyclic alkylene groups preferably have 3 to 12 carbon atoms, more preferably 3 to 6. The groups involved in the combination of chain- and cyclic-alkylene groups preferably have 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. Alkylene groups containing oxygen atoms in the chain may be chain- or cyclic-shaped, and may be straight or branched. Alkylene groups containing oxygen atoms in the chain preferably have 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3.

A linear or branched alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms. The number of C=C bonds in a linear or branched alkenylene group is preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. A cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. The number of C=C bonds in a cyclic alkenylene group is preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 to 2 carbon atoms. An arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. Arylene and alkylene groups preferably have 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among these, chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene groups, arylene groups, and alkylene groups are preferred. 1,2-ethylene, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis-vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), and oxyethylene (especially 1,2-vinyloxy-1,2-ethylene) are more preferred.

The following examples can be cited as alkali generators, but the present invention is not to be construed as being limited thereto.

[Chemical formula 33]

The molecular weight of the non-ionic thermal base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. As a lower limit, it is preferably 100 or more, more preferably 200 or more, and even more 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.

Specific examples of ammonium salts include the following compounds, but the present invention is not limited thereto. [Chemical Formula 34]

Specific examples of imine salts include the following compounds, but the present invention is not limited thereto. [Chemical Formula 35]

When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is preferably 0.3 parts by mass or greater, and even more preferably 0.5 parts by mass or greater. The upper limit is preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. It may be 5 parts by mass or less, or even 4 parts by mass or less. One or more base generators may be used. When two or more types are used, the total amount is preferably within the above range.

<Polymerizable Compound> The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include free radical crosslinking agents and other crosslinking agents.

[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. Preferred free radical polymerizable groups are groups containing ethylenically unsaturated bonds. Examples of such groups containing ethylenically unsaturated bonds include vinyl, allyl, vinylphenyl, (meth)acryl, cis-butylenediimide, and (meth)acrylamide. Among these, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferred groups containing ethylenically unsaturated bonds. From the perspective of reactivity, (meth)acryl is more preferred.

The free radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but compounds having two or more are more preferred. The free radical crosslinking agent may have three or more ethylenically unsaturated bonds. Compounds having two or more ethylenically unsaturated bonds are preferably compounds having 2 to 15 ethylenically unsaturated bonds, more preferably compounds having 2 to 10 ethylenically unsaturated bonds, and even more preferably compounds having 2 to 6 ethylenically unsaturated bonds. In addition, from the perspective of the film strength of the resulting pattern (cured product), the resin composition of the present invention preferably contains a compound having two ethylenically unsaturated bonds in addition to the aforementioned compound having three or more ethylenically unsaturated bonds.

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

Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), or their esters and amides. Preferred are esters of unsaturated carboxylic acids with polyol compounds, and amides of unsaturated carboxylic acids with polyamine compounds. Furthermore, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or thiohydrides with monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, are also preferably used. Also preferred are addition reactions of unsaturated carboxylates or amides having electrophilic substituents such as isocyanate or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, as well as substitution reactions of unsaturated carboxylates or amides having dissociative substituents such as halogen or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, compounds such as unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, and allyl ethers can be used in place of the unsaturated carboxylic acids. For specific examples, see paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357, which are incorporated herein by reference.

Furthermore, the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher at normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trihydroxymethylpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, etc., which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the obtained compound. Compounds obtained by acid esterification, such as urethane (meth)acrylates described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490, multifunctional acrylates or methacrylates such as epoxy acrylates obtained as reaction products of epoxy resins and (meth)acrylic acid, and mixtures thereof, are also preferred. Compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, polyfunctional (meth)acrylates obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, with a polyfunctional carboxylic acid can also be cited.

In addition to the above, preferred free radical crosslinking agents include compounds having a fluorene ring and two or more groups having ethylenically unsaturated bonds, as described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent Application No. 4364216, and cardo resins.

Other examples include the specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, and the vinylphosphonic acid compounds described in Japanese Patent Application Laid-Open No. 02-025493. Furthermore, compounds containing a perfluoroalkyl group described in Japanese Patent Application Laid-Open No. 61-022048 can also be used. Furthermore, those described as photopolymerizable monomers and oligomers in "Journal of the Adhesion Society of Japan," vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Laid-Open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents thereof are incorporated into this specification.

Furthermore, in Japanese Patent Application Laid-Open No. 10-062986, the following compounds described as formula (1) and formula (2) together with their specific examples can also be used as radical crosslinking agents. These compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then performing (meth)acrylic esterification.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as radical crosslinking agents, and these contents are incorporated into this specification.

As free radical crosslinking agents, 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 structures in which the (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomer types can also be used.

Examples of commercially available free radical crosslinking agents include SR-494, a tetrafunctional acrylate having four ethoxy chains, manufactured by Sartomer Company, Inc., SR-209, 231, and 239, bifunctional methacrylates having four vinyloxy chains, manufactured by Sartomer Company, Inc., DPCA-60, a hexafunctional acrylate having a pentyloxy chain, manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having three isobutyloxy chains, urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, and NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

Preferred free radical crosslinking agents include urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open 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. Furthermore, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule, as 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 may be one having an acid group such as a carboxyl group or a phosphoric acid group. Preferred free radical crosslinking agents having an acid group are esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. More preferred are free radical crosslinking agents having an acid group formed by reacting a non-aromatic carboxylic acid anhydride with unreacted hydroxyl groups of an aliphatic polyhydroxy compound. Particularly preferred are free radical crosslinking agents having an acid group formed by reacting a non-aromatic carboxylic acid anhydride with unreacted hydroxyl groups of an aliphatic polyhydroxy compound, wherein the aliphatic polyhydroxy compound is neopentyl triol or dipentyl triol. Commercially available products include polyacid-modified acrylic oligomers such as M-510 and M-520 manufactured by TOAGOSEI CO., LTD.

The preferred acid value of a radical crosslinking agent containing an acid group is 0.1 to 300 mgKOH/g, particularly preferably 1 to 100 mgKOH/g. A radical crosslinking agent with an acid value within this range provides excellent workability during production and, consequently, excellent developability. Furthermore, the polymerizability is good. The acid value is measured in accordance with JIS K 0070:1992.

From the perspective of pattern resolution and film stretchability, bifunctional methacrylates or acrylates are preferably used as the resin composition. Specific compounds include 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, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol dimethacrylate. acrylate, dihydroxymethyltricyclodecane diacrylate, dihydroxymethyltricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates with urethane bonds, and bifunctional methacrylates with urethane bonds. Two or more of these may be used in combination as needed. Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain formula weight of approximately 200. In the resin composition of the present invention, from the perspective of suppressing warping while controlling the elastic modulus of the pattern (cured product), a monofunctional free radical crosslinker can be preferably used as the free radical crosslinker. Monofunctional free radical crosslinking agents that can be used preferably include 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; and alkenyl glycidyl ethers. Monofunctional free radical crosslinking agents with a boiling point of 100°C or higher at normal pressure are also preferred to suppress volatility before exposure. In addition, examples of bifunctional or higher-functional free radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

When a free radical crosslinking agent is present, its content is preferably greater than 0% by mass and less than 60% by mass relative to the total solids content of the resin composition of the present invention. A lower limit of 5% by mass or greater is more preferred. An upper limit of 50% by mass or less is even more preferred, and 30% by mass or less is even more preferred.

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 other than the free radical crosslinking agents described above. In the present invention, other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents described above. Compounds having multiple groups within their molecules that are activated by the photoacid generator or photoalkali generator to promote the formation of covalent bonds with other compounds in the composition or their reaction products are preferred. Compounds having multiple groups within their molecules that are activated by the action of an acid or base to promote the formation of covalent bonds with other compounds in the composition or their reaction products are preferred. The acid or base is preferably one generated from a photoacid generator or photoalkali generator during the exposure step. Other crosslinking agents are preferably compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, and alkoxymethyl groups, and more preferably compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, and alkoxymethyl groups is directly bonded to a nitrogen atom. Other crosslinking agents include, for example, compounds having a structure in which the hydrogen atoms of the amino groups are substituted with acyloxymethyl, hydroxymethyl, or alkoxymethyl groups by reacting formaldehyde or formaldehyde and an alcohol with an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine. The production method of these compounds is not particularly limited, as long as they have the same structure as the compounds produced by the above-described methods. Alternatively, they may be oligomers formed by self-condensation of hydroxymethyl groups of these compounds. Crosslinking agents using melamine as the amino-containing compound are referred to as melamine-based crosslinking agents; crosslinking agents using glycoluril, urea, or alkylene urea are referred to as urea-based crosslinking agents; crosslinking agents using alkylene urea are referred to as alkylene urea-based crosslinking agents; and crosslinking agents using benzoguanamine are referred to as benzoguanamine-based crosslinking agents. Among these, the resin composition of the present invention preferably comprises at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably comprises at least one compound selected from the group consisting of the glycoluril-based crosslinking agents and melamine-based crosslinking agents described below.

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

[Chemical formula 36]

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

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

[Chemical formula 37]

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, R ₁₀₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes to form an alkali-soluble group by the action of an acid (for example, a group that is liberated by the action of an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents a group that is liberated by the action of an acid). R ₁₀₅ independently represents an alkyl group or an alkenyl group, a, b, and c independently represent 1 to 3, d is 0 to 4, e is 0 to 3, and f is 0 to 3. a + d is 5 or less, b + e is 4 or less, and c + f is 4 or less. Examples of R ⁵ in the group represented by -C(R ⁴ ) ₂ COOR ⁵ include -C(R 36 )(R 37 )(R 38 ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and -C(R ₀₁ )(R ₀₂ )(OR ₃₉ ). In the formula, _{R 36 to R 39 independently} represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. _{R 36} and R ₃₇ may be bonded to form a ring. Preferred alkyl groups include those having 1 to 10 carbon atoms, and those having 1 to 5 carbon atoms. The above-mentioned alkyl group may be either linear or branched. As the above-mentioned cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is more preferred. The above-mentioned cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring. The above-mentioned aryl group is preferably an aromatic alkyl group having 6 to 30 carbon atoms, and a phenyl group is more preferred. As the above-mentioned aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferred, and an aralkyl group having 7 to 16 carbon atoms is more preferred. The above-mentioned aralkyl group refers to an aryl group substituted with an alkyl group, and the preferred aspects of the alkyl and aryl groups are the same as the preferred aspects of the above-mentioned alkyl and aryl groups. The above-mentioned alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and an alkenyl group having 3 to 16 carbon atoms is more preferred. Furthermore, these groups may have known substituents as long as the effects of the present invention can be achieved.

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

Preferred groups that decompose to generate alkaline-soluble groups by the action of an acid or that are released by the action of an acid include tertiary alkyl ester groups, acetal groups, cumyl ester groups, and enol ester groups. More preferred are tertiary alkyl ester groups and acetal groups.

Specific examples of compounds having an alkoxymethyl group include the following structures. Examples of compounds having an acyloxymethyl group include compounds obtained by replacing the alkoxymethyl group in the following compounds with an acyloxymethyl group. Examples of compounds having an alkoxymethyl group or an acyloxymethyl group in the molecule include the following compounds, but are not limited to these.

[Chemical formula 38]

[Chemical formula 39]

Compounds containing at least one of an alkoxymethyl group and an acyloxymethyl group can be commercially available or synthesized by known methods. From the perspective of heat resistance, compounds in which the alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or a tricyclic ring are preferred.

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

Specific examples of urea-based crosslinking agents include glycoluril-based crosslinking agents such as monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril; urea-based crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea; Ethyl urea-based crosslinking agents such as monohydroxymethylated ethyl urea, dihydroxymethylated ethyl urea, monomethoxymethylated ethyl urea, dimethoxymethylated ethyl urea, monoethoxymethylated ethyl urea, diethoxymethylated ethyl urea, monopropoxymethylated ethyl urea, dipropoxymethylated ethyl urea, monobutoxymethylated ethyl urea, or dibutoxymethylated ethyl urea; Propylene urea-based crosslinking agents such as monohydroxymethylated propyl urea, dihydroxymethylated propyl urea, monomethoxymethylated propyl urea, dimethoxymethylated propyl urea, monoethoxymethylated propyl urea, diethoxymethylated propyl urea, monopropoxymethylated propyl urea, dipropoxymethylated propyl urea, monobutoxymethylated propyl urea, or dibutoxymethylated propyl urea; 1,3-bis(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

Specific examples of the benzoguanamine-based crosslinking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

In addition, as the compound having at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, a compound having at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used. Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenyl Ketone, methoxymethylphenyl methoxymethyl benzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other crosslinking agents, commercially available products may be used. Preferred commercially available products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLLBisOC-P, DMOM-PC, and DMOM -PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, hereinafter the same) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

Furthermore, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, cyclobutane compounds, and benzophenone compounds as another crosslinking agent.

-Epoxy Compounds (Compounds Containing Epoxy Groups)- Epoxy compounds preferably have two or more epoxy groups per molecule. Epoxy groups undergo crosslinking reactions below 200°C and do not undergo dehydration reactions associated with crosslinking, thus minimizing film shrinkage. Therefore, the inclusion of epoxy compounds is effective in suppressing low-temperature curing and warping of the resin composition of the present invention.

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

Examples of epoxy compounds include bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol epoxy resins or polyol hydrocarbon epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trihydroxymethylpropane triglycidyl ether; polyalkylene glycol epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy epoxy silicones such as polymethyl (glycidyloxypropyl) siloxane. However, the present invention is not limited to these. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICL ON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are product names, DIC CORPORATION), Rika Resin (Registered Trademark) BEO-20E, Rika Resin (Registered Trademark) BEO-60E, Rika Resin (Registered Trademark) HBE-100, Rika Resin (Registered Trademark) DME-100, Rika Resin (Registered Trademark) L-200 (product names, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are product names, ADEKA CORPORATION), CELLOXIDE (Registered Trademark) 2021P, CELLOXIDE (Registered Trademark) 2081, CELLOXIDE (Registered Trademark) 2000, EHPE3150, EPOLEAD (Registered Trademark) GT401, EPOLEAD (Registered Trademark) PB4700, EPOLEAD (Registered Trademark) PB3600 (the above are product names, Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all product names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds can also be preferably used.

[Chemical formula 40]

Wherein, n is an integer from 1 to 5, and m is an integer from 1 to 20.

In the above structure, from the perspective of achieving both heat resistance and elongation, n is preferably 1 to 2 and m is preferably 3 to 7.

-Oxycyclobutane compounds (compounds containing an oxocyclobutyl group)- Examples of oxocyclobutane compounds include compounds containing two or more oxocyclobutane rings in one molecule, 3-ethyl-3-hydroxymethoxycyclobutane, 1,4-bis{[(3-ethyl-3-oxocyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxocyclobutane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxocyclobutyl)methyl]ester. As a specific example, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used. These can be used alone or in combination of two or more.

-Benzotriazole compounds (compounds containing benzoxazolyl groups)- Because of the cross-linking reaction caused by the ring-opening addition reaction, benzotriazole compounds do not produce outgassing during curing, further reducing thermal shrinkage and suppressing warping, making them preferred.

Preferred examples of benzophenone compounds include P-d-type benzophenone, F-a-type benzophenone (product names, manufactured by Shikoku Chemicals Corporation), benzophenone adducts of polyhydroxystyrene resins, and novolac-type dihydrobenzophenone compounds. These can be used alone or in combination of two or more.

The content of the other crosslinking agent is preferably 0.1-30 mass %, more preferably 0.1-20 mass %, even more preferably 0.5-15 mass %, and particularly preferably 1.0-10 mass %, relative to the total solids content of the resin composition of the present invention. The other crosslinking agent may be present in a single species or in two or more species. When two or more other crosslinking agents are present, their total content is preferably within the above range.

<Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes and wiring. Examples of metal adhesion improvers include silane coupling agents containing alkoxysilyl groups, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds containing sulfonamide structures, compounds containing thiourea, phosphoric acid derivatives, β-ketoester compounds, and amino compounds.

[Silane coupling agent] Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, and the compounds described in Japanese Patent Application Laid-Open No. 2014-191252. The compounds described in paragraphs 0060-0061 of JP-A-2014-041264, the compounds described in paragraphs 0045-0052 of JP-A-2014-097594, the compounds described in paragraphs 0055 of JP-A-2014/097594, and the compounds described in paragraphs 0067-0078 of JP-A-2018-173573 are incorporated into this specification. Furthermore, as described in paragraphs 0050-0058 of JP-A-2011-128358, it is also preferred to use two or more different silane coupling agents. Furthermore, the following compounds are also preferred as silane coupling agents. In the following formula, Me represents a methyl group and Et represents an ethyl group.

[Chemical formula 41]

As other silane coupling agents, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-phenylenediaminetrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Trimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-butylenepropylmethyldimethoxysilane, 3-butylenepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These may be used alone or in combination of two or more.

[Aluminum-based bonding agents] Examples of aluminum-based bonding agents include aluminum tris(ethyl acetate)aluminum, aluminum tris(acetylacetone), and aluminum diisopropyl acetate.

Furthermore, as other metal adhesion improvers, the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and the 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, per 100 parts by mass of the specific resin. By setting the content above the lower limit, the adhesion between the pattern and the metal layer is improved. By setting the content below the upper limit, the heat resistance and mechanical properties of the pattern are improved. The metal adhesion improver may be a single type or two or more types may be used. When two or more types are used, their total content is preferably within the above range.

<Migration Inhibitor> The resin composition of the present invention preferably further comprises a migration inhibitor. The inclusion of a migration inhibitor effectively inhibits the migration of metal ions from the metal layer (metal wiring) into the film.

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, morpholine ring, 2H-pyran ring, 6H-pyran ring, trioxadiazole ring), compounds having thiourea and thiohydrin groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole; and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

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

Other migration inhibitors that can be used include the rust preventive described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2011-059656, the compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, and the compound described in paragraph 0166 of International Publication No. 2015/199219. These contents are incorporated into this specification.

Specific examples of migration inhibitors include the following compounds.

[Chemical formula 42]

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 of the present invention.

The number of migration inhibitors may be one or more. When two or more migration inhibitors are used, 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 polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

As specific compounds of the polymerization inhibitor, for example, p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, p-tert-butyl-o-catechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) butylphenol), N-nitrosophenyl hydroxylamine first balsam salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2- Nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy)-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-dihydro-1H,3H-1H)- ... ,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, phenothiazolium, phenanthiophene, 1,1-diphenyl-2-pyrrolohydrazide, dibutylcopper(II)dithiocarbonate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Furthermore, the polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and the compounds described in paragraphs 0031 to 0046 of WO-2015/125469 can also be used, and the contents thereof 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 of the present invention.

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

<Acid Scavenger> To minimize performance changes over time from exposure to heating, the resin composition of the present invention preferably contains an acid scavenger. Acid scavengers are compounds that, by their presence in the system, can capture generated acids. Compounds with low acidity and high pKa are preferred. Preferred acid scavengers include compounds containing amine groups, with primary amines, diamines, tertiary amines, ammonium salts, and tertiary amides being preferred. Primary amines, diamines, tertiary amines, and ammonium salts are preferred, with diamines, tertiary amines, and ammonium salts being even more preferred. Preferred examples of acid scavengers include compounds having an imidazole structure, a diazabicyclic structure, an onium structure, a trialkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having a hydroxyl group and/or an ether bond, and aniline derivatives having a hydroxyl group and/or an ether bond. In the case of an onium structure, the acid scavenger is preferably a salt having a cation selected from ammonium, diazo, iodonium, coronium, phosphonium, pyridinium, and the like, and an anion of an acid having a lower acidity than the acid generated by the acid generator.

Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of acid scavengers with an onium structure include tetrabutylammonium oxide, triarylcorbium hydroxide, benzylmethylcorbium hydroxide, and 2-oxoalkyl-containing corbium hydroxides, specifically triphenylcorbium hydroxide, tri(tertiarybutylphenyl)corbium hydroxide, bis(tertiarybutylphenyl)iodonium hydroxide, benzylmethylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers with a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers with an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers with a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives with hydroxyl and/or ether bonds include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives with hydroxyl and/or ether bonds include N,N-bis(hydroxyethyl)aniline.

Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazobiscycloundecane), DABCO (1,4-diazobiscyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N- Methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N’,N’-tetrabutyl-1,6-hexanediamine, triamine, diaminocyclohexane, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-dianilinoethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, aminopyrrolidine, aminoalkylpyrrolidine, etc.

These acid scavengers may be used singly or in combination. The composition of the present invention may or may not contain an acid scavenger. However, if present, the acid scavenger content is generally 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solids content of the composition.

The preferred ratio of acid generator to acid scavenger is 2.5 to 300 (molar ratio). Specifically, from the perspective of sensitivity and resolution, a molar ratio of 2.5 or greater is preferred, while from the perspective of suppressing the reduction in resolution caused by the thickening of the relief pattern over time after exposure and heat treatment, a molar ratio of 300 or less is preferred. The molar ratio of acid generator to acid scavenger is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

<Other Additives> The resin composition of the present invention may be blended with various additives as needed, within the scope of achieving the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, organic titanium compounds, antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers, and other additives (e.g., defoaming agents, flame retardants, etc.). By appropriately incorporating these ingredients, the physical properties of the film can be adjusted. For information on these ingredients, see, for example, paragraphs 0183 et seq. of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013/0034812) and paragraphs 0101-0104 and 0107-0109 of Japanese Patent Application Publication No. 2008-250074, which are incorporated herein. When these additives are added, their total amount is preferably set to no more than 3% by mass of the solids content of the resin composition of the present invention.

[Surfactants] Surfactants can be used in a variety of ways, including fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. Surfactants can be nonionic, cationic, or anionic.

By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (particularly, fluidity) when prepared as a coating liquid are further enhanced, thereby further improving coating thickness uniformity and liquid conservation. Specifically, when a film is formed using a coating liquid containing a composition containing a surfactant, the interfacial tension between the coating surface and the coating liquid is reduced, improving wettability to the coating surface and enhancing coating properties. Consequently, a uniform film with minimal thickness variations can be formed.

Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC Corporation), Floyd FC430, Floyd FC431, Floyd FC171, Novell FC4430, Novell FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. Fluorine-based surfactants can also be used, including compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and in paragraphs 0117 to 0132 of JP-A-2011-132503, and these contents are incorporated into this specification. Block polymers can also be used as fluorine-based surfactants. Specific examples include the compounds described in Japanese Patent Application Publication No. 2011-89090, the contents of which are incorporated herein. Fluorine-based surfactants can also preferably be fluorine-containing polymers comprising repeating units derived from a (meth)acrylate compound having fluorine atoms and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkoxy groups (preferably ethyleneoxy or propyleneoxy). The following compounds can also be exemplified as fluorine-based surfactants used in the present invention. [Chemical Formula 43]

The weight-average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000. Fluoropolymers having ethylenically unsaturated groups on their side chains can also be used as fluorine-based surfactants. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, which are incorporated herein. Commercially available products include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

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

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by BYK-Chemie GmbH), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP-341, KF6001, and KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

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

Examples of non-ionic surfactants include glycerin, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available products include Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, and D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Co., Ltd.).

Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers Polyflow No. 75, No. 77, No. 90, and No. 95 (manufactured by KYOEISHA CHEMICAL Co., LTD.), and W001 (manufactured by Yusho Co., Ltd.).

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

A single surfactant may be used, or two or more surfactants may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solids content of the composition.

[Higher Fatty Acid Derivatives] To prevent polymerization hindrance caused by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the resin composition of the present invention so that it is unevenly distributed on the surface of the resin composition during the drying process after coating.

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

When the resin composition of the present invention contains higher fatty acid derivatives, the content of the higher fatty acid derivatives is preferably 0.1 to 10% by mass relative to the total solids content of the resin composition of the present invention. The higher fatty acid derivative may be a single type or two or more types. When two or more types are present, the total content of the higher fatty acid derivatives is preferably within the above range.

[Thermal Polymerization Initiator] The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals using thermal energy, thereby initiating or accelerating the polymerization reaction of a polymerizable compound. The addition of a thermal free radical polymerization initiator can also cause the resin and the polymerizable compound to undergo polymerization, thereby further improving solvent resistance. Furthermore, the aforementioned photopolymerization initiator may also function to initiate polymerization using heat and may be added as a thermal polymerization initiator.

Specific examples of thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554, the contents of which are incorporated herein.

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

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

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

[Ultraviolet Absorber] The composition of the present invention may contain a UV absorber. Examples of UV absorbers include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and tris(III)-based UV absorbers. Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-isobutylphenyl)-5-chlorobenzotriazole. 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

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

In the present invention, each of the aforementioned UV absorbers may be used alone or in combination of two or more. The composition of the present invention may or may not contain a UV absorber. However, if included, the content of the UV absorber is preferably 0.001% by mass to 1% by mass, and more preferably 0.01% by mass to 0.1% by mass, relative to the total solids content of the composition of the present invention.

[Organic Titanium Compound] The resin composition of this embodiment may contain an organic titanium compound. Because the resin composition contains an organic titanium compound, it can form a resin layer with excellent chemical resistance even when curing at low temperatures.

Examples of usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of these organic titanium compounds are listed below in I) to VII): I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are preferred, as they provide excellent storage stability of the resin composition and allow for a good curing pattern. Specific examples include titanium diisopropyl bis(triethanolamine), titanium di(n-butanol)bis(2,4-pentanedione), titanium diisopropyl bis(2,4-pentanedione), titanium diisopropyl bis(tetramethylheptanedione), and titanium diisopropyl bis(ethyl acetylacetate). II) Tetraalkoxy titanium compounds: for example, titanium tetra(n-butanol), titanium tetraethanol, titanium tetra(2-ethylhexanol), titanium tetraisobutanol, titanium tetraisopropanol, titanium tetramethanol, titanium tetramethoxypropanol, titanium tetramethylphenoxide, titanium tetra(n-nonanol), titanium tetra(n-propanol), titanium tetrastearyl alcohol, and titanium tetra[bis{2,2-(allyloxymethyl)butanol}]. III) Titanium cyclopentadienyl trimethoxide compounds: Examples include titanium pentamethylcyclopentadienyl trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium. IV) Titanium monoalkoxy compounds: Examples include titanium tris(dioctyl phosphate)isopropylate and titanium tris(dodecylphenylsulfonate)isopropylate. V) Titanium oxide compounds: Examples include titanium bis(pentanedione) oxide, titanium bis(tetramethylheptanedione) oxide, and titanium phthalocyanine oxide. VI) Titanium tetraacetylacetonate compounds: Examples include titanium tetraacetylacetonate. VII) Titanium ester coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanium salt, etc.

Among these, the preferred organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the perspective of exhibiting better chemical resistance. In particular, titanium diisopropylate (ethyl acetylacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When an organic titanium compound is added, the amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or greater, the resulting cured pattern exhibits excellent heat resistance and chemical resistance. On the other hand, when the amount is 10 parts by mass or less, the storage stability of the composition is improved.

[Antioxidant] The composition of the present invention may contain an antioxidant. By including an antioxidant as an additive, the elongation characteristics and adhesion to metal materials of the cured film can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (adjacent position) are preferred. Preferred substituents include substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Furthermore, the antioxidant is preferably a compound having a phenolic group and a phosphite group in the same molecule. Furthermore, phosphorus-based antioxidants can also be preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphinylcycloheptadien-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tetriblyldibenzo[d,f][1,3,2]dioxaphosphinylcycloheptadien-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tetriblyl-6-methylphenyl)phosphite. Examples of commercially available antioxidants include Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80, and Adekastab AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants, and this disclosure is incorporated herein. Furthermore, the composition of the present invention may contain a potential antioxidant, if desired. Potential antioxidants include compounds in which the site where the antioxidant is exerted is protected by a protecting group, and compounds that exert their antioxidant activity by removing the protecting group upon heating at 100-250°C or heating at 80-200°C in the presence of an acid/base catalyst. Potential antioxidants include compounds described in International Publication Nos. 2014/021023, 2017/030005, and JP-A-2017-008219, the contents of which are incorporated herein. Examples of potential commercial antioxidants include ADEKA ARKLSGPA-5001 (manufactured by ADEKA CORPORATION). Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and compounds represented by formula (3).

[Chemical formula 44]

In general formula (3), ^R₅ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ^R₆ represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ^R₇ represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), or a monovalent to tetravalent organic group containing at least one of an oxygen atom and a nitrogen atom. k represents an integer from 1 to 4.

The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic and phenolic hydroxyl groups in the resin. Furthermore, it can inhibit metal oxidation by providing a rust-proofing effect on metal materials.

Because it can act simultaneously on both the resin and the metal material, k is preferably an integer of 2 to 4. Examples of R ⁷ include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof. The group may further have a substituent. Among these, alkyl ether groups and -NH- are preferred from the perspectives of solubility in developer solutions and metal adhesion. From the perspectives of interaction with the resin and metal adhesion during metal complex formation, -NH- is more preferred.

As examples of the compound represented by the general formula (3), the following can be cited, but the structure is not limited to the following.

[Chemical formula 45]

[Chemical formula 46]

[Chemical formula 47]

[Chemical formula 48]

The antioxidant addition amount is preferably 0.1 to 10 parts by weight relative to the resin, and more preferably 0.5 to 5 parts by weight. An addition amount of 0.1 parts by weight or greater improves elongation and adhesion to metals, even in high-temperature and high-humidity environments. Furthermore, an addition amount of 10 parts by weight or less enhances the sensitivity of the resin composition, for example, through interaction with the photosensitizer. A single antioxidant may be used, or two or more may be used. When two or more antioxidants are used, their combined amount is preferably within the above range.

[Anti-agglomerating agent] The resin composition of this embodiment may contain an anti-agglomerating agent as needed. Examples of such anti-agglomerating agents include sodium polyacrylate.

In the present invention, an anti-aggregating agent may be used alone or in combination of two or more. The composition of the present invention may or may not contain an anti-aggregating agent. However, if included, the anti-aggregating agent content is preferably 0.01% by mass to 10% by mass, and more preferably 0.02% by mass to 5% by mass, relative to the total solids content of the composition of the present invention.

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

In the present invention, a phenolic compound may be used alone or in combination of two or more. The composition of the present invention may or may not contain a phenolic compound. However, if a phenolic compound is contained, the content of the phenolic compound is preferably 0.01% by mass to 30% by mass, and more preferably 0.02% by mass to 20% by mass, relative to the total solids content of the composition of the present invention.

[Other Polymer Compounds] Examples of other polymer compounds include silicone resins, (meth)acrylic acid polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, cresol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified products having introduced crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

In the present invention, other polymer compounds may be used singly or in combination. The composition of the present invention may or may not contain other polymer compounds. However, if included, the content of the other polymer compounds is preferably 0.01% by mass to 30% by mass, and more preferably 0.02% by mass to 20% by mass, relative to the total solids content of the composition of the present invention.

<Resin Composition Properties> The viscosity of the resin composition of the present invention can be adjusted by adjusting the solids concentration of the resin composition. From the perspective of coating film thickness, a viscosity of 1,000 ^mm² /s to 12,000 ^mm² /s is preferred, 2,000 ^mm² /s to 10,000 ^mm² /s is more preferred, and 3,000 ^mm² /s to 8,000 ^mm² /s is even more preferred. Within this range, a highly uniform coating film is easily obtained. At a speed of 1,000 mm ² /s or less, it is difficult to apply the film with the required thickness for, for example, a redistribution insulation film. At a speed of 12,000 mm ² /s or more, the surface morphology of the coating may deteriorate.

<Regarding Restrictions on Substances Contained in the Resin Composition> The resin composition of the present invention preferably has a moisture 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. A moisture content exceeding 2.0% may impair the storage stability of the resin composition. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the storage container.

From the perspective of insulation, the metal content of the resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, excluding metals contained in complexes of organic compounds and metals. If multiple metals are contained, the total content of these metals is preferably within the above range.

Furthermore, as methods for reducing metal impurities accidentally contained in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as the raw materials constituting the resin composition of the present invention; filtering the raw materials constituting the resin composition of the present invention through a filter; and lining the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination.

Considering the use of the resin composition of the present invention as a semiconductor material, the halogen atom content is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the perspective of wiring corrosion resistance. In particular, the halogen atom content is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm in the form of halogen ions. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferred that the total chlorine and bromine ions, or the total chlorine and bromine ions, each fall within the above-mentioned ranges. Preferred methods for adjusting the halogen atom content include ion exchange treatment.

Conventional containers can be used as containers for the resin composition of the present invention. Furthermore, to prevent contaminants from entering the raw materials or the resin composition of the present invention, it is also preferable to use a multilayer bottle with an inner wall composed of six layers of six different resins, or a bottle with a seven-layer structure composed of six different resins. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351.

<Cured Resin Composition> The resin composition of the present invention can be cured to obtain a cured product of the resin composition. The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The resin composition is preferably cured by heating, with the heating temperature preferably being in the range of 120°C to 400°C, more preferably in the range of 140°C to 380°C, and particularly preferably in the range of 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited and can be selected from various shapes, such as film, rod, sphere, or granular, depending on the intended use. In the present invention, the cured product is preferably in the form of a film. Furthermore, by patterning the resin composition, the shape of the cured product can be selected according to the intended purpose, such as forming a protective film on the wall surface, creating a conductive hole (beer hall), adjusting impedance or electrostatic capacitance, or providing heat dissipation. The cured product (including the cured film) preferably has a thickness of 0.5 μm to 150 μm. The resin composition of the present invention preferably exhibits a shrinkage rate of 50% or less during curing, more preferably 45% or less, and even more preferably 40% or less. Shrinkage refers to the percentage change in volume of the resin composition before and after curing and can be calculated using the following formula. Shrinkage rate [%] = 100 - (volume after hardening ÷ volume before hardening) × 100

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

<Resin Composition Preparation> 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 conventional methods. Mixing can be performed using a stirring blade, a ball mill, or a rotating pot. The temperature during mixing is preferably 10-30°C, more preferably 15-25°C.

Furthermore, to remove foreign matter such as dust and particles from the resin composition of the present invention, it is preferably filtered using a filter. For example, the filter pore size may be 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. When the filter is made of polyethylene, HDPE (high-density polyethylene) is more preferred. The filter may be pre-cleaned with an organic solvent. During the filtering step, multiple filters may be connected in series or in parallel. When using multiple filters, filters of different pore sizes or materials can be combined. For example, a 1μm HDPE filter can be connected in series as the first stage, and a 0.2μm HDPE filter can be connected in series as the second stage. Furthermore, various materials can be filtered multiple times. Multiple filtration cycles can be used for cyclic filtration. Furthermore, filtration can be performed after pressurization. When pressurization and filtration are performed, the pressurization pressure can be, for example, 0.01 MPa to 1.0 MPa, preferably 0.03 MPa to 0.9 MPa, more preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa. In addition to filtration using a filter, impurity removal using an adsorbent can also be performed. Filtering and impurity removal using an adsorbent can also be combined. Known adsorbents can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. Alternatively, the resin composition filled in the bottle may be filtered using a filter and then degassed under reduced pressure.

(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. More preferably, the method for producing a cured product of the present invention includes the film-forming step, an exposure step of selectively exposing the film formed in the film-forming step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern. The method for producing a cured product of the present invention particularly preferably includes the film-forming step, the exposure step, the development step, and at least one of a heating step of heating the pattern obtained in the development step and a post-development exposure step of exposing the pattern obtained in the development step. Furthermore, the manufacturing method of the present invention preferably includes the aforementioned film-forming step and the step of heating the film. The following describes each step in detail.

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

[Substrate] The type of substrate can be appropriately selected depending on the application, but is not particularly limited. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, evaporated films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, either a substrate formed of metal or a substrate having a metal layer formed by electroplating or evaporation); paper; SOG (Spin-On-Glass); TFT (Thin Film Transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). In the present invention, semiconductor substrates are particularly preferred, with silicon substrates, Cu substrates, and mold substrates being even more preferred. Furthermore, a bonding layer and an oxide layer, such as one made of hexamethyldisilazane (HMDS), may be provided on the surface of the substrate. The shape of the substrate is not particularly limited and may be circular or rectangular. The dimensions of the substrate are, for example, a circular substrate with a diameter of 100 to 450 mm, preferably 200 to 450 mm. For a rectangular substrate, for example, a short side of 100 to 1000 mm, preferably 200 to 700 mm. The substrate may be, for example, a plate-shaped substrate (substrate), preferably a panel-shaped substrate.

When a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer including a cured product) or the surface of a metal layer, the resin layer or the metal layer becomes a base material.

As a method of applying the resin composition of the present invention to a substrate, coating is preferred.

Specific examples of applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and ink jet coating. From the perspective of film thickness uniformity, spin coating, slit coating, spray coating, or ink jet coating is more preferred. From the perspective of film thickness uniformity and productivity, spin coating and slit coating are particularly preferred. By adjusting the solids concentration of the resin composition and coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the substrate shape. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be used for approximately 10 seconds to 3 minutes. Alternatively, a method can be used in which a coating film previously applied to a dummy support using the aforementioned application method is transferred to the substrate. Regarding the transfer method, the present invention can also preferably use the production methods described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Publication No. 2006-047592. Furthermore, a step of removing excess film from the edge of the substrate can be performed. Examples of such a step include edge bead rinsing (EBR) and back rinsing. Furthermore, a pre-wetting step can be employed. Before applying the resin composition to the substrate, various solvents are applied to the substrate to improve the substrate's wettability, and then the resin composition is applied.

<Drying Step> After the film formation step (layer formation step), the film may be subjected to a drying step (drying step) to remove the solvent from the formed film (layer). That is, the method for producing a cured product of the present invention may include a drying step for drying the film formed in the film formation step. The drying step is preferably performed after the film formation step and before the exposure step. The drying temperature of the film in the drying step is preferably 50-150°C, more preferably 70-130°C, and even more preferably 90-110°C. Drying may also be performed by reducing pressure. The drying time can be exemplified as 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

<Exposure Step> The film may be provided in an exposure step for selectively exposing the film. That is, the method for producing a cured product of the present invention may include an exposure step for selectively exposing the film formed in the film forming step. Selective exposure means exposing a portion of the film. Furthermore, selective exposure forms exposed areas (exposed portions) and unexposed areas (unexposed portions) on the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention. For example, an exposure energy of 50 to 10,000 mJ/ ^cm² at a wavelength of 365 nm is preferably used, and 200 to 8,000 mJ/ ^cm² is more preferably used.

The exposure wavelength can be appropriately set within the range of 190-1,000nm, with 240-550nm being optimal.

Regarding the exposure wavelength, if we explain it in terms of its relationship with the light source, we can cite (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-ray (wavelength 436nm), h-ray (wavelength 405nm), i-ray (wavelength 365nm), wide (3 wavelengths of g, h, and i-ray), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser second harmonic 532nm and third harmonic 355nm, etc. With regard to the resin composition of the present invention, exposure based on a high pressure mercury lamp is particularly preferred, and exposure based on i-ray is particularly preferred. This achieves particularly high exposure sensitivity. Preferably, the exposure light used for exposure includes light having a wavelength of 405 nm. The exposure method is not particularly limited, as long as it exposes at least a portion of the film comprising the resin composition of the present invention. Examples include exposure using a photomask and exposure using a laser direct imaging method.

<Post-Exposure Heating Step> The film may be subjected to a post-exposure heating step (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed in the exposure step is heated. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The heating rate during the post-exposure heating step is preferably 1-12°C/minute, more preferably 2-10°C/minute, and even more preferably 3-10°C/minute, from the initial heating temperature to the maximum heating temperature. The heating rate can be appropriately varied during the heating process. The heating mechanism used in the post-exposure heating step is not particularly limited; a conventional hot plate, oven, infrared heater, or the like can be used. Also, heating can be performed in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon during heating.

<Developing Step> The exposed film can be subjected to a developing step in which a pattern is formed by developing the film exposed in the exposing step using a developer. That is, the method for producing a cured product of the present invention can include a developing step in which the film exposed in the exposing step is developed using a developer to form a pattern. The development step removes one of the exposed and unexposed portions of the film, thereby forming a pattern. Developing the film in which the unexposed portions are removed by the developing step is referred to as negative-tone development, while developing the film in which the exposed portions are removed by the developing step is referred to as positive-tone development.

[Developer] Developers used in the developing step include those containing alkaline aqueous solutions or organic solvents.

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

When the developer contains an organic solvent, the organic solvent as the ester preferably includes ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.)), alkyl 3-alkoxy propionates (e.g., 3-alkoxy methyl 2-alkoxypropionate, ethyl 2-methoxypropionate, propyl 2-alkoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.), methyl 2-alkoxypropionate and ethyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, 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-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-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl ester, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like; and as ethers, for example, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like are mentioned; Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone. Preferred examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene. Preferred examples of sulfoxides include dimethyl sulfoxide. Preferred examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol. Preferred examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

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

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

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

[Developer Supply Method] The developer supply method is not particularly limited as long as the desired pattern can be formed. Examples include immersing the film-formed substrate in the developer, using a nozzle to supply the developer to the film formed on the substrate for immersion development, and continuously supplying the developer. The type of nozzle is not particularly limited, and examples include vertical nozzles, shower nozzles, and mist nozzles. From the perspectives of developer permeability, removal of non-image areas, and manufacturing efficiency, a method using a vertical nozzle to supply developer or a method using a mist nozzle for continuous supply is preferred. From the perspective of developer permeability to the image area, a method using a mist nozzle for supply is particularly preferred. Alternatively, a process may be employed in which the developer is continuously supplied using a vertical nozzle, the substrate is rotated to remove the developer, and after drying by rotation, the developer is continuously supplied again using the vertical nozzle, followed by rotating the substrate to remove the developer. This process may also be repeated multiple times. Furthermore, as a method for supplying the developer solution during the development step, a step of continuously supplying the developer solution to the substrate, a step of maintaining the developer solution substantially stationary on the substrate, a step of vibrating the developer solution on the substrate using ultrasound or the like, or a combination of these steps can be employed.

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

In the development step, after the processing using the developer, the pattern may be further cleaned (rinsed) using a rinse solution. Alternatively, a method may be employed in which the rinse solution is supplied before the developer in contact with the pattern has completely dried.

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

When the rinsing liquid contains an organic solvent, the organic solvent includes, for example, esters, preferably ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl 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., 3-alkoxy methyl 2-alkoxypropionate, ethyl 2-methoxypropionate, propyl 2-alkoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.), methyl 2-alkoxypropionate and ethyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, 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-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-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl ester, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like; and as ethers, for example, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like are mentioned; Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone. Preferred examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene. Preferred examples of sulfoxides include dimethyl sulfoxide. Preferred examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol. Preferred examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

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

When the rinse liquid contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more of the rinse liquid. Alternatively, the organic solvent may account for 100% by mass of the rinse liquid.

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

[Rinsing Liquid Supply Method] The method for supplying the rinsing liquid is not particularly limited as long as the desired pattern can be formed. Examples include immersing the substrate in the rinsing liquid, supplying the rinsing liquid to the substrate using a pan, spraying the rinsing liquid, and continuously supplying the rinsing liquid to the substrate using a mechanism such as a vertical nozzle. From the perspectives of rinse liquid permeability, removal of non-image areas, and manufacturing efficiency, there are various methods for supplying rinse liquid using shower nozzles, vertical nozzles, and mist nozzles. Continuous supply using a mist nozzle is preferred, and from the perspective of rinse liquid permeability into the image area, supply using a mist nozzle is even more preferred. The type of nozzle is not particularly limited, and examples include vertical nozzles, shower nozzles, and mist nozzles. Specifically, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the exposed film using a vertical nozzle, and more preferably a step of supplying the rinsing liquid using a spray nozzle. In addition, the rinsing liquid supply method in the rinsing step can include a step of continuously supplying the rinsing liquid to the substrate, a step of maintaining the rinsing liquid substantially stationary on the substrate, a step of vibrating the rinsing liquid on the substrate using ultrasound or the like, and a combination of these methods.

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

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

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

During the heating step, heating is preferably performed at a rate of 1-12°C/minute from the initial heating temperature to the maximum heating temperature. This rate is more preferably 2-10°C/minute, and even more preferably 3-10°C/minute. A rate of 1°C/minute or higher ensures productivity and prevents excessive volatilization of acids or solvents. A rate of 12°C/minute or lower mitigates residual stress in the cured product. In addition, in an oven capable of rapid heating, a rate of 1-8°C/second from the initial heating temperature to the maximum heating temperature is preferably performed, more preferably 2-7°C/second, and even more preferably 3-6°C/second.

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, this refers to the temperature of the dried film (layer). For example, the temperature is preferably increased from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

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

In particular, when forming a multilayer laminate, from the perspective of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher. The upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 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 a rate of 3°C/minute and holding at 120°C for 60 minutes, then heating from 120°C to 180°C at a rate of 2°C/minute and holding at 180°C for 120 minutes. Alternatively, as described in U.S. Patent No. 9,159,547, treatment while irradiating with UV light is also preferred. This pretreatment step can improve membrane properties. The pretreatment step can be performed for a short period of time, from about 10 seconds to 2 hours, preferably from 15 seconds to 30 minutes. Pretreatment can be a two-stage process. For example, the first stage of pretreatment can be performed at a temperature between 100 and 150°C, followed by a second stage of pretreatment at a temperature between 150 and 200°C.

Furthermore, cooling can be performed after heating. The optimal cooling rate is 1-5°C/minute.

To prevent the decomposition of certain resins, it is best to perform the heating process in a low-oxygen environment, such as by flowing an inert gas such as nitrogen, helium, or argon during the heating step and performing the process under reduced pressure. An oxygen concentration of 50 ppm (volume ratio) or less is preferred, and 20 ppm (volume ratio) or less is even more preferred.

The heating mechanism in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared furnace, an electric 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 development if a development step is performed) can be provided in the post-development exposure step of the pattern after the exposure and development step instead of or in addition to the above-mentioned heating step.

That is, the method for producing a cured product of the present invention may include a post-development exposure step, wherein the post-development exposure step exposes the pattern obtained in the development step. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, a cyclization reaction of a polyimide precursor, etc., can be promoted by sensitizing the photobase generator, or a reaction of removing an acid-degradable group can be promoted by sensitizing the photoacid generator. In the post-development exposure step, at least a portion of the pattern obtained in the development step need only be exposed, but preferably, the entire pattern is exposed. The exposure dose in the post-development exposure step is preferably 50 to 20,000 mJ/ ^cm² , more preferably 100 to 15,000 mJ/ ^cm² , calculated as exposure energy at the wavelength to which the photosensitive compound is sensitive. The post-development exposure step can be performed, for example, using the light source described in the exposure step above, preferably broadband light.

<Metal Layer Formation Step> The pattern obtained by the development step (preferably the pattern provided to at least one of the heating step and the post-exposure development step) can be provided to the metal layer formation step, which forms a metal layer on the pattern. That is, the method for producing a cured article of the present invention preferably includes a metal layer formation step, wherein the metal layer is formed on the pattern obtained by the development step (preferably the pattern provided to 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 include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese National Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, U.S. Patent No. 7,888,181B2, and U.S. Patent No. 9,177,926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be used. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be cited. A preferred embodiment of electrolytic plating is electrolytic plating using a copper sulfate or copper cyanide plating solution.

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

Applications Examples of applications for the method of producing a cured product of the present invention and the cured product of the present invention include insulating films for electronic components, interlayer insulating films for redistribution layers, and stress buffering films. Other applications include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), and applications involving patterning by etching insulating films for practical applications such as those described above. For information on these applications, see, for example, "Advanced Functionality and Application Technology of Polyimides" by Science & Technology Co., Ltd., April 2008; "Fundamentals and Development of Polyimide Materials" by Masaaki Kakimoto, CMC Technical Library, November 2011; and "Latest Polyimides: Fundamentals and Applications" by the Japan Polyimide/Aromatic Polymer Research Society, NTS, August 2010.

Furthermore, the method for producing the cured product of the present invention or the cured product of the present invention can also be used in the production of offset printing plates, screen printing plates, and other plates, in the production of etched components, and in the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

(Laminar Body and Laminate Manufacturing Method) The laminate of the present invention refers to a structure having a plurality of layers comprising the cured product of the present invention. The laminate of the present invention is a laminate comprising two or more layers comprising a cured product, and may also be a laminate comprising three or more layers. At least one of the two or more layers comprising a cured product in the laminate is a layer comprising the cured product of the present invention. From the perspective of suppressing shrinkage of the cured product or deformation of the cured product associated with such shrinkage, it is preferred that all layers comprising a cured product in the laminate be layers comprising the cured product of the present invention.

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

The laminate of the present invention preferably includes two or more layers containing a cured product, and preferably includes a metal layer between any of the layers containing the cured product. The metal layer is preferably formed by the metal layer forming step described above. That is, the method for manufacturing the laminate of the present invention preferably includes a metal layer forming step of forming a metal layer on the layer containing the cured product during the multiple steps of the method for manufacturing the cured product. The preferred embodiment of the metal layer forming step is as described above. A preferred example of the laminate is a laminate having a structure comprising at least three layers, stacked in sequence: a first layer comprising a cured product, a metal layer, and a second layer comprising a cured product. Preferably, both the first layer comprising a cured product and the second layer comprising a cured product comprise the cured product of the present invention. The resin composition of the present invention used to form the first layer comprising a cured product and the resin composition of the present invention used to form the second layer comprising a cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a redistribution layer.

<Lamination Step> The method for producing a laminated body of the present invention preferably includes a lamination step. The lamination step comprises a series of steps comprising, on the surface of the pattern (resin layer) or metal layer, performing (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, and (d) a heating step and a post-development exposure step, in order. Alternatively, the method may include repeating (a) the film formation step and (d) the heating step and the post-development exposure step. Furthermore, the method may include (e) a metal layer formation step after at least one of (d) the heating step and the post-development exposure step. It is undeniable that the above-mentioned drying step can be further appropriately included in the layering step.

When a further layering step is performed after the layering step, a surface activation treatment step may be performed after the exposure step, after the heating step, or after the metal layer formation step. An example of the surface activation treatment is plasma treatment. 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 a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer structure, a structure of 2 or more resin layers and 20 or less resin layers is preferred, and a structure of 2 or more resin layers and 9 or less layers is even more preferred. The composition, shape, and film thickness of each of the above-mentioned layers may be the same or different.

In the present invention, it is particularly preferred to form the cured product (resin layer) of the resin composition of the present invention by further covering the metal layer after providing the metal layer. Specifically, an embodiment includes an embodiment in which (a) a film forming step, (b) an exposure step, (c) a development step, (d) a heating step, and at least one of a post-development exposure step, and (e) a metal layer forming step are sequentially repeated. Alternatively, an embodiment in which (a) a film forming step, (d) a heating step, and at least one of a post-development exposure step, and (e) a metal layer forming step are sequentially 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 producing a laminate of the present invention preferably includes a surface activation treatment step of surface-activating at least a portion of the metal layer and the resin composition layer. This surface activation treatment step is typically performed after the metal layer formation step, but it is also possible to perform the surface activation treatment on the resin composition layer after the development step and then perform the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, only on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. Preferably, at least a portion of the metal layer is surface-activated, and preferably, a portion or all of the area of the metal layer where the resin composition layer is formed on the surface is surface-activated. By surface-activating the metal layer, adhesion to the resin composition layer (film) disposed on the metal layer can be improved. Furthermore, preferably, a portion or all of the exposed resin composition layer (resin layer) is also surface-activated. By surface-activating the resin composition layer, adhesion to the metal layer and the resin layer disposed on the surface-activated surface can be improved. In particular, when the resin composition layer is hardened, such as when negative tone development is performed, it is less susceptible to damage from surface treatment, making it easier to improve adhesion. Specifically, the surface activation treatment includes plasma treatment using various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , or _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone, immersion treatment in an organic surface treatment agent containing a compound having at least one amino group and a thiol group after immersion in an aqueous hydrochloric acid solution to remove the oxide film, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. When performing corona discharge treatment, the energy is preferably 500-200,000 J/ ^m2 , more preferably 1000-100,000 J/ ^m2 , and most preferably 10,000-50,000 J/ ^m2 .

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

(Polyimide Precursor and Method for Producing the Same) The polyimide precursor of the present invention has a group containing an ethylenically unsaturated bond, a total content of cyclic imide structures and cyclic isoimide structures of 0 to 0.29 mmol/g, and an amine value of 0.0040 to 1.1100 mmol/g. The polyimide precursor of the present invention has the same meaning as the specific resin described above, and preferred embodiments are also the same.

The following describes the first and second aspects of the method for producing a polyimide precursor of the present invention, but the method is not limited thereto. The first aspect of the method for producing a polyimide precursor of the present invention is a method for producing the polyimide precursor of the present invention, comprising an amidation step of reacting a dicarboxylic acid compound with a diamine compound to obtain an amide compound, and an end-capping step of reacting the amide compound with an amino group-containing end-capping agent. The details of each of these steps are the same as those described in the first aspect of the method for producing the specific resin, and the preferred aspects are also the same.

A second aspect of the method for producing a polyimide precursor of the present invention is a method for producing the polyimide precursor of the present invention, comprising an amidation step of reacting a dicarboxylic acid compound with a diamine compound in the presence of an alkaline catalyst to obtain an amide compound, and an acidic compound addition step of adding an acid to the amide compound. The details of each of these steps are the same as those described in the second aspect of the method for producing the specific resin, and the preferred embodiment is also the same. [Examples]

The following examples provide a more detailed description of the present invention. The materials, amounts, ratios, processing details, and steps described in the following examples may be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are by mass.

<Resin Production Method> Polymers A-1 to A-17 containing repeating units represented by the following formulas (A-1) to (A-17) were synthesized according to the methods described in Synthesis Examples 1 or 2 below. Polymers A-18 to A-24 containing repeating units represented by the following formula (A-1) were synthesized according to the methods described in Synthesis Examples 3 to 9 below. In the following table, where "1" is entered in the "Synthesis Method" column, the resins listed in the table for polymers A-1 to A-17 were synthesized using the same method as described in Synthesis Example 1. In the following table, where "2" is entered in the "Synthesis Method" column, the resins listed in the table for polymers A-1 to A-17 were synthesized using the same method as described in Synthesis Example 2. Polymers A-1 to A-17 contain at least one repeating unit in which a portion of the amidine structure or amidine ester structure in the following repeating units is a cyclic amidine structure or a cyclic isoimide structure. The total content (mmol/g) of the cyclic amidine structure and cyclic isoimide structure contained in polymers A-1 to A-17 is reported in the "Specific Structure Content (mmol/g)" column of the table. In addition, the amine values of polymers A-1 to A-17 are reported in the "Amine Value (mgKOH/g)" column of the table.

[Chemical formula 49] [Chemical formula 50] [Chemical formula 51]

[Synthesis Example 1: Synthesis of Polymer A-1] 23.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.3 g of diphthalic dianhydride (BPDA) were placed in a separable flask. 39.7 g of 2-hydroxyethyl methacrylate (HEMA) and 136.8 g of γ-butyrolactone were added and stirred at room temperature (25°C). 24.7 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm due to the reaction subsided, the mixture was cooled to room temperature and allowed to stand for 16 hours. Next, under ice cooling, a solution of 62.5 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.6 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a solution of 27.4 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.7 g of γ-butyrolactone was added over 60 minutes while stirring. The mixture was then stirred at room temperature for 2 hours. Subsequently, 2.9 g of p-toluenesulfonic acid monohydrate was added, and the mixture was further stirred at room temperature for 1 hour. 7.2 g of ethanol was added to the reaction mixture and stirred for 1 hour. Subsequently, 136.8 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration, resulting in a reaction solution. The resulting reaction solution was added to 716.2 g of ethanol to produce a precipitate consisting of a crude polymer. The resulting crude polymer was filtered and dissolved in 403.5 g of tetrahydrofuran to obtain a crude polymer solution. 37.7 g of water was added to the solution and stirred for 15 minutes. Afterwards, 110.0 g of ion exchange resin UP6040 was added and stirred for 4 hours. The filtrate obtained after filtering the polymer solution was then added dropwise to 8470.3 g of water to precipitate the polymer. The resulting precipitate was filtered and vacuum dried to obtain 76.8 g of powdered polymer A-1. The molecular weight of polymer A-1 was measured by gel permeation chromatography (standard polystyrene conversion) and the weight average molecular weight (Mw) was 20,000.

[Synthesis Example 2: Synthesis of Polymer A-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 diethylene glycol dimethyl ether (diglyme) were mixed and stirred at 60°C for 4 hours to synthesize the diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and 17.0 g of sulfinyl chloride was added over 60 minutes while maintaining the temperature at -10 ± 5°C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 60 minutes at -10±5°C, and the mixture was stirred for 2 hours. Subsequently, a mixed solution of 159.6 g of ethanolamine hydrochloride and 200 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 60 minutes, and the mixture was stirred for 2 hours. Next, the polyimide precursor was precipitated by adding 6000 g of water, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was filtered and dissolved in 500 g of tetrahydrofuran. 6000 g of water (a poor solvent) was added to the resulting solution to precipitate the polyimide precursor. The precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was filtered again and dried at 45°C under reduced pressure for 3 days. 50.3 g of the dried powder was dissolved in 304.3 g of tetrahydrofuran. To this mixture, 18.5 g of water and 50.3 g of ion-exchange resin UP6040 (manufactured by AmberTec) were added and stirred for 4 hours. The ion-exchange resin was then removed by filtration, and 6,000 g of water was added to the resulting polymer solution to obtain a precipitate. The precipitate was filtered and dried at 45°C under reduced pressure for 24 hours to yield 49.6 g of polymer A-2. The molecular weight of polymer A-2 was measured by gel permeation chromatography (based on standard polystyrene) and the weight-average molecular weight (Mw) was 20,000.

[Synthesis Examples 3-9: Synthesis of Polymers A-18-A-24] A-18-A-19: In Synthesis Example 1, the same procedures as in Synthesis Example 1 were followed, using the same raw materials as in Synthesis Example 1, except that the amount of p-toluenesulfonic acid monohydrate added (2.9 g) was changed to 4.4 g in A-18 and 5.8 g in A-19. A-20 to A-24: In Synthesis Example 1, the resins were synthesized using the same raw materials and procedures as in Synthesis Example 1, except that the amount of DCC added (62.5 g) was changed to 62.8 g in A-20, 64.1 g in A-21, 67.2 g in A-22, 89.1 g in A-23, and 96.9 g in A-24.

[Synthesis of Comparative Example Polymer CA-1] 23.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.3 g of diphthalic dianhydride (BPDA) were placed in a separable flask. 39.7 g of 2-hydroxyethyl methacrylate (HEMA) and 136.8 g of γ-butyrolactone were added and stirred at room temperature (25°C). 24.7 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm due to the reaction subsided, the mixture was cooled to room temperature and allowed to stand for 16 hours. Next, under ice cooling, a solution of 62.5 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.6 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a solution of 27.4 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.7 g of γ-butyrolactone was added over 60 minutes while stirring. The mixture was then stirred at room temperature for 2 hours. 7.2 g of ethanol was added to the reaction mixture and stirred for 1 hour. Subsequently, 136.8 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration, resulting in a reaction solution. The resulting reaction solution was added to 716.2 g of ethanol to produce a precipitate consisting of a crude polymer. The crude polymer obtained by filtration was dissolved in 403.5 g of tetrahydrofuran to obtain a crude polymer solution. 37.7 g of water was added to the solution and stirred for 15 minutes. Then, 110.0 g of ion exchange resin UP6040 (AmberTec) was added and stirred for 4 hours. The filtrate obtained after filtering the polymer solution was added dropwise to 8470.3 g of water to precipitate the polymer. The precipitate was filtered and vacuum dried to obtain 77.8 g of powdered polymer CA-1. The molecular weight of the polymer was measured by gel permeation chromatography (based on standard polystyrene) and the weight-average molecular weight (Mw) was 20,000.

[Synthesis of Comparative Example Polymer CA-2] 23.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.3 g of diphthalic dianhydride (BPDA) were placed in a separable flask. 39.7 g of 2-hydroxyethyl methacrylate (HEMA) and 136.8 g of γ-butyrolactone were added and stirred at room temperature (25°C). 24.7 g of pyridine was added while stirring to obtain a reaction mixture. After the exotherm subsided, the mixture was cooled to room temperature and allowed to stand for 16 hours. Next, under ice cooling, a solution of 59.4 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.6 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a solution of 27.4 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.7 g of γ-butyrolactone was added over 60 minutes while stirring. The mixture was then stirred at room temperature for 2 hours. 7.2 g of ethanol was added to the reaction mixture and stirred for 1 hour. Subsequently, 136.8 g of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration, resulting in a reaction solution. The resulting reaction solution was added to 716.2 g of ethanol to produce a precipitate consisting of a crude polymer. The crude polymer obtained by filtration was dissolved in 403.5 g of tetrahydrofuran to obtain a crude polymer solution. 37.7 g of water was added to the solution and stirred for 15 minutes. Then, 110.0 g of ion exchange resin UP6040 (AmberTec) was added and stirred for 4 hours. The filtrate obtained after filtering the polymer solution was added dropwise to 8470.3 g of water to precipitate the polymer. The precipitate was filtered and vacuum dried to obtain 75.1 g of powdered polymer CA-2. The molecular weight of the polymer was measured by gel permeation chromatography (based on standard polystyrene) and the weight-average molecular weight (Mw) was 19,500.

<Examples and Comparative Examples> In each Example, the components listed in the following table were mixed to obtain a respective curable resin composition. Furthermore, in each Comparative Example, the components listed in the following table were mixed to obtain a respective comparative composition. Specifically, the content of each component listed in the table is the amount (parts by mass) listed in parentheses within each column. The resulting curable resin composition and comparative composition were pressure-filtered using a polytetrafluoroethylene filter with a pore width of 0.8 μm. In the table, a "-" indicates that the composition does not contain the corresponding component.

[Table 1] Resin Synthesis method Specific structure content (mmol/g) Amine value (mmol/g) photosensitizer Organometallic complexes Crosslinking agent polymerization inhibitors additives Metal adhesion improver solvent Exposure conditions Exposure wavelength nm Development conditions Vulcanization temperature (℃) Vulcanization method Exposure tolerance Drug resistance Elongation at break Example 1 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 2 A-18 (35) 1 0.14 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 A B B Example 3 A-19 (35) 1 0.00 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 A B B Example 4 A-20 (35) 1 0.28 0.0080 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B A A Example 5 A-21 (35) 1 0.28 0.0500 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B A A Example 6 A-22 (35) 1 0.28 0.1500 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B A A Example 7 A-23 (35) 1 0.28 0.8500 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B A Example 8 A-24 (35) 1 0.28 1.1000 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B C A Example 9 A-2 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 10 A-3 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 11 A-4 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 12 A-6 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B C B Example 13 A-7 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 14 A-8 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 15 A-9 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B C B Example 16 A-10 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 17 A-11 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 18 A-12 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B

[Table 2] Resin Synthesis method Specific structure content (mmol/g) Amine value (mmol/g) photosensitizer Organometallic complexes Crosslinking agent polymerization inhibitors additives Metal adhesion improver solvent Exposure conditions Exposure wavelength nm Development conditions Vulcanization temperature (℃) Vulcanization method Exposure tolerance Drug resistance Elongation at break Example 19 A-13 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B C B Example 20 A-14 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 21 A-15 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 22 A-16 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B C B Example 23 A-17 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B C B Example 24 A-2/A-6 (18/18) 1 0.28 /0.28 0.0040 /0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 25 A-1 (35) 2 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 26 A-2 (35) 2 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 27 A-3 (35) 2 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 28 A-1 (35) 1 0.28 0.0040 B-1 (3.0) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 A A B Example 29 A-1 (35) 1 0.28 0.0040 B-2 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 30 A-1 (35) 1 0.28 0.0040 B-3 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 31 A-1 (35) 1 0.28 0.0040 B-1 (0.7) B-2 (0.7) X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 32 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-2 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 33 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-3 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 34 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-4 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 35 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-5 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 36 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-6 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B

[Table 3] Resin Synthesis method Specific structure content (mmol/g) Amine value (mmol/g) photosensitizer Organometallic complexes Crosslinking agent polymerization inhibitors additives Metal adhesion improver solvent Exposure conditions Exposure wavelength nm Development conditions Vulcanization temperature (℃) Vulcanization method Exposure tolerance Drug resistance Elongation at break Example 37 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-7 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 38 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-8 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 39 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (2.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B A B Example 40 A-1 (35) 1 0.28 0.0040 - - X-1 (2.4) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B A B Example 41 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - Xl/X-2 (1.0/1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B A B Example 42 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-2 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 43 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (6.8) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 A A B Example 44 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-2 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 45 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-3 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 46 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-4 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 47 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 48 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-6 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 49 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-7 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 50 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.4) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B A Example 51 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) - - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B C B Example 52 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) - E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B C B Example 53 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (4.8) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B A B Example 54 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (1.8) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B A B

[Table 4] Resin Synthesis method Specific structure content (mmol/g) Amine value (mmol/g) photosensitizer Organometallic complexes Crosslinking agent polymerization inhibitors additives Metal adhesion improver solvent Exposure conditions Exposure wavelength nm Development conditions Vulcanization temperature (℃) Vulcanization method Exposure tolerance Drug resistance Elongation at break Example 55 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-2 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 56 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-3 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 57 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-4 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 58 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-5 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 59 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-6 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 60 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (2.0) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 61 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) DMSO (11.3) γBL (45.1) M 405 Negative 230 1 B B B Example 62 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (11.3) EL (45.1) M 405 Negative 230 1 B B B Example 63 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) D 405 Negative 230 1 B B B Example 64 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) D 405 Negative 230 1 B B B Example 65 A-1 (35) 1 0.28 0.0040 B-2 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) DMSO (11.3) γBL (45.1) M 405 Negative 230 1 B A A Example 66 A-2 (35) 1 0.28 0.0040 B-2 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) DMSO (11.3) γBL (45.1) M 405 Negative 230 1 B A A Example 67 A-3 (35) 1 0.28 0.0040 B-2 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) DMSO (11.3) γBL (45.1) M 405 Negative 230 1 B A A Example 68 A-4 (35) 1 0.28 0.0040 B-2 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) DMSO (11.3) γBL (45.1) M 405 Negative 230 1 B A A Example 69 A-6 (35) 1 0.28 0.0040 B-2 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) DMSO (11.3) γBL (45.1) M 405 Negative 230 1 B A A Example 70 A-10 (35) 1 0.28 0.0040 B-2 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) DMSO (11.3) γBL (45.1) M 405 Negative 230 1 B A A Example 71 A-17 (35) 1 0.28 0.0040 B-2 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) DMSO (11.3) γBL (45.1) M 405 Negative 230 1 B A A Example 72 A-5 (35) 1 0.28 0.0040 - - - - - E-4 (2.4) E-5 (0.5) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 just 230 1 B B B

[Table 5] Resin Synthesis method Specific structure content (mmol/g) Amine value (mmol/g) photosensitizer Organometallic complexes Crosslinking agent polymerization inhibitors additives Metal adhesion improver solvent Exposure conditions Exposure wavelength nm Development conditions Vulcanization temperature (℃) Vulcanization method Exposure tolerance Drug resistance Elongation at break Example 73 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 74 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-2 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 75 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-3 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 76 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-4 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 77 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 78 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-6 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 79 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-7 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B B Example 80 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 365 Negative 230 1 B B B Example 81 A-1 (35) 1 0.28 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-2 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) NMP (45.1) EL (11.3) M 365 Negative 230 1 B B B Example 82 A-5 (35) 1 0.28 0.0040 - - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-4 (2.4) E-5 (0.5) - F-1 (0.7) NMP (45.1) EL (11.3) M 365 just 230 1 B C B Example 83 A-5 (35) 1 0.28 0.0040 - - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-4 (2.4) E-5 (0.5) - F-1 (0.7) NMP (45.1) EL (11.3) D 405 just 230 1 B C B Example 84 A-18 (35) 1 0.14 0.0040 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 A C B Example 85 A-1 (35) 1 0.28 0.0080 B-1 (1.4) - - C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 B B A Example 86 A-18 (35) 1 0.14 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 2 A B B Example 87 A-1 (35) 1 0.28 0.0080 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 2 B A A Example 88 A-18 (35) 1 0.14 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 200 1 A B B Example 89 A-18 (35) 1 0.14 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 180 1 A B B Comparative example 1 CA-1 (35) 1 0.44 0.0040 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 D D B Comparative example 2 CA-2 (35) 1 0.28 0.0030 B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) NMP (45.1) EL (11.3) M 405 Negative 230 1 C D C

The details of each ingredient listed in Tables 1 to 5 are as follows.

[Resin] ･A-1 to A-24, CA-1 to CA-2: Polymers A-1 to A-24, CA-1 to CA-2 obtained in the above synthesis examples

[Photosensitizer (photoradical polymerization initiator)] ･B-1 to B-3: Compounds with the following structure [Chemical Formula 52]

[Organometallic Complexes] ･X-1: Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium ･X-2: Pentamethylcyclopentadienyltrimethoxytitanium ･X-3: Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium ･X-4: Tetraisopropoxytitanium (Matsumoto Fine Chemical Co., Ltd.) ･X-5: Diisopropoxybis(acetylacetonato)titanium (Matsumoto Fine Chemical Co., Ltd.) ･X-6 to X-8: Compounds with the following structures. [Chemical Formula 53] The above X-1 and X-3 are compounds having the ability to initiate photoradical polymerization.

[Crosslinking agent (polymerizable compound)] ･C-1 to C-2: Compounds with the following structure [Chemical Formula 54]

[Polymerization inhibitors, migration inhibitors] ･D-1 to D-7: Compounds with the following structure [Chemical Formula 55]

[Additives] ･E-1 to E-6: Compounds with the following structure [Chemical Formula 56]

[Metal Adhesion Improver] ･F-1 to F-6: Compounds with the following structure [Chemical Formula 57] In the above structural formula, Me represents a methyl group, and Et represents an ethyl group.

[Solvent] ･NMP: N-methyl-2-pyrrolidone ･EL: Ethyl lactate ･DMSO: Dimethyl sulfoxide ･γBL: γ-butyrolactone

<Evaluation> [Measurement of the Total Content of Cyclic Imine and Cyclic Isoimide Structures] For the resins used in each of the Examples and Comparative Examples, the total molar content of cyclic imide and cyclic isoimide structures contained in 1 g of the resin (polyimide precursor) was measured using the following method. 0.10 g of the resin was dissolved in 0.90 g of deuterated DMSO (dimethylsulfoxide-d6), and the total molar content of the polymer powder was measured using ¹ H NMR. Specifically, the ratio of cyclic imide and cyclic isoimide structures was calculated from the ratio of the proton peaks of the cyclic imide and cyclic isoimide structures to the proton peaks of the total aromatic rings. The measurement results for each resin are reported in the "Specific Structure Content (mmol/g)" column in the table.

[Amine Value Measurement] The amine value of each resin used in each Example or Comparative Example was measured using the following method. After completely dissolving 0.60 g of the resin in 50 mL of diethylene glycol dimethyl ether, 10 mL of acetic acid was added to prepare a measurement solution. This solution was then added dropwise to a 0.01 N (0.01 mol/L) perchloric acid solution in acetic acid to detect the neutralization point and measure the amine value of the resin. The measurement results for each resin are reported in the "Amine Value (mmol/g)" column in the table.

[Evaluation of Exposure Latitude] In each Example or Comparative Example, the prepared curable resin composition or comparative composition was applied to a silicon wafer by spin coating. The silicon wafer was dried on a hot plate at 100°C for 5 minutes, forming a uniform 20μm thick layer of the curable resin composition on the silicon wafer. In the example where the exposure condition was "M," the curable resin composition layer on the silicon wafer was exposed using a stepper. Exposure was performed using light of the wavelength indicated as "Exposure wavelength nm" in the table, using a fuse box mask with a scale of 1μm from 5μm to 25μm. In the case where "D" is entered under the exposure conditions, exposure was performed using a direct exposure device (ADTEC DE-6UH III). Laser direct development exposure was performed at a wavelength of 405 nm, with the exposed area forming a line portion of a line-and-space pattern with 1 μm scale ranging from 5 μm to 25 μm. In the case where "Positive" is entered under the "Development Conditions" column, the exposed curable resin composition layer was developed for 60 seconds using a 2.5% by mass aqueous solution of tetramethylammonium hydroxide and then rinsed with pure water. In the case where "Negative" is entered under the "Development Conditions" column, the exposed curable resin composition layer was developed for 60 seconds using cyclopentanone and then rinsed with PGMEA (propylene glycol monomethyl ether acetate). In this evaluation, the exposure dose was varied at nine different exposure doses: 100, 200, 300, 400, 500, 600, 700, 800, and 900 mJ/ ^cm² . Furthermore, among the patterns obtained after development, the line width of the line pattern with the smallest line width exposed between the line patterns was set as the "minimum line width." Evaluation was conducted based on the following evaluation criteria, based on an exposure dose range where the minimum resolvable line width was 6 to 8 μm. The evaluation results are recorded in the "Exposure Width Tolerance" column in the table. -Evaluation Criteria- A: A minimum line width of 6 to 8 μm can be resolved within a range of more than 8 exposure doses. B: A minimum line width of 6 to 8 μm can be resolved within a range of 5 to 7 exposure doses. C: The minimum line width of 6-8μm can be resolved only within the exposure range of at least one and no more than four. D: The minimum aperture of 6-8μm cannot be resolved within any exposure range.

[Evaluation of Chemical Resistance] -Calculation of Dissolution Rate- In each Example or Comparative Example, a photosensitive film was formed on a silicon wafer using the same method as used for forming the photosensitive film in the exposure latitude evaluation described above. Thereafter, in each Example or Comparative Example, exposure was performed using the same method as used in the exposure latitude evaluation, except that, for the examples where "M" was entered in the "Exposure Conditions" column, the entire surface of the photosensitive film was exposed without using a photomask, and for the examples where "D" was entered in the "Exposure Conditions" column, the entire surface of the photosensitive film was exposed with a laser. Resin films were obtained by exposure using the same method as used in the exposure latitude evaluation described above. However, no exposure was performed in the examples where "Positive" was entered in the "Development Conditions" column. In the example listed as "1" in the "Vulcanization Method" column, the resin film was heated at a rate of 10°C/min in a nitrogen atmosphere using a hot plate. After reaching the temperature listed in the "Vulcanization Temperature (°C)", the temperature was maintained for 3 hours to form a cured product (cured film). In the example listed as "2" in the "Vulcanization Method" column, the resin films obtained in each example were heated at a rate of 10°C/min in a nitrogen atmosphere using an infrared lamp heater (RTP-6, manufactured by ADVANCE RIKO, Inc.). After reaching the temperature listed in the "Vulcanization Temperature (°C)", the temperature was maintained for 3 hours to form a cured product (cured film). The resulting cured product was immersed in the following chemical under the following conditions, and the dissolution rate was calculated. Chemical: A 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and a 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Evaluation Conditions: The cured product was immersed in the chemical at 75°C for 15 minutes. The film thickness before and after immersion was compared, and the dissolution rate (nm/min) was calculated. The obtained dissolution rate values were evaluated according to the following evaluation criteria and recorded in the "Chemical Resistance" column. The lower the dissolution rate, the better the chemical resistance. -Evaluation Criteria- A: Dissolution rate less than 250 nm/min. B: Dissolution rate of 250 nm/min or greater and less than 500 nm/min. C: Dissolution rate is 500 nm/min or greater and less than 750 nm/min. D: Dissolution rate is 750 nm/min or greater.

[Evaluation of Elongation at Break] The curable resin compositions or comparative compositions prepared in each of the Examples and Comparative Examples were applied to a silicon wafer by spin coating to form a resin layer. The resulting resin layer was dried on a hot plate at 100°C for 5 minutes, resulting in a uniform curable resin layer of approximately 15 μm in thickness. In the examples listed as "negative" in the Development Conditions column in the table, the entire surface of the curable resin layer on the silicon wafer was exposed with an exposure energy of 500 mJ/ ^cm² . The exposure method was the same as that used in the chemical resistance evaluation described above, with the exposure wavelength indicated in the "Exposure Wavelength (nm)" column of the table. In the case where "Positive" is indicated in the "Development Conditions" column of the table, no exposure was performed. In the case where "1" is indicated in the "Vulcanization Method" column, the exposed curable resin composition layer was heated at a rate of 10°C/min using a hot plate in a nitrogen atmosphere. After reaching the temperature indicated in the "Vulcanization Temperature (°C)" column, the temperature was maintained for 3 hours. In the example listed as "2" in the "Vulcanization Method" column, the resin films obtained in each example were heated at a rate of 10°C/min in a nitrogen atmosphere using an infrared lamp heater (RTP-6, manufactured by ADVANCE RIKO, Inc.) to the temperature indicated in the "Vulcanization Temperature (°C)" and then maintained at that temperature for 3 hours. The cured curable resin composition layer (cured product) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution and peeled from the silicon wafer. The peeled cured product was punched using a punch to produce test specimens with a width of 3 mm and a length of 30 mm. The elongation in the longitudinal direction of the obtained test specimens was measured using a TENSILON tensile tester at a crosshead speed of 300 mm/min, 25°C, and 65% relative humidity (RH) in accordance with JIS-K6251. Each measurement was performed five times, and the arithmetic mean of the elongation at break (elongation at break) of the test specimens from these five measurements was used as the index value. Evaluation was performed according to the following evaluation criteria, and the results are reported in the "Elongation at Break" column of the table. The higher the index value, the better the film strength of the cured product. -Evaluation Criteria- A: The index value is 60% or higher. B: The index value is 55% or higher and less than 60%. C: The index value is less than 55%.

The above results demonstrate that the curable resin composition of the present invention exhibits excellent exposure latitude and the resulting cured product exhibits excellent chemical resistance. The resin used in Comparative Example 1 has a combined content of cyclic imide and cyclic isoimide structures exceeding 0.29 mmol/g. This indicates that the use of this resin results in poor exposure latitude. Furthermore, the resin used in Comparative Example 2 has an amine value of less than 0.0040 mmol/g. This indicates that the use of this resin results in poor chemical resistance.

<Example 101> The curable resin composition used in Example 1 was applied in layers to the surface of a copper thin layer formed on a resin substrate with a copper thin layer formed on the surface by spin coating. The film was dried at 100°C for 4 minutes to form a 20μm-thick photosensitive film. The film was then exposed using a stepper (Nikon Co., Ltd., NSR1505 i6). Exposure was performed at a wavelength of 365nm through a mask (a binary mask with a 1:1 line and space pattern and a line width of 10μm). After exposure, the film was heated at 100°C for 4 minutes. Following heating, the film was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern. Next, the temperature was raised at a rate of 10°C/minute in a nitrogen atmosphere until it reached 230°C. It was then maintained at 230°C for 120 minutes, forming a redistribution layer interlayer insulating film. This redistribution layer interlayer insulating film exhibited excellent insulating properties. Semiconductor devices were fabricated using this redistribution layer interlayer insulating film, and normal operation was confirmed.

without.

Claims (20)

A curable resin composition contains a polyimide precursor having a group containing an ethylenically unsaturated bond or a polar conversion group, a total content of cyclic imide structures and cyclic isoimide structures of 0.01 to 0.29 mmol/g, and an amine value of 0.0040 to 1.1100 mmol/g. The hardening resin composition as described in claim 1 further contains a photopolymerization initiator. The curable resin composition as described in claim 2, wherein the photopolymerization initiator is an oxime compound. The hardening resin composition according to any one of claims 1 to 3, further comprising a polymerizable compound. The hardening resin composition according to any one of claims 1 to 3, further comprising an organometallic complex. The hardening resin composition as described in claim 5, wherein the organometallic complex is a metallocene compound. The hardening resin composition of claim 5, wherein the metal contained in the organometallic complex is at least one metal selected from the group consisting of titanium, zirconium, and einsteinium. The hardening resin composition according to any one of claims 1 to 3 is used to form a photosensitive film for negative tone development. The curable resin composition according to any one of claims 1 to 3 is used to form an interlayer insulating film for a redistribution layer. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 9. A laminate comprising two or more layers comprising the hardened material according to claim 10, wherein a metal layer is included between any of the layers comprising the hardened material. A method for producing a cured product, comprising a film-forming step of applying the curable resin composition according to any one of claims 1 to 9 to a substrate to form a film. The method for manufacturing a cured product as described in claim 12 includes an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern. The method for producing a cured product as described in claim 13, wherein the exposure light used in the aforementioned exposure comprises light having a wavelength of 405 nm. The method for producing a cured product as described in claim 13, wherein the exposure is performed by direct laser imaging. The method for manufacturing a cured product as described in claim 12 includes a heating step of heating the film at 50 to 450°C. A semiconductor device comprising the hardened material according to claim 10. A polyimide precursor has a group containing an ethylenically unsaturated bond or a polar conversion group, a total content of cyclic imide structures and cyclic isoimide structures of 0.01 to 0.29 mmol/g, and an amine value of 0.0040 to 1.1100 mmol/g. A method for producing a polyimide precursor, comprising: an amidation step of reacting a dicarboxylic acid compound with a diamine compound to obtain an amide compound; and an end-capping step of reacting the amide compound with an end-capping agent having an amino group. A method for producing a polyimide precursor, comprising: an amidation step of reacting a dicarboxylic acid compound with a diamine compound in the presence of an alkaline catalyst to obtain an amide compound; and an acidic compound addition step of adding an acid to the amide compound.