TWI890798B - Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Abstract

The present invention provides a curable resin composition, a cured film formed by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate. The curable resin composition comprises: at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole; and a compound B having a polymerizable group and an azole group.

Description

Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device

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

Polyimide and polybenzoxazole have excellent heat resistance and insulation properties, making them suitable for a variety of applications. While these applications are not particularly limited, examples include use as insulating films, sealing materials, and protective films for packaging semiconductor devices. They are also used as base films and coverlay films for flexible substrates.

For example, in the aforementioned applications, polyimide or polybenzoxazole is used in the form of a curable resin composition comprising at least one resin selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, and a polybenzoxazole precursor. This curable resin composition is applied to a substrate, for example, by coating, to form a resin film. The film is then exposed, developed, and heated as needed to form a cured film on the substrate. The polyimide precursor and the polybenzoxazole precursor are cyclized, for example, by heating, to form polyimide and polybenzoxazole, respectively, in the cured film. Because curable resin compositions can be applied using known coating methods, they offer a high degree of design freedom in terms of shape, size, and application location, resulting in excellent manufacturing flexibility. In addition to the high performance offered by polyimide and polybenzoxazole, this superior manufacturing flexibility is expected to expand the industrial applications of these curable resin compositions.

For example, Patent Document 1 describes a composition comprising (A) a polyimide precursor, (B) a compound containing a heterocyclic structure having a nitrogen atom with a pKa of 8.30 to 8.80, and (C) a resin containing 5-amino-1H-tetrazole.

Patent Document 1: Japanese Patent Application Publication No. 2012-002281

When producing a cured film composed of a curable resin composition and in contact with metal, it is desirable to improve the adhesion between the cured film and the metal. Examples of such metals include metals included in metal layers such as conductive layers, including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper, aluminum, and alloys containing these metals are preferred, copper or alloys containing copper are more preferred, and copper is even more preferred. For example, in a laminate comprising a metal layer and a cured film in contact with the metal layer, it is desirable to improve the adhesion between the metal layer and the cured film.

An object of the present invention is to provide a curable resin composition capable of producing a cured film having excellent adhesion to metal, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate.

Representative embodiments of the present invention are described below. <1> A curable resin composition comprising: at least one resin selected from the group consisting of polyimide prodrugs, polybenzoxazole prodrugs, polyimides, and polybenzoxazoles; and a compound B having a polymerizable group and an azole group. <2> The curable resin composition described in <1>, wherein the compound B has at least one group selected from the group consisting of an amino group, a urethane group, and a urea group. <3> The curable resin composition described in <1> or <2>, wherein the compound B has, as the polymerizable group, at least one group selected from the group consisting of a free radical polymerizable group and an alkoxysilyl group. <4> The curable resin composition according to any one of <1> to <3>, wherein the azole group in the compound B is a group represented by the following formula (B-1) or the following formula (B-2); [Chemical Formula 1] In formula (B-1), ^RB1 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, ^ZB1 to ^ZB4 each independently represent = ^CRB7- or a nitrogen atom, ^RB7 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, and at least one of ^RB1 and ^RB7 included in formula (B-1) represents a bonding site with a structure having a polymerizable group; In formula (B-2), ^RB2 to ^RB6 each independently represent a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, ^ZB5 and ^ZB6 each independently represent = ^CRB8- or a nitrogen atom, and R ^B8 represents a bonding site to a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group not having a polymerizable group, and at least one of ^RB2 to ^RB6 and ^RB8 included in formula (B-2) represents a bonding site to a structure having a polymerizable group. <5> The curable resin composition according to any one of <1> to <4>, wherein the compound B comprises a compound B having a molecular weight of less than 2,000. <6> The curable resin composition according to any one of <1> to <5>, wherein the compound B comprises a resin. <7> The curable resin composition according to any one of <1> to <6>, further comprising a compound C having an azole group and not having a polymerizable group. <8> The curable resin composition as described in <7>, wherein the compound C is a compound represented by the following formula (C-1) or the following formula (C-2); [Chemical Formula 2] In formula (C-1), Z ¹ to Z ⁴ each independently represent ═CR ⁷ - or a nitrogen atom, R ¹ represents a hydrogen atom or a monovalent organic group, R ⁷ represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (C-1) does not contain a polymerizable group. In formula (C-2), Z ⁵ to Z ⁶ each independently represent ═CR ⁸ - or a nitrogen atom, R ² to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, R ⁸ represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (C-2) does not contain a polymerizable group. <9> The curable resin composition according to any one of <1> to <8>, wherein at least one resin selected from the group consisting of the polyimide prodrug, polybenzoxazole prodrug, polyimide, and polybenzoxazole has a polymerizable group that is polymerizable with the polymerizable group in the compound B. <10> The curable resin composition according to any one of <1> to <9>, further comprising a compound D as a silane coupling agent having a polymerizable group different from an alkoxysilyl group and not having an azole group. <11> The curable resin composition according to <10>, wherein at least one resin selected from the group consisting of the polyimide precursor, polybenzoxazole precursor, polyimide, and polybenzoxazole has a polymerizable group that is polymerizable with the polymerizable group in the compound D. <12> The curable resin composition according to any one of <1> to <11>, further comprising a compound E as a silane coupling agent that does not have either a polymerizable group other than an alkoxysilyl group or an azole group. <13> The curable resin composition according to any one of <1> to <12>, which is used for forming an interlayer insulating film for a redistribution layer. <14> A cured film formed by curing the curable resin composition described in any one of <1> to <13>. <15> A laminate comprising two or more layers of the cured film described in <14>, and comprising a metal layer between any of the cured films. <16> A method for producing a cured film, comprising: a film forming process of applying the curable resin composition described in any one of <1> to <13> to a substrate to form a film. <17> The method for producing a cured film as described in <16>, comprising: an exposure process of exposing the film; and a development process of developing the film. <18> A method for producing a cured film according to <16> or <17>, comprising: a heating process of heating the film at 50 to 450°C. <19> A semiconductor device comprising the cured film according to <14> or the laminate according to <15>. [Effects of the Invention]

According to the present invention, there are provided a curable resin composition capable of producing a cured film having excellent adhesion to metal, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate.

The following describes the main embodiments of the present invention. However, the present invention is not limited to the specified embodiments. In this specification, numerical ranges expressed using symbols such as "to" indicate the ranges including the numerical values before and after the "to" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as the intended function of the process is achieved. In the notation of groups (atomic radicals) in this specification, the notation "substituted" or "unsubstituted" includes both groups (atomic radicals) without substituents and groups (atomic radicals) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, active light or radiation such as electron beams. In this specification, "(meth)acrylate" refers to both or either "acrylate" or "methacrylate," "(meth)acrylic acid" refers to both or either "acrylic acid" or "methacrylic acid," and "(meth)acryl" refers to both or either "acryl" or "methacryl." In this specification, Me in a 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 term "total solids" refers to the total mass of all components of a composition after removing the solvent. Furthermore, the term "solids concentration" refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are defined as polystyrene-equivalent values determined by gel permeation chromatography (GPC). In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220GPC (manufactured by TOSOH CORPORATION) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, or TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise specified, these molecular weights are determined using THF (tetrahydrofuran) as the eluent. Furthermore, unless otherwise specified, GPC measurements are performed using a UV (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of the layers constituting a laminate is described as "upper" or "lower," it suffices to state that other layers exist above or below the standard layer in question among the multiple layers. In other words, a third layer or element may be interposed between the standard layer and the other layers, and the standard layer and the other layers do not need to be in contact. Furthermore, unless otherwise specified, the direction in which the layers are stacked relative to the substrate is referred to as "upper," or in the case of a photosensitive layer, the direction from the substrate toward the photosensitive layer is referred to as "upper," and the opposite direction is referred to as "lower." This designation of the up and down directions is for convenience within this specification; in actual practice, the "upper" direction in this specification may differ from the vertical direction. In this specification, unless otherwise specified, each component in a composition may contain two or more compounds corresponding to that component. Furthermore, unless otherwise specified, the content of each component in a composition refers to the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a preferred combination is considered a more preferred combination.

(Curing Resin Composition) The curable resin composition of the present invention comprises: at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimides, and polybenzoxazoles (hereinafter also referred to as the "specific resin"); and compound B, which is a compound having a polymerizable group and an azole group.

The curable resin composition of the present invention may be either a negative-working or positive-working curable resin composition, but negative-working curable resin compositions are preferred. A negative-working curable resin composition is one in which, when a layer formed from the curable resin composition is exposed to light, the unexposed portions (non-exposed portions) are removed by a developer. A positive-working curable resin composition is one in which, when a layer formed from the curable resin composition is exposed to light, the exposed portions (exposed portions) are removed by a developer.

The curable resin composition of the present invention can produce a cured film with excellent adhesion to metal. While the mechanism for achieving this effect is unclear, it is speculated as follows.

The curable composition of the present invention, containing a compound B having both a polymerizable group and an azole group, produces a cured film exhibiting excellent adhesion to metal. It is believed that the azole groups in compound B coordinate with the metal surface, and that the polymerizable groups in compound B polymerize within the cured film, resulting in the presence of a polymer of compound B on the metal surface within the cured film. The presence of this polymer is believed to provide an anchoring effect on cured resins such as polyimide, thereby enhancing adhesion. This enhanced adhesion effect is particularly pronounced when the specific resin, such as polyimide, contains a polymerizable group, or when the curable resin composition contains a silane coupling agent. This is presumably because polymerization also occurs between the specific resin and compound B, or between the silane coupling agent and compound B, in the cured film.

Furthermore, when manufacturing a laminate comprising a film composed of a curable resin composition, the metal layer and the cured film may be laminated, for example, by forming a metal layer on a cured film composed of a curable resin composition, and then forming another cured film composed of a curable resin composition on the metal layer. The curable resin composition of the present invention is believed to suppress interlayer peeling between resin layers and between metal layers even in such a laminate. This is presumably due to the presence of the relatively soft polymer of Compound B between the hard resin, such as polyimide, and the hard metal. In the present invention, suppressing interlayer peeling between resin layers and between metal layers and resin layers in a laminate is also referred to as "excellent adhesion during multi-layer lamination."

Here, Patent Document 1 neither describes nor suggests a curable resin composition containing a compound B having a polymerizable group and an azole group.

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

<Specific Resin> The curable resin composition of the present invention comprises at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor. The curable resin composition of the present invention preferably comprises a polyimide or a polyimide precursor as the specific resin, and more preferably comprises a polyimide precursor.

Furthermore, the specific resin preferably has a polymerizable group. Examples of polymerizable groups in the specific resin include known polymerizable groups such as free radical polymerizable groups, epoxy groups, cyclobutyl oxy groups, hydroxymethyl groups, and alkoxymethyl groups. Preferred free radical polymerizable groups include groups having an ethylenically unsaturated bond. Examples of groups having an ethylenically unsaturated bond include groups having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, or a vinylphenyl group, (meth)acrylamide groups, (meth)acryloyloxy groups, and the like. (meth)acryloyloxy groups are preferred. Preferred polymerizable groups in the specific resin include those capable of polymerizing with the polymerizable group in compound B described below. Examples of combinations of polymerizable groups include combinations where the specific resin has a free radical polymerizable group and compound B has a free radical polymerizable group, or combinations where the specific resin has an epoxy group and compound B has an epoxy group. In these embodiments, it is believed that in the cured film, the polymerizable groups in the specific resin polymerize with the polymerizable groups in compound B, strengthening the bond between the specific resin and compound B and further improving the adhesion of the resulting cured film to metal.

When the curable resin composition includes compound D, described below, the specific resin preferably has a polymerizable group that is polymerizable with the polymerizable group in compound D. Examples of combinations of polymerizable groups include combinations where the specific resin has a free radical polymerizable group and compound D has a free radical polymerizable group, or combinations where the specific resin has an epoxy group and compound D has an epoxy group. In this embodiment, it is believed that in the cured film, the polymerizable group in the specific resin polymerizes with the polymerizable group in compound D, strengthening the bond between the specific resin and compound D and further improving the adhesion of the resulting cured film to metal. Furthermore, in this embodiment, compound B preferably has an alkoxysilyl group. In this manner, in the cured film, the polymerizable groups in the specific resin polymerize with the polymerizable groups in compound D, and the alkoxysilyl groups in compound B fuse with compound D, which acts as a silane coupling agent. This is believed to strengthen the bonds between the compounds and further enhance the adhesion of the resulting cured film to metal.

Furthermore, the specific resin preferably contains a radically polymerizable group. When the specific resin contains a radically polymerizable group, the curable resin composition preferably contains a photoradical polymerization initiator (described below) as a photosensitizer, more preferably contains the photoradical polymerization initiator (described below) and a radical crosslinking agent (described below) as a photosensitizer, and even more preferably contains the photoradical polymerization initiator (described below), a radical crosslinking agent (described below) and a sensitizer (described below) as a photosensitizer. Such a curable resin composition can, for example, form a negative-type photosensitive layer. Also, the specific resin may contain a polarity-converting group such as an acid-degradable group. When the specific resin has an acid-degradable group, the curable resin composition preferably includes a photoacid generator, described below, as a photosensitizer. This curable resin composition can be used to form, for example, a chemically amplified positive-type photosensitive layer or a negative-type photosensitive layer.

[Polyimide Precursor] The type of the polyimide precursor used in the present invention is not particularly limited, but it is preferably one containing a repeating unit represented by the following formula (2). Formula (2) [Chemical Formula 3] 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 containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Groups composed of linear or branched aliphatic groups having 2 to 20 carbon atoms, cyclic aliphatic groups having 6 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or combinations thereof are preferred. Groups containing aromatic groups having 6 to 20 carbon atoms are even more preferred. As a particularly preferred embodiment of the present invention, a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is independently an aromatic group, and L is a group consisting of an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, or -NHCO-, or a combination of two or more thereof. The preferred ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. One or more diamines may be used. Specifically, a diamine comprising a group consisting of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferred, and a diamine comprising a group consisting of an aromatic group having 6 to 20 carbon atoms is even more preferred. Examples of aromatic groups include the following.

【Chemical formula 4】 In the formula, A is preferably 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. More preferably, it is 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- . Even more preferably, it is _-CH2- , -O-, -S-, _-SO2- , -C( _CF3 ) _2- , or -C( _CH3 ) _2- . In the formula, * indicates a bonding site to another structure.

Specifically, the diamine may be at least one selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine. ; m- or p-phenylenediamine, diaminotoluene, 4,4’- or 3,3’-diaminobiphenyl, 4,4’-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4’- and 3,3’-diaminodiphenylmethane, 4,4’- and 3,3’-diaminodiphenylsulfone, 4,4’- and 3,3’-diaminodiphenylsulfide, 4,4’- or 3,3’-diaminobenzophenone, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 2,2-diaminodiphenyl (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-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfonate 、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'-diamino Aminodiphenylmethane, 2,4- and 2,5-diaminoisopropylbenzene, 2,5-dimethyl-p-phenylenediamine, ethylguanidinium, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1 ,5-Bis(4-aminophenyl)decafluoropentane, 1,7-Bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy) )biphenyl, 4,4’-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4’-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfonium, 4,4’-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfonium, 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’-hexafluorotriphenylmethane and 4,4’-diaminotetraphenyl.

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

In addition, the following diamines can also be preferably used. [Chemical Formula 5]

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

From the 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 a group consisting of an aliphatic alkyl group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -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 a fluorine atom, -O-, -CO-, -S-, or -SO ₂ -. The aliphatic alkyl group herein is preferably an alkylene group.

Furthermore, from the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 6] In formula (51), ^R50 to ^R57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of ^R50 to ^R57 is a fluorine atom, a methyl group, or a trifluoromethyl group. 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 7] In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl group. Examples of diamine compounds that provide the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These compounds may be used alone or in combination of two or more.

Furthermore, R ¹¹¹ may also be a structure containing a polymerizable group. For example, R ¹¹¹ may be a structure derived from a diamine compound having a polymerizable group. The diamine compound having a polymerizable group is not particularly limited, but compounds containing an aromatic ring structure are preferred, and compounds having a structure containing an amine group and a polymerizable group directly bonded to the aromatic ring structure are even more preferred. As the polymerizable group, a group comprising an ethylenically unsaturated group, a cyclic ether group, a hydroxymethyl group, or an alkoxymethyl group is preferred; a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, a cis-butylenediamide group, a vinylphenyl group, an epoxy group, an oxacyclobutyl group, a hydroxymethyl group, or an alkoxymethyl group is more preferred; and a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group, or an alkoxymethyl group is even more preferred.

Furthermore, when R ¹¹¹ is a structure containing a polymerizable group, R ¹¹¹ is preferably a structure represented by the following formula (1-1). [Chemical Formula 8] In formula (1-1), ^Y1 represents an n+2 valent group containing an aromatic hydrocarbon group, ^P1 represents a group containing a polymerizable group, n represents an integer greater than 1, and * represents the bonding site to the nitrogen atom to which ^R111 in formula (2) is bonded.

-Y ¹ - In formula (1-1), Y ¹ represents an n+2 valent group containing an aromatic hydrocarbon group. The aromatic hydrocarbon group in Y ¹ is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, further preferably a group obtained by removing two or more hydrogen atoms from a benzene ring, and particularly preferably a group obtained by removing three or more hydrogen atoms from a benzene ring. In formula (1-1), it is preferred that both of the bonding sites in Y ¹ to the two *s described in formula (1-1) are aromatic hydrocarbon groups. In other words, it is preferred that the two *s described in formula (1-1) are directly bonded to the aromatic hydrocarbon ring structure contained in Y ¹ . In formula (1-1), it is preferred that both the bonding sites of ^Y1 and ^P1 are aromatic hydrocarbon groups. In other words, it is preferred that ^P1 is directly bonded to the aromatic hydrocarbon ring structure contained in ^Y1 .

^Y1 preferably comprises at least one structure selected from the group consisting of the structures represented by the following formulas (A2-1) to (A2-5), and more preferably at least one structure selected from the group consisting of the structures represented by the above formulas (A2-1) to (A2-5). [Chemical Formula 9] In formulas (A2-1) to (A2-5), R ^A211 to R ^A214 , R ^A221 to R ^A224 , R ^A231 to R ^A238 , R ^A241 to R ^A248 and R ^A251 to R ^A258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group or a halogen atom, L A231 and L ^A241 each independently represent a single bond, a carbonyl group, a sulfonyl group, a divalent saturated alkyl group, a divalent unsaturated alkyl group, a heteroatom, a heterocyclic group or a halogenated alkylene group, at least one of R ^A211 to R A214 , at least one of R ^A221 to R ^A224 , R A231 to R A238 , R A241 to R A248 and R A251 to R ^A258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, ^{a hydroxyl} group, a cyano group, a halogenated ^alkyl group or a halogenated alkylene group, At least one of ^A238 , at least one of R ^A241 to R ^A248 , and at least one of R ^A251 to R ^A258 may be a bonding site with ^P1 in the above formula (1-1), and * each independently represents a bonding site with other structures.

Among these, from the viewpoint of solvent solubility, Y ¹ preferably comprises a structure represented by any one of Formulas (A2-1) to (A2-4), and more preferably a structure represented by any one of Formulas (A2-2) or (A2-4).

In formulas (A2-1) to (A2-5), R ^A211 to R ^A214 , R ^A221 to R ^A224 , R ^A231 to R ^A238 , R ^A241 to R ^A248 , and R ^A251 to R ^A258 do not include a bonding site to the carbonyl group in formula (1-1) above. However, at least one of R ^A211 to R ^A214 , at least one of R ^A221 to R ^A224 , at least one of R ^A231 to R ^A238 , at least one of R ^A241 to R ^A248 , and at least one of R ^A251 to R ^A258 may be a bonding site to P ¹ in formula (1-1) above. In formula (A2-1), when R ^A211 to R ^A214 are not the bonding site to P ¹ , R ^A211 to R ^A214 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom. From the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is even more preferred. Examples of the halogen atom or the halogen atom in the alkyl halides in R ^A211 to R ^A214 include fluorine, chlorine, bromine, and iodine, with chlorine and bromine atoms being preferred. In Formula (A2-2), R ^A221 to R ^A224 have the same meanings as R ^A211 to R ^A214 in Formula (A2-1), respectively, and preferred embodiments thereof are also the same. In formula (A2-3), R ^A231 to R ^A238 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogen atom. From the perspective of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms is more preferred, and a hydrogen atom or a alkyl group having 1 to 6 carbon atoms is even more preferred. Examples of the halogenated alkyl group or the halogenated atom in R ^A231 to R ^A238 include fluorine, chlorine, bromine, and iodine atoms, with a chlorine atom or a bromine atom being preferred. In formula (A2-3), L represents a single ^bond , a divalent saturated alkyl group having 1 to 6 carbon atoms, a divalent unsaturated alkyl group having 5 to 24 carbon atoms, -O-, -S-, -NR ^-N- , a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms. It is more preferably a single bond, a saturated alkyl group having 1 to 6 carbon atoms, -O-, or a heterocyclic group. It is even more preferably a single bond or -O-. ^RN represents a hydrogen atom or a alkyl group, more preferably a hydrogen atom, an alkyl group, or an aryl group, even more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. The divalent unsaturated alkyl group may be a divalent aliphatic unsaturated alkyl group or a divalent aromatic alkyl group, with divalent aromatic alkyl groups being preferred. Preferred heterocyclic groups include, for example, groups obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocyclic ring, and more preferably, groups obtained by removing two hydrogen atoms from a ring structure such as a pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, pyrrole ring, furan ring, thiophene ring, piperidine ring, tetrahydropyran ring, pyridine ring, or morpholine ring. These heterocyclic rings may further form fused rings with other heterocyclic or alkyl rings. The number of ring members in the heterocyclic group is preferably 5 to 10, more preferably 5 or 6. Furthermore, the heteroatom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the halogen atom in the halogenated alkylene group include fluorine, chlorine, bromine, and iodine atoms, with chlorine or bromine atoms being preferred. In formula (A2-4), R ^A241 to R ^A248 and L ^A241 have the same meanings as R ^A231 to R ^A238 and L ^A231 in formula (A2-3), respectively, and preferred embodiments thereof are also the same. In formula (A2-5), R ^A251 to R ^A258 have the same meanings as R ^A211 to R ^A214 in formula (A2-1), respectively, and preferred embodiments thereof are also the same.

In formula (A2-1), at least one of ^RA211 to ^RA214 preferably bonds to the ^P1 site in formula (1-1), more preferably one of ^RA211 to ^RA214 bonds to the ^P1 site, and ^RA213 preferably bonds to the ^P1 site. In formula (A2-2), at least one of ^RA221 to ^RA224 preferably bonds to the ^P1 site in formula (1-1), more preferably one of ^RA221 to ^RA224 bonds to the ^P1 site, and ^RA223 preferably bonds to the ^P1 site. In formula (A2-3), at least one of ^RA231 to ^RA238 preferably bonds to the ^P1 in formula (1-1). More preferably, two of ^RA231 to ^RA238 bond to the ^P1 . Further preferably, one of ^RA231 to ^RA234 and one of ^RA235 to ^RA238 (a total of two) bond to the ^P1 . Particularly preferably, both ^RA231 and ^RA238 bond to the ^P1 . In formula (A2-4), at least one of ^RA241 to ^RA248 preferably bonds to the ^P1 in formula (1-1). More preferably, two of ^RA241 to ^RA248 bond to the ^P1 . Further preferably, one of ^RA241 to ^RA244 and one of ^RA245 to ^RA248 (a total of two) bond to the ^P1 . Particularly preferably, both ^RA241 and ^RA248 bond to the ^P1 . In formula (A2-5), at least one of ^RA251 to ^RA258 preferably bonds to the ^P1 in formula (1-1). More preferably, two of ^RA251 to ^RA258 bond to the ^P1 . Further preferably, one of ^RA251 to ^RA254 and one of ^RA255 to ^RA258 (a total of two) bond to the ^P1 . Particularly preferably, two of ^RA253 and ^RA257 bond to the ^P1 .

In formulas (A2-1) to (A2-5), the two * are preferably the * in formula (1-1). In other words, the two nitrogen atoms to which R ¹¹¹ in formula (2) is bonded are preferably directly bonded to the positions represented by the two * in formulas (A2-1) to (A2-5).

Among these, ^Y1 is preferably a group represented by the following formula (Y-1) or (Y-2). [Chemical Formula 10] In formula (Y-1), ^RY11 , ^RY12 , and ^RY13 have the same meanings as ^RA211 , ^RA212 , and ^RA214 in formula (A2-1), respectively, and preferred embodiments thereof are also the same. In formula (Y-2), ^RY21 to ^RY26 have the same meanings as ^RA242 to ^RA247 in formula (A2-4), respectively, and preferred embodiments thereof are also the same. In formula (Y-1) or formula (Y-2), * represents the bonding site to the two nitrogen atoms bonded to ^R111 in formula (2), and # represents the bonding site to ^P1 in formula (1-1).

-P ¹ - In formula (1-1), P ¹ represents a group containing a polymerizable group. Preferred polymerizable groups include groups containing an ethylenically unsaturated group, a cyclic ether group, a hydroxymethyl group, or an alkoxymethyl group. More preferred are vinyl groups, (meth)allyl groups, (meth)acrylamido groups, (meth)acryloyloxy groups, cis-butylenediamide groups, vinylphenyl groups, epoxy groups, cyclohexyloxy groups, hydroxymethyl groups, or alkoxymethyl groups. Even more preferred are (meth)acryloyloxy groups, (meth)acrylamido groups, epoxy groups, hydroxymethyl groups, or alkoxymethyl groups. The number of polymerizable groups contained in P ¹ is 1 or more, preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.

Furthermore, ^P1 is preferably a group represented by the following formula (P-1). [Chemical Formula 11] In formula (P-1), ^L represents a single bond or an m+1 valent linking group, ^A represents a polymerizable group, m represents an integer greater than 1, and * represents the bonding site to ^Y. In formula (P-1), ^L is preferably a single bond, a alkyl group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR ^N -, or a group containing two or more of these bonds. More preferably, L represents a single bond, a alkyl group, an ether bond, a carbonyl group, -NR ^N -, or a group containing two or more of these bonds. ^RN represents a hydrogen atom or a alkyl group, more preferably a hydrogen atom, an alkyl group, or an aryl group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. The alkyl group in ^L1 is preferably a saturated aliphatic alkyl group having 1 to 30 carbon atoms, an aromatic alkyl group having 6 to 30 carbon atoms, or a group represented by a combination thereof. More preferably, it is a saturated aliphatic alkyl group having 1 to 10 carbon atoms, a group obtained by removing two or more hydrogen atoms from a benzene ring, or a group represented by a bond thereof.

In formula (P-1), ^A2 is preferably a vinyl group, a (meth)allyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, a cis-butylenediamide group, a vinylphenyl group, an epoxy group, an oxocyclobutyl group, a hydroxymethyl group, or an alkoxymethyl group, and more preferably a (meth)acryloxy group, a (meth)acrylamide group, an epoxy group, a hydroxymethyl group, or an alkoxymethyl group.

In formula (P-1), m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, further preferably an integer of 1 to 5, particularly preferably 1 or 2, and most preferably 1.

Furthermore, ^P1 is preferably a group represented by the following formula (P-2) or formula (P-3). [Chemical Formula 12] In formula (P-2), ^A represents a polymerizable group, and * represents the bonding site with ^Y. In formula (P-2), A has the same ^meaning as ^A in formula (P-1), and preferred embodiments are also the same. In formula (P-3), ^A represents a polymerizable group, ^L represents a alkyl group or a alkyl group and an ether bond, carbonyl group, thioether bond, sulfonyl group, -NR ^N -, or a group containing two or more of these groups, ^Z represents an ether bond, ester bond, urethane bond, urea bond, amide bond, or carbonate bond, and * represents the bonding site with ^{Y. RN} is as described above. In formula (P- ³ ), A has the same meaning as ^A in formula (P-1), and preferred embodiments are also the same. In formula (P-3), ^L2 is preferably an alkyl group, a (poly)alkoxylene group, or a group represented by a combination thereof. The alkyl group is preferably an alkylene group, a divalent aromatic alkyl group, or a group represented by a combination thereof, and an alkylene group is more preferred. In this specification, a (poly)alkoxylene group refers to an alkoxylene group or a polyalkoxylene group. Furthermore, in the present invention, a polyalkoxylene group refers to a group in which two or more alkoxylene groups are directly bonded. The alkylene groups in the multiple alkoxylene groups contained in the polyalkoxylene group may be the same or different. When the polyalkoxylene group contains multiple alkoxylene groups having different alkylene groups, the arrangement of the alkoxylene groups in the polyalkoxylene group may be random, block-like, or alternating. The alkylene groups are preferably those having 1 to 30 carbon atoms, more preferably those having 1 to 20 carbon atoms, and even more preferably those having 1 to 10 carbon atoms. The aromatic alkyl groups are preferably those having 6 to 30 carbon atoms, more preferably those having 6 to 20 carbon atoms, more preferably phenylene or naphthylene, and particularly preferably phenylene. The alkylene groups in the (poly)alkoxylene groups are preferably those having 2 to 10 carbon atoms, more preferably those having 2 to 4 carbon atoms, more preferably ethylene or propylene, and even more preferably ethylene. The number of alkoxylene groups in the polyalkoxylene group (the number of repetitions of the polyalkoxylene group) is preferably 2 to 20, more preferably 2 to 10, even more preferably 2 to 5, and particularly preferably 2 to 4. In formula (P-3), ^Z represents an ether bond, ester bond, urethane bond, urea bond, amide bond, or carbonate bond, with ester bond, urethane bond, urea bond, or amide bond being more preferred. In the present invention, when simply described as "ester bond,""urethanebond," or "amide bond," the orientation of such bonds is not limited. For example, when ^Z represents an ester bond, the bonding site of Z ^{to L} can be either a carbon atom or an oxygen atom in the ester bond.

R ¹¹⁵ in formula (2) 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 13] In formula (5), R ¹¹² is preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO ₂ -, and -NHCO-, and combinations thereof; more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, and -SO ₂ -; and 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 can include a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride. A single tetracarboxylic dianhydride may be used, or two or more may be used. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 14] In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-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 dicarboxylic dianhydride, anhydride, 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 groups and C1-6 alkyl derivatives thereof.

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

It is also preferred that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, an example of R ¹¹¹ is a residual group of a diaminophenol derivative.

^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group. Preferably, at least one of ^R113 and ^R114 contains a polymerizable group, and more preferably, both contain polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, free radicals, or the like, with free radical polymerizable groups being preferred. Specific examples of the polymerizable group in the specific resin include groups having an ethylenically unsaturated bond, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxadiazole groups, benzoxazolyl groups, blocked isocyanate groups, hydroxymethyl groups, and amino groups. Free radical polymerizable groups in polyimide precursors and the like are preferably groups having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III). The group represented by the following formula (III) is preferred.

【Chemical formula 15】

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In formula (III), * represents a bonding site with another structure. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, or a polyalkyleneoxy group. Preferred examples of R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, and a polyalkyleneoxy group. Ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -, and a polyalkyleneoxy group are more preferred, and a polyalkyleneoxy group is even more preferred. In the present invention, a polyalkoxyl group refers to a group having two or more alkoxyl groups directly bonded thereto. The alkylene groups in the multiple alkoxyl groups contained in the polyalkoxyl group may be the same or different. When the polyalkoxyl group contains multiple alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be random, block-like, or alternating. The carbon number of the alkylene group (including the carbon number of the substituent, if the alkylene group has a substituent) is preferably 2 or more, 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. The alkylene group may be substituted. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. The number of alkoxy groups in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the perspective of solvent solubility and solvent resistance, the polyalkoxy group is preferably a polyethoxy group, a polypropoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group formed by bonding multiple ethoxy groups and multiple propoxy groups. Polyethoxy groups or polypropoxy groups are more preferred, and polyethoxy groups are even more preferred. In the group formed by bonding multiple ethoxy groups and multiple propoxy groups, the ethoxy and propoxy groups may be arranged randomly, in blocks, or in an alternating pattern. Preferred aspects of the number of repetitions of the ethoxy groups in these groups are as described above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include aromatic groups and aralkyl groups having an acidic group bonded to one, two, or three carbon atoms, preferably one carbon atom, constituting an aryl group. Specifically, examples include aromatic groups having 6 to 20 carbon atoms and aralkyl groups having an acidic group. More specifically, examples include phenyl groups having an acidic group and benzyl groups having an acidic group. The acidic group is preferably an OH group. More preferably, R ¹¹³ or R ¹¹⁴ is a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, or a 4-hydroxybenzyl group.

From the perspective of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. Monovalent organic groups preferably include linear or branched alkyl groups, cyclic alkyl groups, and aromatic groups, with aromatic-substituted alkyl groups being more preferred. The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched, or cyclic. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, 2-ethylhexyl, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy), 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy, and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy). The cyclic alkyl group may be monocyclic or polycyclic. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, borndiyl, bicyclohexyl, and pinenyl. Among these, cyclohexyl is most preferred from the perspective of achieving both high sensitivity and stability. Furthermore, preferred aromatically substituted alkyl groups are linear alkyl groups substituted with the aromatic groups described below. Specifically, the aromatic group includes a substituted or unsubstituted benzene ring, a naphthyl ring, a pentadiene ring, an indene ring, an azulene ring, a heptalene ring, an indenene ring, a perylene ring, a condensed pentaphenyl ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a condensed tetraphenyl ring, a chrysene ring, a tert-phenylene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyridine ring, a pyrimidine ring, a pyrimidine ring, an indole ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinoline ring, a quinoline ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthidine ring, an acridine ring, a phenanthroline ring, a thienyl ring, a chromene ring, a benzothiophene ring, a phenanthiophene ring, or a phenanthroline ring. A benzene ring is most preferred.

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.

At least one of ^R113 and ^R114 may be a polar conversion group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. 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 are more preferred. Specific examples of acid-degradable groups include t-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, t-butoxycarbonylmethyl, and trimethylsilyl ether groups. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuryl group is preferred.

Furthermore, the polyimide precursor preferably contains fluorine atoms in its structural units. 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 diamine components 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). In other words, at least one of the polyimide precursors used in the present invention preferably has a repeating unit represented by formula (2-A). By adopting such a structure, the exposure latitude can be further expanded. Formula (2-A) [Chemical Formula 16] 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 are polymerizable groups.

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

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

As an embodiment of the polyimide precursor of the present invention, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of all repeating units are repeating units represented by formula (2) can be exemplified.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000. Furthermore, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The molecular weight dispersity of the polyimide precursor is preferably 2.5 or greater, more preferably 2.7 or greater, and even more preferably 2.8 or greater. There is no specific upper limit for the molecular weight dispersion of the polyimide precursor. For example, 4.5 or less is preferred, 4.0 or less is more preferred, 3.8 or less is even more preferred, 3.2 or less is even more preferred, 3.1 or less is even more preferred, 3.0 or less is even more preferred, and 2.95 or less is particularly preferred. In this specification, molecular weight dispersion is calculated as weight-average molecular weight/number-average molecular weight.

[Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer primarily composed of an organic solvent. In this specification, an alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more per 100 g of a 2.38 mass % tetramethylammonium aqueous solution at 23°C. From the perspective of pattern formation, a polyimide dissolution of 0.5 g or more is preferred, and a polyimide dissolution of 1.0 g or more is even more preferred. The upper limit of the dissolution amount is not particularly limited, but is preferably 100 g or less. Furthermore, from the perspective of the resulting organic film's strength and insulation properties, polyimides preferably have multiple imide structures in their main chain. In this specification, "main chain" refers to the longest bond in the polymer molecules that make up the resin, and "side chain" refers to any other bonds.

-Fluorine Atom- From the perspective of the film strength of the resulting organic film, it is preferred that the polyimide contain fluorine atoms. The fluorine atom is preferably contained in R ¹³² in the repeating unit represented by formula (4) described below or in R ¹³¹ in the repeating unit represented by formula (4) described below, and more preferably contained in R ¹³² in the repeating unit represented by formula (4) described below or in R ¹³¹ in the repeating unit represented by formula (4) described below as a fluorinated alkyl group. The amount of fluorine atoms is preferably 1 to 50 mol/g, more preferably 5 to 30 mol/g, relative to the total mass of the polyimide.

-Silicon Atoms- From the perspective of the film strength of the obtained organic film, polyimide preferably contains silicon atoms. For example, the silicon atom is preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later, and is more preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described later as an organic modified (poly)siloxane structure described later. In addition, the above-mentioned silicon atoms or the above-mentioned organic modified (poly)siloxane structure may also be contained in the side chain of the polyimide, but it is more preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 0.01 to 5 mol/g, and more preferably 0.05 to 1 mol/g.

-Ethylenically Unsaturated Bonds- From the perspective of the resulting organic membrane strength, polyimides preferably have ethylenically unsaturated bonds. Polyimides may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but ethylenically unsaturated bonds in the side chains are preferred. These ethylenically unsaturated bonds are preferably free-radically polymerizable. It is preferred that an ethylenically unsaturated bond is contained in R ¹³² in the repeating unit represented by the formula (4) described below or in R ¹³¹ in the repeating unit represented by the formula (4) described below. It is more preferred that an ethylenically unsaturated bond is contained in R ¹³² in the repeating unit represented by the formula (4) described below or in R ¹³¹ in the repeating unit represented by the formula (4) described below as a group having an ethylenically unsaturated bond. Among these, it is preferred that an ethylenically unsaturated bond is contained in R ¹³¹ in the repeating unit represented by the formula (4) described below. It is more preferred that an ethylenically unsaturated bond is contained in R ¹³¹ in the repeating unit represented by the formula (4) described below as a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include groups directly bonded to an aromatic ring and having a vinyl group which may be substituted, such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).

【Chemical formula 17】

In formula (IV), R ²⁰ represents a hydrogen atom or a methyl group, preferably a methyl group.

In formula (IV), ^R21 represents an alkylene group having 2 to 12 carbon atoms, -O- _CH2CH (OH) _CH2- , -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms; the number of carbon atoms repeated is 1 to 12, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), or a group formed by combining two or more of these groups.

Among these, ^R21 is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1). [Chemical Formula 18] In formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkoxyene group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these groups. X represents an oxygen atom or a sulfur atom. * represents a bonding site to another structure. ● represents a bonding site to the oxygen atom bonded to ^R201 in formula (III). Preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in L in formulas (R1) to (R3) are the same as the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in ^R21 described above. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred embodiments are also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (e.g., 2-isocyanateethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) is obtained, for example, by reacting a polyimide having a hydroxyl group, such as a phenolic hydroxyl group, with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate). From the perspective of solvent solubility and solvent resistance, the polyalkoxy group is preferably a polyethoxy group, a polypropoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group formed by bonding multiple ethoxy groups to multiple propoxy groups. Polyethoxy groups or polypropoxy groups are more preferred, and polyethoxy groups are even more preferred. In the group formed by bonding multiple ethoxy groups to multiple propoxy groups, the ethoxy and propoxy groups may be arranged randomly, in blocks, or in an alternating pattern. Preferred aspects of the number of repetitions of the ethoxy group and the like in these groups are as described above.

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

The amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g. In addition, from the perspective of production suitability, the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.

- Crosslinking groups other than ethylenically unsaturated bonds - The polyimide may have crosslinking groups other than ethylenically unsaturated bonds. Examples of crosslinking groups other than ethylenically unsaturated bonds include cyclic ether groups such as epoxy groups and cyclobutylene groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups. Crosslinking groups other than ethylenically unsaturated bonds are preferably contained in R ¹³¹ in the repeating unit represented by formula (4) described below. The amount of crosslinking groups other than ethylenically unsaturated bonds is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g, relative to the total mass of the polyimide. Furthermore, from the perspective of production suitability, the amount of crosslinking groups other than ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g.

-Polarity Converting Group- The polyimide may have a polarity converting group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiment is also the same.

-Acid Value- When polyimide is subjected to alkaline development, from the perspective of improving developability, the acid value of the polyimide is preferably 30 mgKOH/g or greater, more preferably 50 mgKOH/g or greater, and even more preferably 70 mgKOH/g or greater. Furthermore, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. When the polyimide is developed using a developer primarily composed of an organic solvent (e.g., "solvent development" described below), the acid value of the polyimide is preferably 2-35 mgKOH/g, more preferably 3-30 mgKOH/g, and even more preferably 5-20 mgKOH/g. The acid value is measured by a known method, for example, the method described in JIS K 0070:1992. In addition, the acid groups contained in the polyimide preferably have a pKa of 0-10, and more preferably 3-8, from the perspective of balancing storage stability and development properties. The pKa value represents the equilibrium constant, Ka, expressed as its negative common logarithm, pKa, taking into account the dissociation reaction that releases hydrogen ions from an acid. In this specification, pKa values are calculated using ACD/ChemSketch (registered trademark), unless otherwise specified. Alternatively, reference may be made to the values listed in the "Chemical Handbook, 5th Revised Edition, Basic Edition," edited by the Chemical Society of Japan. When the acid group is a polyacid such as phosphoric acid, the pKa value described above is the first dissociation constant. Preferably, the polyimide contains at least one acid group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

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

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably comprises a repeating unit represented by the following formula (4), and more preferably comprises a repeating unit represented by the formula (4) and a polymerizable group. Formula (4) [Chemical Formula 19] In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When a polymerizable group is present, the polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , as shown in the following formula (4-1) or formula (4-2), or may be located at the end of the polyimide. Formula (4-1) [Chemical Formula 20] In formula (4-1), R ¹³³ is a polymerizing group, and the other groups have the same meanings as in formula (4). Formula (4-2) [Chemical Formula 21] At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group. If not a polymerizable group, it is an organic group. The other groups have the same meanings as in formula (4).

The polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polyimide precursor. R ¹³¹ represents a divalent organic group. Examples of the divalent organic group include the same ones as R ¹¹¹ in formula (2), and the preferred range is also the same. In addition, R ¹³¹ includes a diamine residue remaining after removing the amino group of a diamine. Examples of the diamine include aliphatic, cycloaliphatic, or aromatic diamines. As specific examples, examples of R ¹¹¹ in formula (2) of the polyimide precursor can be cited.

From the perspective of more effectively suppressing warping during calcination, R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain. More preferred is a diamine residue containing two or more ethylene glycol chains or propylene glycol chains, or both, in a single molecule. Even more preferred is a diamine residue containing no aromatic rings.

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

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

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

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

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

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

In order to improve the storage stability of the composition, it is preferred to seal the ends of the polyimide backbone chain with a capping agent such as a monoamine, anhydride, monocarboxylic acid, monoacyl chloride, or monoactive ester compound. Among these, monoamines are more preferably used. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy- 5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these end-capping agents may be used, and multiple different end groups may be introduced by reacting multiple end-capping agents.

- Imidization rate (ring closure rate) - From the perspective of the film strength and insulation properties of the resulting organic film, the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the above imidization rate is not particularly limited, as long as it is 100% or less. The above imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ^-1 , which is an absorption peak derived from the imide structure, is determined. Then, after the polyimide is heat-treated at 350°C for 1 hour, the infrared absorption spectrum is measured again, and the peak intensity P2 near 1377 cm ^-1 is determined. Using the obtained peak intensities P1 and P2, the imidization rate of the polyimide can be calculated according to the following formula: Imidization rate (%) = (peak intensity P1 / peak intensity P2) x 100

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

Polyimide can be synthesized by the following methods: a method of reacting tetracarboxylic dianhydride with a diamine compound (a portion of which is replaced by a monoamine end-capping agent) at low temperature; a method of reacting tetracarboxylic dianhydride (a portion of which is replaced by an acid anhydride, a monoacyl chloride compound, or a monoactive ester end-capping agent) with a diamine compound at low temperature; a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting the diester in the presence of a diamine (a portion of which is replaced by a monoamine end-capping agent) and a fusing agent; a method of reacting tetracarboxylic dianhydride with an alcohol and then reacting the diester in the presence of a diamine (a portion of which is replaced by a monoamine end-capping agent) and a fusing agent; A polyimide precursor can be obtained by forming a diester from tetracarboxylic dianhydride and an alcohol, followed by chlorination of the remaining dicarboxylic acid, and reacting the resulting product with a diamine (partially replaced with a monoamine end-capping agent). This product can then be completely imidized using a known imidization method. Alternatively, the imidization reaction can be stopped midway to introduce a partial imide structure. Furthermore, a partial imide structure can be introduced by mixing a fully imidized polymer with the polyimide precursor. Commercially available polyimides include Durimide (registered trademark) 284 (manufactured by Fujifilm Co., Ltd.) and Matrimide 5218 (manufactured by Huntersman).

The weight-average molecular weight (Mw) of the polyimide can be 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. A weight-average molecular weight of 5,000 or higher can improve the folding resistance of the cured film. To achieve an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. When two or more polyimides are present, it is preferred that at least one polyimide have a weight-average molecular weight within the above range.

[Polybenzoxazole precursor] The structure of the polybenzoxazole precursor used in the present invention is not particularly limited, but preferably comprises a repeating unit represented by the following formula (3). Formula (3) [Chemical Formula 22] In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

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

Preferred dicarboxylic acid residues include those containing an aliphatic group and those containing an aromatic group, with those containing an aromatic group being more preferred. Preferred dicarboxylic acids containing an aliphatic group include those containing a linear or branched (preferably linear) aliphatic group, and those composed of a linear or branched (preferably linear) aliphatic group and two -COOH groups are more preferred. The linear or branched (preferably linear) aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethyl Pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, docosanedioic acid, diglycolic acid acid) and the dicarboxylic acid represented by the following formula, etc.

【Chemical formula 23】 (In the formula, Z is a alkyl group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

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

【Chemical formula 24】 In the formula, A represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ -, and * independently represents a bonding site with other structures.

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

In formula (3), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, it has the same meaning as R ¹¹⁵ in formula (2) above, and the preferred range is also the same. ¹²² is also preferably a group derived from a diaminophenol derivative. Examples of the group derived from a diaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfonium, 4,4'-diamino-3,3'-dihydroxydiphenylsulfonium, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis- (4-Amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferred.

【Chemical formula 25】 In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , or -NHCO-; * and # each represent a bonding site to another structure. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a alkyl group, and more preferably a hydrogen atom or an alkyl group. Furthermore, ^R122 is preferably a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, among a total of 4 * and #, any 2 are bonding sites to the nitrogen atom bonded to R ¹²² in formula (3), and the other 2 are bonding sites to the oxygen atom bonded to R ¹²² in formula (3). It is preferred that 2 * are bonding sites to the oxygen atom bonded to R ¹²² in formula (3), and 2 # are bonding sites to the nitrogen atom bonded to R ¹²² in formula (3). Or, 2 * are bonding sites to the nitrogen atom bonded to R ¹²² in formula (3), and 2 # are bonding sites to the oxygen atom bonded to R ¹²² in formula (3). It is more preferred that 2 * are bonding sites to the oxygen atom bonded to R 122 in formula (3). It is further preferred that the two #s are bonding sites to the oxygen atom to which ^{R 122} is bonded, and the two #s are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded.

【Chemical formula 26】

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

【Chemical formula 27】 (In formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the bisaminophenol derivative represented by formula (As) above.)

In the above formula (As), it is particularly preferred to have a substituent at R ₃ , which is adjacent to the phenolic hydroxyl group, because this brings the carbonyl carbon of the amide bond and the hydroxyl group closer together, further enhancing the effect of achieving a high cyclization rate during curing at low temperatures.

In the above formula (As), it is preferred that R ₂ and R ₃ are both alkyl groups because they can maintain high transparency to i-rays and a high cyclization rate during curing at low temperatures.

Furthermore, in the above formula (As), _R1 is more preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene and substituted alkylene groups for _R1 include linear or branched alkyl groups having 1 to 8 carbon atoms. Among these, -CH2-, -CH(CH3)-, and -C(CH3 _{) 2-} are particularly _preferred from the perspective of achieving a well-balanced polybenzoxazole precursor that maintains high transparency to I-rays and a high cyclization rate during low-temperature curing while also providing sufficient solubility in solvents _.

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

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, the contents of which are incorporated herein, but are not limited thereto.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating units of formula (3). From the perspective of suppressing the warping associated with ring closure, it is preferred to contain a diamine residue represented by the following formula (SL) as the other type of repeating structural unit.

【Chemical formula 28】 In formula (SL), Z has an a-structure and a b-structure. R ^1s is a hydrogen atom or a alkyl group having 1 to 10 carbon atoms, R ^2s is a alkyl group having 1 to 10 carbon atoms, and at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group. The remaining groups are hydrogen atoms or organic groups having 1 to 30 carbon atoms and may be the same or different. The polymerization of the a-structure and the b-structure can be block or random. The molar percentage of the Z moiety is 5 to 95 molar percent for the a-structure, 95 to 5 molar percent for the b-structure, and a + b equals 100 molar percent.

In formula (SL), preferred Z includes those where R ^5s and R ^6s in structure b are phenyl groups. Furthermore, the molecular weight of the structure represented by formula (SL) is preferably 400-4,000, and more preferably 500-3,000. By setting the molecular weight within this range, the elastic modulus of the polybenzoxazole prodiol after dehydration and ring closure can be more effectively reduced, achieving both the effect of suppressing warp and the effect of improving solvent solubility.

When the diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferred to further include tetracarboxylic acid residues remaining after removing the anhydride groups from tetracarboxylic dianhydride as repeating units. Examples of such tetracarboxylic acid residues include R ¹¹⁵ in formula (2).

For example, when a polybenzoxazole precursor is used in the composition described below, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. Furthermore, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or greater, more preferably 1.5 or greater, and even more preferably 1.6 or greater. There is no particular upper limit for the molecular weight dispersion of the polybenzoxazole precursor. For example, 2.6 or less is preferred, 2.5 or less is more preferred, 2.4 or less is even more preferred, 2.3 or less is even more preferred, and 2.2 or less is even more preferred.

[Polybenzoxazole] Polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but compounds represented by the following formula (X) are preferred, and compounds represented by the following formula (X) having a polymerizable group are even more preferred. The polymerizable group is preferably a free radical polymerizable group. Alternatively, compounds represented by the following formula (X) having a polar conversion group such as an acid-decomposable group may be used. [Chemical Formula 29] In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When a polarity-converting group such as a polymerizable group or an acid-degradable group is present, the polymerizable group or the acid-degradable group may be located on at least one of R ¹³³ and R ¹³⁴ , or may be located at the terminal of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2). Formula (X-1) [Chemical Formula 30] In formula (X-1), at least one of R ¹³⁵ and R ¹³⁶ is a polymerizable group or an acid-decomposable group or a polarity-converting group. If not a polymerizable group or an acid-decomposable group or a polarity-converting group, it is an organic group. The other groups have the same meanings as in formula (X). Formula (X-2) [Chemical Formula 31] In formula (X-2), R ¹³⁷ is a polar conversion group such as a polymerizable group or an acid-decomposable group, and the others are substituents. The other groups have the same meanings as in formula (X).

The polymerizable group or the polarity-converting group such as the acid-decomposable group has the same meaning as the polymerizable group described above for the polyimide precursor.

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

R ¹³⁴ represents a tetravalent organic group. As an example of a tetravalent organic group, R ¹²² in formula (3) of the polybenzoxazole precursor can be cited. Preferred examples are the same as R ^122. For example, the four bonders of the tetravalent organic group exemplified as R ¹²² bond to the nitrogen atom and oxygen atom in the above formula (X) to form a fused ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. [Chemical Formula 32]

The oxazolidation rate of polybenzoxazole is preferably 85% or higher, and more preferably 90% or higher. An oxazolidation rate of 85% or higher reduces membrane shrinkage caused by ring closure during oxazolidation by heating, effectively suppressing warping.

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

Polybenzoxazoles can be obtained, for example, by reacting a bisaminophenol derivative with a compound selected from a dicarboxylic acid containing R ¹³³ , a dicarboxylic acid dichloride of such a dicarboxylic acid, and a dicarboxylic acid derivative to obtain a polybenzoxazole precursor, followed by oxazolidation using a known oxazolidation method. Furthermore, in the case of dicarboxylic acids, active ester-type dicarboxylic acid derivatives obtained by pre-reacting with 1-hydroxy-1,2,3-benzotriazole, etc., can be used to improve reaction yields.

The weight-average molecular weight (Mw) of the polybenzoxazole is preferably 5,000-70,000, more preferably 8,000-50,000, and even more preferably 10,000-30,000. A weight-average molecular weight of 5,000 or greater improves the folding resistance of the cured film. To achieve an organic film with excellent mechanical properties, a weight-average molecular weight of 20,000 or greater is particularly preferred. When two or more polybenzoxazoles are present, it is preferred that at least one of the polybenzoxazoles has a weight-average molecular weight within the above range.

[Method for Producing Polyimide Precursors, Etc.] Polyimide precursors, etc. are obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or dicarboxylic acid derivative is halogenated using a halogenating agent and then reacted with the diamine. In the method for producing polyimide precursors, etc., it is preferred to use an organic solvent during the reaction. The organic solvent may be one or two or more. The organic solvent can be appropriately specified depending on the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (DGE), N-methylpyrrolidone, and N-ethylpyrrolidone. Polyimides can be produced by synthesizing a polyimide precursor and then cyclizing it through methods such as thermal imidization or chemical imidization (for example, by promoting the cyclization reaction with a catalyst). Polyimides can also be synthesized directly.

Alternatively, the synthesis may be performed using a non-halogen catalyst instead of the halogenating agent. As the non-halogenating catalyst, any known amidated catalyst containing no halogen atoms can be used without particular limitation. Examples include boroxine compounds, N-hydroxy compounds, tertiary amines, phosphates, amine salts, urea compounds, and carbodiimide compounds. Examples of the carbodiimide compound include N,N'-diisopropylcarbodiimide and N,N'-dicyclohexylcarbodiimide.

-Capping Agents- When manufacturing polyimide precursors, it is preferable to cap the ends of the polyimide precursor with a capping agent such as an acid anhydride, monocarboxylic acid, monoacyl chloride, or monoactive ester to further improve the storage stability of the composition. As the end-capping agent, it is more preferable to use a monoamine. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Naphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 4-aminostyrene, etc. Two or more of these can be used, and multiple different end groups can be introduced by reacting multiple end-capping agents.

-Solid Precipitation- The production of polyimide precursors may include a solid precipitation process. Specifically, the polyimide precursor in the reaction solution is precipitated in water and then dissolved in a solvent such as tetrahydrofuran, in which the polyimide precursor is soluble, to precipitate the solid. The polyimide precursor is then dried to obtain a powdered polyimide precursor.

[Content] The content of the specific resin in the 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 composition. Furthermore, the content of the resin in the 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 composition. The composition of the present invention may contain only one specific resin or two or more. When containing two or more specific resins, the total amount is preferably within the above range.

Furthermore, the curable resin composition of the present invention preferably comprises at least two resins. Specifically, the curable resin composition of the present invention may comprise a total of two or more specific resins and other resins described below, or may comprise two or more specific resins, but it is preferred that the curable resin composition comprises two or more specific resins. When the curable resin composition of the present invention comprises two or more specific resins, for example, it is preferred that the curable resin composition comprises a polyimide precursor having different structures derived from dianhydride (R ¹¹⁵ in the above formula (2)).

<Other Resins> The composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins"). Examples of other resins include polyamide imide, polyamide imide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, and acrylic resins. For example, by further adding an acrylic resin, a composition with excellent coatability can be obtained, and an organic film with excellent solvent resistance can be obtained. For example, by adding a highly polymerizable acrylic resin with a weight-average molecular weight of 20,000 or less to the composition, instead of or in addition to the crosslinking agent (also called a polymerizable compound) described below, the coating properties of the composition and the solvent resistance of the organic film can be improved.

When the composition of the present invention contains other resins, the content of the other resins, relative to the total solids content of the composition, 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. Furthermore, the content of the other resins in the composition of the present invention, relative to the total solids content of the composition, 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. In a preferred embodiment of the composition of the present invention, the content of other resins can be low. In this embodiment, the content of other resins relative to the total solids content of the composition 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. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or greater. The composition of the present invention may contain only one other resin or two or more. When containing two or more other resins, the total amount is preferably within the above range.

<Compound B> The curable resin composition of the present invention contains Compound B, which is a compound having a polymerizable group and an azole group.

[Polymerizable Group] Examples of the polymerizable group in compound B include known polymerizable groups such as free radical polymerizable groups, alkoxysilyl groups, epoxy groups, cyclobutyl groups, hydroxymethyl groups, alkoxymethyl groups, and (blocked) isocyanate groups. Among these, compound B preferably contains at least one group selected from the group consisting of free radical polymerizable groups and alkoxysilyl groups from the perspective of adhesion of the cured film to metal.

The alkoxysilyl group may be any of monoalkoxysilyl, dialkoxysilyl, and trialkoxysilyl. However, trialkoxysilyl is preferred from the perspective of the cured film's adhesion to metal. The alkoxy group in the alkoxysilyl group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and even more preferably an ethoxy group.

The radically polymerizable group is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, or a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloxy group, and the like. The (meth)acryloxy group is preferred. Compound B may have only one polymerizable group or two or more. Furthermore, Compound B may have only one type of polymerizable group or two or more. For example, it may have both a radically polymerizable group and an alkoxysilyl group.

[Azolyl] The azole group in Compound B can be any group that is a heterocyclic five-membered ring compound containing one or more nitrogen atoms as ring members, and having a structure in which one or more hydrogen atoms are removed from a heterocyclic five-membered ring compound that may have a substituent or a fused ring structure. However, a heterocyclic five-membered ring compound containing only one or more nitrogen atoms and one or more carbon atoms as ring members, and having a structure in which one or more hydrogen atoms are removed from a heterocyclic five-membered ring compound that may have a substituent, is preferred. From the perspective of the adhesion of the cured film to metal, the azole group is preferably a group having a structure in which one or more hydrogen atoms are removed from a pyrrole ring, pyrazole ring, indazole ring, imidazole ring, benzimidazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, benzotriazole ring, or tetrazole ring. More preferably, it is a group having a structure in which one or more hydrogen atoms are removed from an imidazole ring, benzimidazole ring, 1,2,4-triazole ring, or benzotriazole ring.

Furthermore, the azole group in compound B is preferably a group represented by the following formula (B-1) or the following formula (B-2). [Chemical Formula 33] In formula (B-1), ^RB1 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, ^ZB1 to ^ZB4 each independently represent = ^CRB7- or a nitrogen atom, ^RB7 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, and at least one of ^RB1 and ^RB7 included in formula (B-1) represents a bonding site with a structure having a polymerizable group; In formula (B-2), ^RB2 to ^RB6 each independently represent a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, ^ZB5 and ^ZB6 each independently represent = ^CRB8- or a nitrogen atom, and R ^B8 represents a bonding site to a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group not having a polymerizable group. At least one of ^RB2 to ^RB6 and ^RB8 included in formula (B-2) represents a bonding site to a structure having a polymerizable group.

In formula (B-1), ^RB1 represents a bonding site to a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group. A bonding site to a structure having a polymerizable group is more preferred. The monovalent organic group in ^RB1 is not particularly limited; any known organic group can be used as long as the effects of the present invention are achieved. However, alkyl groups or amino groups are preferred, and alkyl groups or amino groups are more preferred. The number of carbon atoms in the alkyl or alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 4. The amino group may be substituted or unsubstituted.

In formula (B-1), Z ^B1 to Z ^B4 independently represent =CR ^B7 - or a nitrogen atom. Preferred embodiments include two of Z ^B1 to Z ^B4 being nitrogen atoms and two being =CR ^B7 -, one of Z ^B1 to Z ^B4 being a nitrogen atom and three being =CR ^B7 -, or three of Z ^B1 to Z ^B4 being nitrogen atoms and one being =CR ^B7 -. Among these, ^ZB1 and ^ZB3 are nitrogen atoms and ^ZB2 and ^ZB4 are = ^CRB7- ; ZB1 and ZB2 are nitrogen atoms and ^ZB3 and ^ZB4 are = ^CRB7- ; ZB2 is a nitrogen atom and ^ZB1 , ^ZB3 , and ^ZB4 are =CRB7-; or ^ZB1 , ^ZB2 , and ^ZB3 are nitrogen atoms and ^ZB4 are = ^CRB7- . ^ZB1 and ^ZB3 are nitrogen atoms and ZB2 and ^ZB4 are = ^CRB7- . More preferably, ^ZB1 and ^ZB3 are nitrogen atoms and ^ZB2 and ^ZB4 are = ^CRB7- . ^RB7 is preferably a hydrogen atom or a monovalent organic group. Furthermore, when ^ZB1 , ^ZB2 , and ^ZB3 are nitrogen atoms and ^ZB4 is = ^CRB7- , ^RB7 is preferably a bonding site with a structure having a polymerizable group. Preferred aspects of the monovalent organic group in ^RB7 are the same as preferred aspects of the monovalent organic group in ^RB1 described above.

At least one of ^RB1 and ^RB7 included in formula (B-1) represents a bonding site to a structure having a polymerizable group, and preferably at least ^RB1 represents a bonding site to a structure having a polymerizable group. Furthermore, in formula (B-1), an embodiment in which only ^RB1 represents a bonding site to a structure having a polymerizable group, and ^RB7 each independently represents a hydrogen atom or a monovalent organic group, is also a preferred embodiment of the present invention.

In formula (B-2), Z ^B5 and Z ^B6 each independently represent =CR ^B8 - or a nitrogen atom. Preferred embodiments include those in which both Z ^B5 and Z ^B6 represent nitrogen atoms, or those in which Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 -. In formula (B-2), when both Z ^B5 and Z ^B6 represent nitrogen atoms, ^RB6 preferably represents a bonding site with a structure having a polymerizable group. Furthermore, in formula (B-2), when both Z ^B5 and Z ^B6 represent nitrogen atoms and only ^RB6 represents a bonding site with a structure having a polymerizable group, this is also a preferred embodiment of the present invention. In formula (B-2), when Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 -, ^RB8 preferably represents a bonding site with a structure having a polymerizable group. Furthermore, in formula (B-2), when Z ^B5 represents a nitrogen atom, Z ^B6 represents =CR ^B8 -, and only ^RB8 represents a bonding site with a structure having a polymerizable group, this is also one of the preferred aspects of the present invention.

In formula (B-2), ^RB2 to ^RB5 each independently represent a hydrogen atom or a monovalent organic group without a polymerizable group. Preferred embodiments of the monovalent organic group in ^RB2 to ^RB5 are the same as the preferred embodiments of the monovalent organic group in ^RB1 described above. In formula (B-2), when ^ZB5 represents a nitrogen atom and ^ZB6 represents = ^CRB8- , ^RB6 preferably represents a hydrogen atom or a monovalent organic group without a polymerizable group. Preferred embodiments of the monovalent organic group in ^RB6 are the same as the preferred embodiments of the monovalent organic group in ^RB1 described above. In other cases, ^RB6 preferably represents a bonding site to a structure having a polymerizable group. In particular, when Z ^B5 represents a nitrogen atom and Z ^B6 represents =CR ^B8 -, ^RB8 preferably represents a bonding site to a structure having a polymerizable group. In formula (B-2), ^RB8 preferably represents a bonding site to a structure having a polymerizable group. When both Z ^B5 and Z ^B6 represent =CR ^B8 -, one ^RB8 preferably represents a bonding site to a structure having a polymerizable group, and the other preferably represents a hydrogen atom or a monovalent organic group. Preferred embodiments of the monovalent organic group in ^RB8 are the same as those for the monovalent organic group in ^RB1 described above.

At least one of ^RB2 to ^RB6 , and ^RB8 included in formula (B-2) represents a bonding site to a structure having a polymerizable group, and preferably at least ^RB6 or ^RB8 represents a bonding site to a structure having a polymerizable group. Furthermore, in formula (B-2), an embodiment in which only one of ^RB6 and ^RB8 represents a bonding site to a structure having a polymerizable group, and the other of ^RB6 and RB8 and ^{RB2 to RB5} independently represent a hydrogen atom or a monovalent organic group is also a preferred embodiment of the present invention.

Among these, the azole group is preferably a group represented by any one of the following formulas (B-3) to (B-6). [Chemical Formula 34]

In formulas (B-3) to (B-6), ^RB9 to ^RB20 each independently represent a hydrogen atom or a monovalent organic group without a polymerizable group, and * represents a bonding site to a structure having a polymerizable group. Preferred embodiments of the monovalent organic group in ^RB9 to ^RB20 in formulas (B-3) to (B-6) are the same as those for the monovalent organic group in ^RB1 described above.

From the perspective of the resulting cured film's adhesion to metal, it is preferred that compound B contain at least one group selected from the group consisting of an amino group, a carbamate group, and a urea group. It is speculated that the presence of at least one group selected from the group consisting of an amino group, a carbamate group, and a urea group in compound B promotes the interaction between compound B and the specific resin, thereby improving the adhesion of the cured film to metal. The amino group, carbamate group, and urea group may be directly bonded to the azole group or bonded via a linking group. The linking group is preferably a alkyl group or a group formed by a bond between a alkyl group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) _2- , and ^-NRN- , with a alkyl group being more preferred. The above-mentioned ^RN represents a hydrogen atom or a alkyl group, and is more preferably a hydrogen atom, an alkyl group, or an aryl group, further preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. As the above-mentioned alkyl group, a saturated aliphatic alkyl group is preferred, and an alkylene group is more preferred. The carbon number of the above-mentioned alkyl group or alkylene group is preferably 2 to 20, and more preferably 2 to 10. When compound B has an amino group, a carbamate group, or a urea group, compound B preferably has a structure represented by the following formula (B-7), (B-8), or formula (B-9) as a structure containing the above-mentioned azole group and the amino group, carbamate group, or urea group. [Chemical Formula 35] In formula (B-7), ^X1 represents an oxazolyl group, ^L1 represents a single bond or a divalent linking group, ^RB21 represents a hydrogen atom or a monovalent organic group, and * represents the bonding site to the structure having a polymerizable group. In formula (B-8), ^X2 represents an oxazolyl group, ^L2 represents a single bond or a divalent linking group, ^RB22 represents a hydrogen atom or a monovalent organic group, and * represents the bonding site to the structure having a polymerizable group. In formula (B-9), ^X3 represents an oxazolyl group, ^L3 represents a single bond or a divalent linking group, ^RB23 and ^RB24 each independently represent a hydrogen atom or a monovalent organic group, and * represents the bonding site to the structure having a polymerizable group. In formula (B-7), preferred embodiments of the oxazolyl group in ^X1 are as described above. The bonding site with the structure of the polymerizable group in the aforementioned azole group corresponds to the bonding site with ^L1 in formula (B-7). In formula (B-7), the divalent linking group in ^L1 is preferably a alkyl group or a group represented by a bond between a alkyl group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) _2- , and ^-NRN- , with a alkyl group being more preferred. ^RN is as described above. The alkyl group is preferably a saturated aliphatic alkyl group, and more preferably an alkylene group. The alkyl group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. In formula (B-7), ^RB21 represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom. Preferred embodiments of the monovalent organic group in ^RB21 are the same as those for ^RB1 described above. In formula (B-8), ^X2 has the same meaning as ^X1 in formula (B-7), ^L2 has the same meaning as ^L1 in formula (B-7), and ^RB22 has the same meaning as ^RB21 in formula (B-7), and preferred embodiments are also the same. In formula (B-9), ^X3 has the same meaning as ^X1 in formula (B-7), ^L3 has the same meaning as ^L1 in formula (B-7), and ^RB23 and ^RB24 each independently have the same meaning as ^RB21 in formula (B-7), and preferred embodiments are also the same.

Compound B may be a compound with a molecular weight of less than 2,000 (hereinafter referred to as "low-molecular compound B") or a resin (hereinafter referred to as "resin B"). From the perspective of the cured film's adhesion to metal, it is also preferred that the curable resin composition contain both low-molecular compound B and resin B.

[Low Molecular Weight Compound B] The molecular weight of low molecular weight compound B is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less. The number of polymerizable groups in low molecular weight compound B is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, and more preferably 1 or 2. The number of azole groups in low molecular weight compound B is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

The low molecular weight compound B is preferably a compound represented by the following formula (BL-1). [Chemical Formula 36]

In formula (BL-1), ^XLA represents an oxazolyl group, ^LLA represents a single bond or an m+1 valent linking group, ^XLB represents a polymerizable group, n represents an integer of 1 or greater, and m represents an integer of 1 or greater. Preferred embodiments of the oxazolyl group in ^XLA in formula (BL-1) are as described above. In formula (BL-1), ^LLA preferably represents a single bond, an alkyl group, or a group represented by a bond between a alkyl group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) _2- , and ^-NRN- . ^RN is as described above. The alkyl group is preferably a saturated aliphatic alkyl group, and more preferably an alkylene group. The alkyl group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. Furthermore, in formula (BL-1), an embodiment in which L ^LA is a group represented by the following formula (L-1) or formula (L-2) is also a preferred embodiment of the present invention. [Chemical Formula 37] In formula (L-1), ^L1 represents a single bond or a divalent linking group, ^RB21 represents a hydrogen atom or a monovalent organic group, ^L3 represents an n1+1 valent linking group, n1 represents an integer of 1 or greater, # represents the bonding site to the oxazolyl group, and * represents the bonding site to the polymerizable group. In formula (L-2), ^L2 represents a single bond or a divalent linking group, ^RB22 and ^RB23 each independently represent a hydrogen atom or a monovalent organic group, ^L4 represents an n2+1 valent linking group, n2 represents an integer of 1 or greater, # represents the bonding site to the oxazolyl group, and * represents the bonding site to the polymerizable group. In formula (L-1), ^L1 and ^RB21 have the same meanings as ^L1 and ^RB21 in formula (B-7), respectively, and preferred embodiments are also the same. In formula (L-1), ^L3 is preferably an alkyl group or a group represented by a bond between an alkyl group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) _2- , and ^-NRN- . ^RN is as described above. The alkyl group is preferably a saturated aliphatic alkyl group, and more preferably an alkylene group. The alkyl group or alkylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10. In formula (L-1), n1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1. In formula (L-2), L ² , ^RB22 , and ^RB23 have the same meanings as L ² , ^RB22 , and ^RB23 in formula (B-8), respectively, and preferred embodiments thereof are also the same. In formula (L-2), L ⁴ has the same meaning as L ³ in formula (L-1), and preferred embodiments thereof are also the same. In formula (L-2), n 2 is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1. In formula (BL-1), preferred embodiments of the polymerizable group in X ^LB are as described above. In formula (BL-1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1. When n is 2 or greater, the plurality of L ^LA and X ^LB included in formula (BL-1) may be the same or different. In formula (BL-1), m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1. When m is 2 or greater, the plurality of X ^LB included in formula (BL-1) may be the same or different.

[Resin B] Resin B is a resin having repeating units containing azole groups and repeating units containing polymerizable groups. Preferably, it is a resin having repeating units containing azole groups and polymerizable groups. More preferably, it is a resin having repeating units containing azole groups and repeating units containing polymerizable groups. The weight-average molecular weight of Resin B is preferably 2,000 to 100,000, more preferably 3,000 to 70,000, and even more preferably 5,000 to 50,000. Resin B is preferably an acrylic resin.

Resin B preferably comprises a repeating unit containing an azole group, and preferably comprises a repeating unit represented by the following formula (BA-1). [Chemical Formula 38] In formula (BA-1), ^L represents a single bond or a divalent linking group, X represents an ^oxazolyl group, and R represents a hydrogen atom or a methyl group. In formula (BA-1), ^L represents a single bond or a divalent linking group. The divalent linking group is preferably a alkyl group or a group formed by a bond between a alkyl group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) _2- , and -NR ^N -, with a alkyl group being more preferred. ^RN is as described above. The alkyl group is preferably a saturated aliphatic alkyl group, and more preferably an alkylene group. The alkyl group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. Among these, ^L3 is preferably a single bond, a group represented by the following formula (BA-1-1), or a group represented by the following formula (BA-1-2). [Chemical Formula 39] In formula (BA-1-1) or formula (BA-1-2), ^L4 represents a divalent linking group, ^L5 represents a single bond or a divalent linking group, ^L6 represents a divalent linking group, ^L7 represents a single bond or a divalent linking group, * represents the bonding site to the carbonyl group in formula (BA-1), ^A1 and ^A2 represent -O- or -NR ^N -, and # represents the bonding site to ^X3 in (BA-1).

In formula (BA-1-1), ^L4 is preferably a alkyl group or a group represented by a bond between a alkyl group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) _2- , and ^-NRN- . A alkyl group is more preferred. ^RN is as described above. The alkyl group is preferably a saturated aliphatic alkyl group, and more preferably an alkylene group. The alkyl group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.

In formula (BA-1-1), ^L5 is preferably a single bond. When ^L5 is a divalent linking group, preferred embodiments of ^L5 are the same as those for ^L1 in formula (B-7) above, which is a divalent linking group.

In formula (BA-1-2), ^L6 has the same meaning as ^L4 in formula (BA-1-1), and preferred embodiments are also the same.

In formula (BA-1-2), ^L7 is preferably a divalent linking group. When ^L7 is a divalent linking group, preferred aspects of ^L7 are the same as those for ^L2 in formula (B-8) above, which is a divalent linking group.

In formula (BA-1-1) or formula (BA-1-2), ^A1 and ^A2 represent -O- or -NR ^N -, preferably -O-. ^RN is as described above.

In formula (BA-1), the preferred embodiment of the oxazolyl group in X ³ is as described above. The bonding site with the structure having the polymerizable group in the above-mentioned oxazolyl group corresponds to the bonding site with L ³ in formula (BA-1).

Resin B may contain only one type of repeating unit represented by formula (BA-1), or may contain two or more types of repeating units represented by formula (BA-1).

Resin B preferably contains a repeating unit represented by the following formula (BA-2) as a repeating unit containing a polymerizable group. [Chemical Formula 40] In formula (BA-2), A ³ represents -O- or -NR ^N -, ^LP1 represents a divalent linking group, ^XP1 represents a polymerizable group, and R represents a hydrogen atom or a methyl group.

In formula (BA-2), A ³ represents -O- or -NR ^N -, preferably -O-. ^{RN is} as described above.

In formula (BA-2), L ^P1 represents a divalent linking group, preferably a alkyl group or a group formed by a bond between a alkyl group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) _2- , and -NR ^N -, with a alkyl group being more preferred. ^RN is as described above. The alkyl group is preferably a saturated aliphatic alkyl group, and more preferably an alkylene group. The alkyl group or alkylene group preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms.

X ^P1 represents a polymerizable group, preferably an alkoxysilyl group, an epoxy group, an oxacyclobutyl group, or a radical polymerizable group, and more preferably an alkoxysilyl group. Preferred embodiments of the alkoxysilyl group and the radical polymerizable group are as described above.

Resin B may contain only one type of repeating unit represented by formula (BA-2) or two or more types of repeating units represented by (BA-2). In particular, it is a preferred embodiment of the present invention for Resin B to contain multiple types of repeating units represented by formula (BA-2) each having different polymerizable groups. In this embodiment, Resin B preferably includes repeating units represented by formula (BA-2) containing an alkoxysilyl group as a polymerizable group and repeating units represented by formula (BA-2) containing a group different from the alkoxysilyl group as a polymerizable group.

Furthermore, the resin B may further have repeating units other than the repeating units represented by the above-mentioned formula (BA-1) or formula (BA-2).

[Specific Examples] Specific examples of Compound B include the compounds used in the Examples, but are not limited thereto.

[Content] The content of Compound B is preferably 0.05-10% by mass, more preferably 0.10-5% by mass, and even more preferably 0.15-2% by mass, relative to the total solids content of the curable resin composition of the present invention. The curable resin composition of the present invention may contain only one type of Compound B or two or more types of Compound B. When containing two or more types of Compound B, the total amount is preferably within the above range.

<Compound C> From the perspective of the resulting cured film's adhesion to metal, the curable resin composition of the present invention preferably further comprises Compound C, which is a compound having no polymerizable group but having an azole group. Preferred embodiments of the azole group in Compound C are the same as those of Compound B described above. Also, Compound C is a compound having no polymerizable group, and the details of the polymerizable group are the same as those of Compound B described above.

Compound C is preferably a compound represented by the following formula (C-1) or the following formula (C-2). [Chemical Formula 41] In formula (C-1), Z ¹ to Z ⁴ each independently represent ═CR ⁷ - or a nitrogen atom, R ¹ represents a hydrogen atom or a monovalent organic group, R ⁷ represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (C-1) does not contain a polymerizable group. In formula (C-2), Z ⁵ to Z ⁶ each independently represent ═CR ⁸ - or a nitrogen atom, R ² to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, R ⁸ represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (C-2) does not contain a polymerizable group.

^In formula (C-1), Z ¹ to Z ⁴ independently represent ═CR ⁷ - or a nitrogen atom. Preferred embodiments include ^one nitrogen atom and ^three ═CR ⁷ -, two nitrogen atoms and two ^{═CR 7 - ,} and three nitrogen atoms and one ═CR ^{7 -} . Among these, the embodiment in which ^Z1 and ^Z3 are nitrogen atoms and ^Z2 and ^Z4 are = ^CR7- , the embodiment in which Z1 and ^Z2 are nitrogen atoms and ^Z3 and ^Z4 are = ^CR7- , or the embodiment in which ^Z1 , ^{Z2 and Z3} are nitrogen atoms and ^Z4 is = ^CR7- is preferred; the embodiment in which Z1 and ^Z3 are nitrogen atoms and ^Z2 and ^Z4 are = ^CR7- , or the embodiment ⁱⁿ which ^Z1 , ^Z2 and ^Z3 are nitrogen atoms and ^Z4 is = ^CR7- is further preferred.

In formula (C-1), ^R1 is preferably a hydrogen atom or a alkyl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom. The carbon number of the alkyl group or alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4.

In formula (C-1), preferred embodiments of R ⁷ are the same as those of R ¹ .

In formula (C-2), ^Z5 and ^Z6 each independently represent = ^CR8- or a nitrogen atom. Preferably, both ^Z5 and ^Z6 represent a nitrogen atom, or ^Z5 represents a nitrogen atom and ^Z6 represents = ^CR8- .

In formula (C-2), R ² to R ⁶ and R ⁸ are each independently preferably a hydrogen atom or a alkyl group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.

[Molecular Weight] The molecular weight of compound C is preferably 67-500, more preferably 68-300.

[Specific Examples] Specific examples of Compound C include the compounds used in the Examples, but are not limited thereto.

[Content] The content of Compound C is preferably 0.05-10% by mass, more preferably 0.10-5% by mass, and even more preferably 0.15-2% by mass, relative to the total solids content of the curable resin composition of the present invention. The curable resin composition may contain only one type of Compound C or two or more types of Compound C. When containing two or more types of Compound C, the total amount is preferably within the above range.

<Compound D> The curable resin composition of the present invention preferably further comprises a silane coupling agent having a polymerizable group different from an alkoxysilyl group and not having an azole group.

Compound D preferably comprises an alkoxysilyl group and a polymerizable group different from the alkoxysilyl group. Preferred embodiments of the alkoxysilyl group in Compound D are the same as those of the alkoxysilyl group in Compound B described above. Additionally, Compound D does not contain an azole group; the details of the azole group are the same as those for the azole group in Compound B described above.

Examples of polymerizable groups other than the alkoxysilyl group in compound D include known polymerizable groups such as free radical polymerizable groups, epoxy groups, cyclobutyl oxy groups, hydroxymethyl groups, alkoxymethyl groups, and (blocked) isocyanate groups. Free radical polymerizable groups or epoxy groups are preferred. Preferred aspects of the free radical polymerizable group in compound D are the same as those described above for the free radical polymerizable group in compound B.

As compound D, a compound having a structure represented by the following formula (DA-1) is preferred. [Chemical Formula 42] In formula (DA-1), R ^D1 to R ^D3 each independently represent an alkyl group, L ^D1 represents a divalent linking group, and X ^D1 represents a polymerizable group.

In formula (DA-1), R ^D1 to R ^D3 are each independently preferably an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, and more preferably an ethyl group.

In formula (DA-1), L ^D1 represents a divalent linking group, preferably a alkyl group or a group formed by a bond between a alkyl group and at least one group selected from the group consisting of -O-, -S-, -C(=O)-, -S(=O) _2- , and -NR ^N -, with a alkyl group being more preferred. ^RN is as described above. Furthermore, an embodiment in which L ^D1 has at least one group selected from the group consisting of an amino group and a urea group is also a preferred embodiment of the present invention.

In formula (DA-1), X ^D1 represents a polymerizable group, and preferred embodiments of the polymerizable group are as described above.

Compound D may be a compound with a molecular weight of less than 2,000 (hereinafter referred to as "low-molecular compound D") or a resin (hereinafter referred to as "resin D"). From the perspective of the cured film's adhesion to metal, it is also preferred that the curable resin composition contain both low-molecular compound D and resin D.

[Low-molecular-weight compound D] The molecular weight of low-molecular-weight compound D is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less. The number of polymerizable groups other than the alkoxysilyl groups in low-molecular-weight compound D is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. Low-molecular-weight compound D is a compound represented by formula (DA-1) above, preferably having a molecular weight within the above-mentioned range.

[Resin D] Resin D is preferably a resin having repeating units containing an alkoxysilyl group and repeating units containing a polymerizable group different from the alkoxysilyl group, or preferably a resin having repeating units containing both an alkoxysilyl group and a polymerizable group different from the alkoxysilyl group. More preferably, it is a resin having repeating units containing an alkoxysilyl group and repeating units containing a polymerizable group different from the alkoxysilyl group. The weight-average molecular weight of Resin D is preferably 2,000 to 100,000, more preferably 3,000 to 70,000, and even more preferably 5,000 to 50,000. Resin D is preferably an acrylic resin.

Preferred examples of the repeating units containing an alkoxysilyl group and the repeating units containing a polymerizable group different from the alkoxysilyl group in the resin D include the repeating units represented by the above-mentioned formula (BA-2).

Furthermore, the resin D may further have repeating units other than the repeating units represented by the above formula (BA-2).

[Specific Examples] Specific examples of Compound D include the compounds used in the Examples, but are not limited thereto.

[Content] The content of Compound D is preferably 0.05-10% by mass, more preferably 0.10-5% by mass, and even more preferably 0.15-2% by mass, relative to the total solids content of the curable resin composition of the present invention. The curable resin composition may contain only one type of Compound D or two or more types of Compound D. When containing two or more types of Compound D, the total amount is preferably within the above range.

<Compound E> The curable resin composition of the present invention preferably further comprises Compound E, which is a silane coupling agent that does not have either a polymerizable group other than an alkoxysilyl group or an azole group. Compound E is preferably a compound that has an alkoxysilyl group but does not have either a polymerizable group other than an alkoxysilyl group or an azole group. Compound E is a compound that does not have a polymerizable group other than an alkoxysilyl group. However, the details of the polymerizable group other than an alkoxysilyl group have the same meaning as the polymerizable group other than the alkoxysilyl group in Compound D described above. Compound E is a compound that does not have an azole group. The details of the azole group have the same meaning as the azole group in Compound B described above.

Examples of compound E 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, the compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Laid-Open No. 2014-191252, the compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Laid-Open No. 2014-041264, and the compounds described in paragraph 0055 of International Publication No. 2014/097594, which do not have a polymerizable group other than an alkoxysilyl group or an azole group. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferred to use two or more different silane coupling agents. Also, the following compound is preferably used as compound E. In the following formula, Et represents an ethyl group.

【Chemical formula 43】

[Content] The content of Compound E is preferably 0.05-10% by mass, more preferably 0.10-5% by mass, and even more preferably 0.15-2% by mass, relative to the total solids content of the curable resin composition of the present invention. The curable resin composition may contain only one type of Compound E or two or more types of Compound E. When containing two or more types of Compound E, the total amount is preferably within the above range.

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

As esters, preferred examples 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, methyl 3- ethyl ethoxypropionate, 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, etc., ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate.

Preferred examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate acetate, ethyl thiocyanate acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.

Preferred ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosan, and dihydrolevoglucosan.

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

As the sulfoxides, dimethyl sulfoxide is preferably exemplified.

Preferred amides include N-methyl-2-pyrrolidone, N-ethyl-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 alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol.

From the perspective of improving the properties of the coated surface, it is also preferable to use a solvent in the form of a mixture of two or more solvents.

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, or a mixture of two or more of these solvents is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. Furthermore, combinations of N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, or cyclopentanone and γ-butyrolactone are also preferred.

The curable resin composition of the present invention preferably includes an ester, and more preferably includes a lactone-based solvent. Lactone-based solvents refer to solvents containing a lactone structure, and examples thereof include γ-butyrolactone, ε-caprolactone, and δ-valerolactone. The content of the lactone-based solvent relative to the total mass of the solvent is not particularly limited, but is preferably 30-100 mass%, more preferably 40-95 mass%, and even more preferably 50-90 mass%.

From the perspective of coating properties, the solvent content is preferably such that the total solids concentration of the curable resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 40 to 70% by mass. The solvent content can be adjusted based on the desired coating thickness and coating method.

The solvent may be contained in one type or in two or more types. When two or more types of solvents are contained, it is preferred that the total amount of the solvents be within the above range.

<Photosensitive Agent> The composition of the present invention preferably contains a photosensitizer. Preferably, the photosensitizer is a photopolymerization initiator.

[Photopolymerization Initiator] The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer. Preferably, the photopolymerization initiator is a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, photoradical polymerization initiators that are sensitive to light in the ultraviolet to visible range are preferred. Alternatively, an activator that reacts with a photoexcited sensitizer to generate active radicals may be used. Preferably, the oxime compound described below is used as the photoradical polymerization initiator.

The photoradical polymerization initiator preferably contains at least one compound having a molar absorbance of at least about 50 L·mol ^-1 •cm ^-1 in the range of about 300-800 nm (preferably 330-500 nm). The molar absorbance of the compound can be measured using known methods. For example, it is preferably measured using a UV-visible spectrophotometer (Varian Cary-5 spectrophotometer) 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 an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron aromatic complexes. For details of these, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are 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 (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

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

As hydroxyacetophenone-based initiators, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As aminoacetophenone-based initiators, compounds described in Japanese Patent Application Laid-Open No. 2009-191179, which have a maximum absorption wavelength matching a light source having a wavelength of 365 nm or 405 nm, can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. Commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can also be used.

Examples of the metallocene compound include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF).

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

Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, and compounds described in JP-A-2006-342166.

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 composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. Oxime-based photopolymerization initiators have a linking group of >C=N-O-C(=O)- in the molecule.

【Chemical formula 44】

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 Japanese Patent Application Publication No. 2012-014052) can also be preferably used. Furthermore, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. Furthermore, DFI-091 (manufactured by Daito Chemix Corporation) can be used. Furthermore, the oxime compound having the following structure can also be used. [Chemical Formula 45]

Oxime compounds having a fluorene ring can also be used as photopolymerization initiators. Specific examples of oxime compounds having a fluorene ring include compounds described in Japanese Patent Application Publication No. 2014-137466 and Japanese Patent No. 06636081.

As a photopolymerization 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.

Alternatively, oxime compounds containing fluorine atoms can 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.

Preferred oxime compounds include oxime compounds having specific substituents as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

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, cyclopentadiene-benzyl-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. Further preferred is at least one compound selected from the group consisting of trihalogenomethyl triphosphine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds. The use of metallocene compounds or oxime compounds is even more preferred, and oxime compounds are still more preferred.

Furthermore, the photoradical polymerization initiator may include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michelle'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 with aromatic ring condensations such as alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Furthermore, compounds represented by the following formula (I) may be used.

【Chemical formula 46】

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, 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 a phenyl group or a biphenyl group substituted with at least one of the following: 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 47】

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.

When a photopolymerization initiator is included, its content is preferably 0.1-30 mass% relative to the total solids content of the composition of the present invention, more preferably 0.1-20 mass%, even more preferably 0.5-15 mass%, and even more preferably 1.0-10 mass%. The photopolymerization initiator may be present in a single species or in two or more species. When two or more photopolymerization initiators are present, their total amount is preferably within the above range.

[Photoacid Generator] The composition of the present invention preferably includes a photoacid generator as a photosensitizer. By including a photoacid generator, for example, acid is generated in the exposed areas of the composition layer, increasing the solubility of the exposed areas in a developer (e.g., an alkaline aqueous solution), thereby producing a positive pattern in which the exposed areas are removed by the developer. Furthermore, by including a polymerizable compound other than the photoacid generator and the radically polymerizable compound described below, for example, by utilizing the acid generated in the exposed areas to promote the crosslinking reaction of the polymerizable compound, the exposed areas can be made less easily removed by the developer than the unexposed areas. In this manner, a negative pattern can be produced.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include quinonediazide compounds, onium salt compounds such as diazonium salts, phosphonium salts, codonium salts, and iodonium salts, sulfonate compounds such as imide sulfonates, oxime sulfonates, diazonium disulfonates, disulfonium disulfonates, and o-nitrobenzyl sulfonates.

Examples of quinonediazide compounds include those in which a quinonediazide sulfonic acid is bonded to a polyhydroxy compound via an ester bond, those in which a quinonediazide sulfonic acid is bonded to a polyamine compound via a sulfonamide bond, and those in which a quinonediazide sulfonic acid is bonded to a polyhydroxypolyamine compound via at least one of an ester bond and a sulfonamide bond. In the present invention, for example, it is preferred that at least 50 mol% of the total functional groups of the polyhydroxy compound or polyamine compound be substituted with quinonediazide groups.

In the present invention, the quinonediazide can preferably be either 5-naphthoquinonediazidesulfonyl or 4-naphthoquinonediazidesulfonyl. 4-naphthoquinonediazidesulfonyl compounds absorb in the i-ray region of mercury lamps and are suitable for i-ray exposure. 5-naphthoquinonediazidesulfonyl compounds absorb in the g-ray region of mercury lamps and are suitable for g-ray exposure. In the present invention, 4-naphthoquinonediazidesulfonyl compounds or 5-naphthoquinonediazidesulfonyl compounds are preferably selected based on the exposure wavelength. Furthermore, a naphthoquinonediazidesulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group may be contained in the same molecule, or a 4-naphthoquinonediazidesulfonyl ester compound and a 5-naphthoquinonediazidesulfonyl ester compound may be contained.

These naphthoquinone diazide compounds can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by known methods. The use of these naphthoquinone diazide compounds further improves resolution, sensitivity, and film residue rate. Examples of these naphthoquinone diazide compounds include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or esters of these compounds.

Examples of the onium salt compound or sulfonate salt compound include compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.

The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter referred to as an "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it contains an oxime sulfonate group, but oxime sulfonate 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 48】

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 group and alkoxy group in ^X3 may have a substituent. 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 ³⁴ 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.

Particularly preferred are compounds 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.

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, and the contents thereof are incorporated herein.

【Chemical formula 49】

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 a substituent T.

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 a compound, when 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 a substituent T. In formulas (OS-103), (OS-104), or (OS-105), Xs is 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). 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 50]

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.

Other preferred embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formula (OS-101) and formula (OS-102).

【Chemical formula 51】

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 form a ring. In this case, the ring may be condensed to form a fused ring with a benzene ring. R ^u1 to R ^u4 are preferably a hydrogen atom, a halogen atom, or an alkyl group. Furthermore, at least two of R ^u1 to R ^u4 are bonded to form an aryl group. Among them, the embodiment in which all of R ^u1 to R ^u4 are hydrogen atoms is preferred. Each of the above substituents may further have a substituent.

The compound represented by formula (OS-101) is more preferably a compound represented by formula (OS-102). In addition, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring in the above-mentioned oxime sulfonate compound may be any one of these, or a mixture may be used. Specific examples of the compound represented by formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of JP-A-2011-209692 and paragraphs 0195 to 0207 of JP-A-2015-194674, the contents of which are incorporated herein. Among the above-mentioned compounds, b-9, b-16, b-31, and b-33 are preferred.

In addition, commercially available photoacid generators can also be used. Examples include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250 and Omnicat 270 (all manufactured by IGM Resins B.V.), Irgacure 250, Irgacure 270, and Irgacure 290 (all manufactured by BASF), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

As a more preferred example, the compound represented by the following structural formula can also be cited. [Chemical Formula 52]

Organic halogenated compounds can also be used as photoacid generators. 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 Among the compounds described in "Chemistry" 1 (No. 3), (1970), etc., in particular, oxazole compounds substituted with a trihalomethyl group: S-triadium compounds can be cited. More preferably, s-triadium derivatives in which at least one mono-, di-, or trihalomethyl substituted methyl group is bonded to the s-triadium ring can be cited. Specifically, for example, 2,4,6-tris(monochloromethyl)-s-triadium, 2,4,6-tris(dichloromethyl)-s-triadium, 2,4,6-tris(trichloromethyl)-s-triadium, 2-methyl-4,6-bis(trichloromethyl)-s-triadium, 2-n-propyl-4,6-bis(trichloromethyl)-s-triadium can be cited. tris-1-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris-1-], 2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris-1-], 2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris-1-], 2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris-1-], 2-[1-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris-1-], phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-trithionyl, 2-phenylvinyl-4,6-bis(trichloromethyl)-s-trithionyl, 2-(p-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-trithionyl, 2-(p-isopropoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-trithionyl, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-trithionyl, 2-(4-naphthyloxyphenyl)- Naphthyl)-4,6-bis(trichloromethyl)-s-trithionyl, 2-phenylthio-4,6-bis(trichloromethyl)-s-trithionyl, 2-benzylthio-4,6-bis(trichloromethyl)-s-trithionyl, 2,4,6-tris(dibromomethyl)-s-trithionyl, 2,4,6-tris(tribromomethyl)-s-trithionyl, 2-methyl-4,6-bis(tribromomethyl)-s-trithionyl, 2-methoxy-4,6-bis(tribromomethyl)-s-trithionyl, etc.

As the photoacid generator, an organic borate compound can also be used. Specific examples of organic borate compounds include Japanese Patent Application Nos. 62-143044, 62-150242, 9-188685, 9-188686, 9-188710, 2000-131837, 2002-107916, 2764769, and 2000-310808, as well as Kunz and Martin's "Rad Tech '98. Proceedings April 19-22, 1998, Chicago" etc., the organic borate salts described in Japanese Patent Laid-Open No. 6-157623, Japanese Patent Laid-Open No. 6-175564, Japanese Patent Laid-Open No. 6-175561, the organic boron-zirconium complexes or organic boron-oxygen-zirconium complexes described in Japanese Patent Laid-Open No. 6-175554, Japanese Patent Laid-Open No. 6-175553 Organoboron phosphonium complexes described in Japanese Patent Application Laid-Open No. 9-188710, organoboron transition metal coordination complexes such as Japanese Patent Application Laid-Open No. 6-348011, Japanese Patent Application Laid-Open No. 7-128785, Japanese Patent Application Laid-Open No. 7-140589, Japanese Patent Application Laid-Open No. 7-306527, and Japanese Patent Application Laid-Open No. 7-292014.

As the photoacid generator, a disulfide compound can also be used. Examples of the disulfide compound include compounds described in Japanese Patent Application Laid-Open No. 61-166544 and 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. 390, Copper salts described in the specifications of Patent No. 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), selenium salts described in J.V.Crivello et al, J.Polymer Sci., Polymer Chem.Ed., 17, 1047 (1979), arsenic salts, pyridinium salts and other onium salts described in C.S.Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), etc.

Examples of onium salts include those represented by the following general formulas (RI-I) to (RI-III). [Chemical Formula 53] 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 1 to 12 carbon atoms, an alkynyl group having 1 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, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 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. ^Z11- 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), Ar21 and Ar22 each independently represent 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 1 to 12 carbon atoms, an alkynyl group having 1 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, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 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. ^Z21- represents a monovalent anion, and is selected from halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, thiosulfonic acid ions, and sulfate ions. From the perspectives 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), R31, R32, and R33 each independently represent an aryl group having 20 or fewer carbon atoms, which may have 1 to 6 substituents, or an alkyl, alkenyl, or alkynyl group. Preferably, an aryl group is preferred from the perspectives of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 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, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 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. ^Z31- 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. In terms of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, and carboxylic acid ions are preferred.

As a specific example, the following can be cited. [Chemical Formula 54] 【Chemical formula 55】 【Chemical formula 56】 【Chemical formula 57】

When a photoacid generator is included, its content is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, and even more preferably 2-15% by mass, relative to the total solids content of the composition of the present invention. The photoacid generator may be present in a single species or in combination of two or more species. When two or more species are present, their combined content is preferably within the above range.

[Photobase Generator] The curable resin composition of the present invention may contain a photobase generator as a photosensitizer. By containing a photobase generator and a crosslinking agent (described below) in the curable resin composition, for example, the base generated in the exposed areas promotes the cyclization of a specific resin and the crosslinking reaction of the crosslinking agent, thereby rendering the exposed areas less susceptible to removal by a developer than the unexposed areas. This allows for the production of negative patterns.

The photoalkali generator is not particularly limited as long as it generates alkali by exposure, and any known photoalkali generator can be used. For example, M. Shirai and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kadoka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006) describe that transition metal compound complexes, substances having structures such as ammonium salts, substances in which the amidine moiety is potentially oxidized by forming salts with carboxylic acids, ionic compounds in which the base component is neutralized by forming salts, and non-ionic compounds in which the base component is potentially oxidized through carbamate bonds or oxime bonds, such as carbamate derivatives, oxime ester derivatives, and acyl compounds. In the present invention, more preferred examples of the photoalkali generator include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, and oxime derivatives.

The alkaline substance generated from the photoalkali generator is not particularly limited, but examples thereof include compounds having amino groups, particularly polyamines such as monoamines and diamines, and amidines. From the perspective of the imidization rate, it is preferred that the alkaline substance have a high pKa in DMSO (dimethyl sulfoxide) with the conjugated acid. A pKa of 1 or greater is preferred, and 3 or greater is even more preferred. There is no particular upper limit for the pKa, but 20 or less is preferred. Here, the pKa value represents the logarithm of the reciprocal of the first dissociation constant of an acid. The values listed in Determination of Organic Structures by Physical Methods (authors: Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; editors: Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955) or Data for Biochemical Research (author: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959) can be found. For compounds not listed in these documents, the pKa value calculated from the structural formula using the ACD/pKa software (manufactured by ACD/Labs) was used as the pKa value.

From the perspective of the storage stability of curable resin compositions, photoalkali generators that do not contain salts in their structure are preferred. It is also preferred that the nitrogen atoms in the generated alkali moiety have no charge. It is also preferred that the generated alkali is potentially converted to alkali via covalent bonds, and that the alkali generation mechanism is one in which the covalent bonds between the nitrogen atoms in the generated alkali moiety and adjacent atoms are broken to generate the alkali. Photoalkali generators that do not contain salts in their structure are neutral, resulting in better solvent solubility and a longer shelf life. For these reasons, the amine generated from the photobase generator used in the present invention is preferably a primary or secondary amine. Furthermore, from the perspective of the chemical resistance of the pattern, a photobase generator containing a salt in its structure is preferred.

Furthermore, based on the above reasons, as a photoalkali generator, as described above, the generated base is preferably potentially converted using a covalent bond, and the generated base is preferably potentially converted using an amide bond, a carbamate bond, or an oxime bond. Examples of the photoalkali generator of the present invention include those having a cinnamylamide structure as disclosed in Japanese Patent Application Publication No. 2009-080452 and International Publication No. 2009/123122, those having a carbamate structure as disclosed in Japanese Patent Application Publication No. 2006-189591 and Japanese Patent Application Publication No. 2008-247747, and those having an oxime structure or an aminoformyloxime structure as disclosed in Japanese Patent Application Publication No. 2007-249013 and Japanese Patent Application Publication No. 2008-003581. However, the present invention is not limited to these, and any other known photoalkali generator structure can be used.

In addition, examples of photoalkali generators include compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of Japanese Patent Application Laid-Open No. 2012-093746, compounds described in paragraphs 0022 to 0069 of Japanese Patent Application Laid-Open No. 2013-194205, compounds described in paragraphs 0026 to 0074 of Japanese Patent Application Laid-Open No. 2013-204019, and compounds described in paragraph 0052 of International Publication No. 2010/064631.

In addition, commercially available photoalkali generators can be used. Examples include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), and A2502, B5085, N0528, N1052, O0396, O0447, and O0448 (manufactured by Tokyo Chemical Industry Co., Ltd.).

When a photobase generator is included, its content is preferably 0.1 to 30 mass%, more preferably 0.1 to 20 mass%, and even more preferably 2 to 15 mass%, relative to the total solids content of the curable resin composition of the present invention. The photobase generator may be present in a single species or in two or more species. When two or more photobase generators are present, their combined content is preferably within the above range.

<Thermal Polymerization Initiator> The 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 to initiate or accelerate the polymerization reaction of a polymerizable compound. The addition of a thermal free radical polymerization initiator allows the polymerization reaction of the resin and the polymerizable compound to proceed even during the heating process described below, thereby further improving solvent resistance.

Specific examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When a thermal polymerization initiator is included, its content is preferably 0.1-30 mass %, more preferably 0.1-20 mass %, and even more preferably 5-15 mass %, relative to the total solids content of the 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, their total amount is preferably within the above range.

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

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 preferred to select a thermal acid generator that does not generate acid during drying (pre-bake: approximately 70-140°C) after applying the composition to the substrate, but generates acid during the final heating (curing: approximately 100-400°C) after patterning during subsequent exposure and development. This can suppress sensitivity loss during development and is therefore preferable. The thermal decomposition starting temperature is determined as the peak temperature of the lowest exothermic 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 starting temperature include the Q2000 (manufactured by TA Instruments).

The acid generated by the thermal acid generator is preferably a strong acid, such as an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, or butanesulfonic acid, or a halogenated alkylsulfonic acid 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 film and less deterioration of the physical properties of the organic film, those that produce alkylsulfonic acids having 1 to 4 carbon atoms or halogenated alkylsulfonic acids having 1 to 4 carbon atoms are more preferred, such as (4-hydroxyphenyl)dimethylcopperium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylcopperium methanesulfonate, benzyl(4-hydroxyphenyl)methylcopperium methanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylcopperium methanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copperium methanesulfonate, (4-hydroxyphenyl)dimethylcopperium trifluoromethanesulfonate, Preferred thermal acid generators include (4-((methoxycarbonyl)oxy)phenyl)dimethylcopperium trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylcopperium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylcopperium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copperium trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophen-2(5H)-ylidene)-2-(o-tolyl)propionitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

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

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.

<Onium Salt> The curable resin composition of the present invention may further contain an onium salt. In particular, when the curable resin composition of the present invention contains a polyimide prodrug or a polybenzoxazole prodrug as the specific resin, inclusion of an onium salt is preferred. The type of onium salt is not particularly limited, but preferred examples include ammonium salts, ammonium salts, stibnium salts, iodine salts, and phosphonium salts. Among these, ammonium salts or ammonium salts are preferred from the perspective of high thermal stability, and codonium salts, iodonium salts, or phosphonium salts are preferred from the perspective of compatibility with polymers.

Onium salts are salts of cations and anions having an onium structure. These cations and anions may or may not be covalently bonded. That is, onium salts may be intramolecular salts, with cations and anions within the same molecular structure, or intermolecular salts, with cations and anions ionically bonded between separate molecules. Intermolecular salts are preferred. Furthermore, in the curable resin composition of the present invention, the cations or cation molecules and the anions or anions may be ionically bonded or dissociated. As the cation in the onium salt, ammonium cation, pyridinium cation, coronium cation, iodine cation or phosphonium cation is preferred, and at least one cation selected from the group consisting of tetraalkylammonium cations, coronium cations and iodine cations is more preferred.

The onium salt used in the present invention may be a thermal alkali generator described below. A thermal alkali generator refers to a compound that generates a base upon heating, and examples thereof include compounds that generate a base upon heating to 40°C or higher. Examples of onium salts include those described in paragraphs 0122-0138 of International Publication No. 2018/043262. In addition, onium salts used in the field of polyimide precursors may be used without particular limitation.

When the curable resin composition of the present invention contains an onium salt, the onium salt content is preferably 0.1 to 50 mass% relative to the total solids content of the curable resin composition of the present invention. The lower limit is preferably 0.5 mass% or greater, more preferably 0.85 mass% or greater, and even more preferably 1 mass% or greater. The upper limit is more preferably 30 mass% or less, more preferably 20 mass% or less, and even more preferably 10 mass% or less. It may also be 5 mass% or less, or even 4 mass% or less. The onium salts may be used alone or in combination. When two or more are used, the total amount is preferably within the above range.

<Thermoalkali generator> The curable resin composition of the present invention may further contain a thermoalkali generator. In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain a thermoalkali generator. Other thermoalkali generators may be compounds corresponding to the above-mentioned onium salts, or thermoalkali generators other than the above-mentioned onium salts. Examples of thermoalkali generators other than the above-mentioned onium salts include non-ionic thermoalkali generators. Examples of non-ionic thermoalkali generators include compounds represented by formula (B1) or formula (B2). [Chemical Formula 58]

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 cannot all have carboxyl groups. 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 carbon atoms in a hydrocarbon system. 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 the nitrogen atom, the structure is not limited thereto.

In formulas (B1) and (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 a single ring or a fused ring, with a single ring or a fused ring formed by condensing two single rings being preferred. The single ring is preferably a 5-membered or 6-membered ring, with a 6-membered ring being more preferred. The single ring is preferably a cyclohexane ring or a benzene ring, with a cyclohexane 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 arylalkyl 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 achieving the effects 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. ^Rb1 and ^Rb2 are particularly preferably linear, branched, or cyclic alkyl groups which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), more preferably cycloalkyl groups which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), 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), arylalkyl 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 arylalkenyl group (preferably 8-24 carbon atoms, more preferably 8-20 carbon atoms, and even more preferably 8-16 carbon atoms), an alkoxy group (preferably 1-24 carbon atoms, more preferably 2-18 carbon atoms, and even more preferably 3-12 carbon atoms), an aryloxy group (preferably 6-22 carbon atoms, more preferably 6-18 carbon atoms, and even more preferably 6-12 carbon atoms), or an arylalkoxy group (preferably 7-23 carbon atoms, more preferably 7-19 carbon atoms, and even more preferably 7-12 carbon atoms). Among these, cycloalkyl groups (preferably 3-24 carbon atoms, more preferably 3-18 carbon atoms, and even more preferably 3-12 carbon atoms), arylalkenyl groups, and arylalkoxy 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 59]

In the formula, ^Rb11 and ^Rb12 , as well as ^Rb31 and ^Rb32 , are the same 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 arylalkyl 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 a range that allows the effects of the present invention to be exerted. Among them, ^Rb13 is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 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 arylalkyl 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 arylalkyl 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.

The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a). [Chemical Formula 60]

^Rb11 and ^Rb12 have the same meanings as ^Rb11 and ^Rb12 in formula (B1-1). ^Rb15 and ^Rb16 are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 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), or arylalkyl groups (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 atoms, or methyl groups. Rb ¹⁷ 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 arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), among which aryl group is preferred.

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 examples of the compound serving as a thermal alkali generator among the above-mentioned onium salts or specific examples of the thermal alkali generator other than the above-mentioned onium salts include the following compounds.

【Chemical formula 61】

【Chemical formula 62】

【Chemical formula 63】

The content of other alkali generators is preferably 0.1 to 50 mass% relative to the total solids content of the curable resin composition of the present invention. The lower limit is more preferably 0.5 mass% or greater, and even more preferably 1 mass% or greater. The upper limit is more preferably 30 mass% or less, and even more preferably 20 mass% or less. One or more alkali generators may be used. When two or more are used, the total amount is preferably within the above range.

<Crosslinking Agent> The curable resin composition of the present invention preferably contains a crosslinking agent. Examples of the crosslinking agent include free radical crosslinkers and other crosslinking agents.

<Free Radical Crosslinking Agent> The curable resin composition of the present invention preferably further comprises 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, and (meth)acryloyl groups. Among these, (meth)acryloyl groups are preferred as the groups containing ethylenically unsaturated bonds, and from the perspective of reactivity, (meth)acryloyl groups are even more preferred.

The radical crosslinking agent may be any compound having one or more ethylenically unsaturated bonds, with compounds having two or more being more preferred. The compound having two ethylenically unsaturated bonds is preferably a compound having two of the aforementioned groups containing ethylenically unsaturated bonds. In addition, from the perspective of the film strength of the resulting pattern (cured film), the curable resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as the radical crosslinking agent. Compounds having three or more ethylenically unsaturated bonds are preferably compounds having 3 to 15 ethylenically unsaturated bonds, more preferably compounds having 3 to 10 ethylenically unsaturated bonds, and even more preferably compounds having 3 to 6 ethylenically unsaturated bonds. Furthermore, the compound having three or more ethylenically unsaturated bonds is preferably a compound having three or more of the aforementioned groups containing ethylenically unsaturated bonds, more preferably a compound having 3 to 15 groups, even more preferably a compound having 3 to 10 groups, and particularly preferably a compound having 3 to 6 groups. In addition, from the perspective of the film strength of the resulting pattern (cured film), it is also preferred that the curable resin composition of the present invention contain a compound having two ethylenically unsaturated bonds and the aforementioned compound having three or more ethylenically unsaturated bonds.

The molecular weight of the free 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 free 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, preferably 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 sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, are also preferably used. Furthermore, addition products of unsaturated carboxylates or amides having electron-withdrawing substituents such as isocyanate or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, as well as substitution products of unsaturated carboxylates or amides having ionizing substituents such as halogen groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, can also be preferably used. 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 a specific example, reference can be made to paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357, the contents of which are incorporated into this specification.

Furthermore, the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher at normal pressure. Examples thereof include compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as 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, hexylene glycol (meth)acrylate, trihydroxymethylpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, and then (meth)acrylating the resulting mixture. Esterified compounds, 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, epoxy acrylates that are reaction products of epoxy resins and (meth)acrylic acid, and polyfunctional acrylates or methacrylates, and mixtures thereof, are also preferred. Compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. Also exemplified are 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.

Furthermore, as preferred radical crosslinking agents other than those mentioned above, compounds having a fluorene ring and two or more groups containing ethylenically unsaturated bonds, or cardo resins, as described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent Application No. 4364216, etc., can also be used.

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 the Journal of the Japan Association for Adhesion, 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, compounds described in Japanese Patent Application Laid-Open No. 10-062986 as formula (1) and formula (2) together with specific examples thereof, in which ethylene oxide or propylene oxide is added to a polyfunctional alcohol and then (meth)acrylic acid is esterified, can also be used as radical crosslinking agents.

In addition, 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. Oligomers of these can also be used.

Examples of commercially available free radical crosslinking agents include SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethoxy chains; SR-209, 231, and 239 manufactured by Sartomer Company, Inc., which are bifunctional methacrylates having four ethoxy chains; DPCA-60 manufactured by Nippon Kayaku Co., Ltd., which is a hexafunctional acrylate having six pentyloxy chains; TPA-330 manufactured by Nippon Kayaku Co., Ltd., which is 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 also 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 aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and more preferred are free radical crosslinking agents having an acid group 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 by reacting a non-aromatic carboxylic acid anhydride with unreacted hydroxyl groups of an aliphatic polyhydroxy compound, wherein the aliphatic polyhydroxy compound is a compound of neopentatriol or dipentatriol. Examples of commercially available products include polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD., such as M-510 and M-520.

The preferred acid value of a free radical crosslinking agent containing an acid group is 0.1 to 40 mgKOH/g, particularly 5 to 30 mgKOH/g. A free radical crosslinking agent with an acid value within this range provides excellent workability during production and, consequently, excellent developability. Furthermore, it exhibits good polymerizability. Furthermore, from the perspective of developing speed during alkaline development, the preferred acid value of a free radical crosslinking agent containing an acid group is 0.1 to 300 mgKOH/g, particularly 1 to 100 mgKOH/g. The acid value is measured in accordance with JIS K 0070:1992.

From the viewpoint of pattern resolution and film stretchability, the curable resin composition of the present invention preferably uses a bifunctional methacrylate or acrylate. Specific compounds that can be used include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 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 diacrylate. Dimethacrylate, dihydroxymethyl-tricyclodecane diacrylate, dihydroxymethyl-tricyclodecane dimethacrylate, bisphenol A EO adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, bifunctional acrylates with a urethane bond, and bifunctional methacrylates with a urethane bond. Two or more of these may be used in combination as needed. Furthermore, from the perspective of suppressing warping associated with controlling the elastic modulus of the pattern (cured film), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional free radical crosslinking agent, preferably used are (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate. As a monofunctional free radical crosslinking agent, compounds with a boiling point above 100°C at normal pressure are also preferred in order to suppress volatility before exposure.

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 curable 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, the total amount thereof is preferably within the above range.

<Other Crosslinking Agents> The curable resin composition of the present invention preferably contains a crosslinking agent other than the free radical crosslinking agent described above. In the present invention, the "other crosslinking agent" refers to a crosslinking agent other than the free radical crosslinking agent described above. Preferably, the compound has multiple groups within its molecule that, upon exposure to light by the photosensitive agent, promote the formation of covalent bonds between other compounds in the composition or their reaction products. Preferably, the compound has multiple groups within its molecule that, upon exposure to light by the photosensitive agent, promote the formation of covalent bonds between other compounds in the composition or their reaction products. Preferably, the acid or base is generated from a photoacid generator or photoalkali generator serving as the photosensitive agent during the exposure process. As other crosslinking agents, compounds having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are even more preferred. Examples of other crosslinking agents include compounds having a structure in which the hydrogen atoms of amino groups are substituted with hydroxymethyl or alkoxymethyl groups by reacting formaldehyde or formaldehyde and an alcohol with amino-containing compounds such as melamine, acetylene carbamide, urea, alkylene urea, and benzoguanamine. The production methods of these compounds are not particularly limited, as long as the compounds have the same structure as the compounds produced by the above methods. Alternatively, oligomers formed by self-condensation of the hydroxymethyl groups of these compounds may be used. 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 curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluril-based crosslinking agents and melamine-based crosslinking agents described below.

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

Specific examples of urea-based crosslinking agents include monohydroxymethylated acetylene carbamide, dihydroxymethylated acetylene carbamide, trihydroxymethylated acetylene carbamide, tetrahydroxymethylated acetylene carbamide, monomethoxymethylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monoethoxymethylated acetylene carbamide, diethoxymethylated acetylene carbamide, triethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, tripropoxymethylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide, or tetrabutoxymethylated acetylene carbamide, etc. Urea-based crosslinkers such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, and bisbutoxymethyl urea; Ethyl urea-based crosslinkers such as monohydroxymethylated ethyl urea or dihydroxymethylated ethyl urea, monomethoxymethylated ethyl urea, dimethoxymethylated ethyl urea, monoethoxymethylated ethyl urea, diethoxymethylated ethyl urea, monopropoxymethylated ethyl urea, dipropoxymethylated ethyl urea, monobutoxymethylated ethyl urea, and dibutoxymethylated ethyl urea; Propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea; 1,3-bis(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

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

Furthermore, as the compound having at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group is 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) benzophenone, 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 curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, cyclohexane compounds, and benzoxazolium compounds as an additional 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 reducing film shrinkage. Therefore, the inclusion of epoxy compounds is effective in suppressing low-temperature curing and warping in curable resin compositions.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. A 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 group-containing silicones such as polymethyl (glycidyloxypropyl) siloxane. Specifically, we can cite 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) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICL ON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (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, Rika Resin (registered trademark) BEO-20E (these are trade names, manufactured by DIC Corporation), Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (trade names, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (these are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD (registered trademark) GT400, CELVENUS (registered trademark) B0134, B0177 (the above are trade 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 trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[Oxycyclobutane compounds (Oxycyclobutyl compounds)] Examples of oxycyclobutane compounds include compounds having two or more oxycyclobutane rings per molecule, 3-ethyl-3-hydroxymethyloxycyclobutane, 1,4-bis[(3-ethyl-3-oxycyclobutyl)methoxy]methyl]benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl]ester. As a specific example, the ARON OXETANE series manufactured by TOAGOSEI CO., LTD. (e.g., OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used. These can be used alone or in combination of two or more.

[Benzoxazone compounds (compounds containing a benzoxazolyl group)] Benzoxazone compounds are preferred because they do not produce outgassing during curing due to the cross-linking reaction derived from a ring-opening addition reaction. Furthermore, they reduce thermal shrinkage and suppress warping.

Preferred examples of benzoxazolium compounds include B-a-type benzoxazolium, B-m-type benzoxazolium, P-d-type benzoxazolium, and F-a-type benzoxazolium (trade names, manufactured by Shikoku Chemicals Corporation), benzoxazolium adducts of polyhydroxystyrene resins, and phenol novolac-type dihydrobenzoxazolium compounds. These compounds 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 hardening 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.

<Sulfonamide Compounds, Thiourea Compounds> From the perspective of improving the adhesion of the resulting pattern (cured film) to the substrate, the curable resin composition of the present invention preferably further comprises at least one compound selected from the group consisting of sulfonamide compounds and thiourea compounds.

[Compounds having a sulfonamide structure] The sulfonamide structure is represented by the following formula (S-1). [Chemical Formula 64] In formula (S-1), R represents a hydrogen atom or an organic group. R may bond with another structure to form a ring structure. * each independently represents a bonding site with another structure. Preferably, R is the same group as ^R2 in formula (S-2). The compound having a sulfonamide structure may have two or more sulfonamide structures, and preferably has one or more sulfonamide structures.

The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical Formula 65] In formula (S-2), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent organic group. Two or more of R ¹ , R ² , and R ³ may be bonded to form a ring structure. Preferably, R ¹ , R ² , and R ³ each independently represent a monovalent organic group. Examples of R ¹ , R ² , and R ³ include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a combination of two or more of these groups. Preferred alkyl groups include those having 1 to 10 carbon atoms, and more preferably those having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl. Preferred cycloalkyl groups include cycloalkyl groups having 5 to 10 carbon atoms, and more preferred cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Preferred alkoxy groups include alkoxy groups having 1 to 10 carbon atoms, and more preferred alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Preferred alkoxysilyl groups include alkoxysilyl groups having 1 to 10 carbon atoms, and more preferred alkoxysilyl groups include 1 to 4 carbon atoms. Examples of the alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of the aryl group include those having 6 to 20 carbon atoms, and those having 6 to 12 carbon atoms. These aryl groups may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include groups obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, an oxadiazole ring, a pyrimidine ring, a pyridine ring, a piperidine ring, a piperidine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a trioxadiazole ring.

Among these, compounds in which R ¹ is an aryl group and R ² and R ³ are independently a hydrogen atom or an alkyl group are preferred.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthylsulfonamide, naphthyl-1-sulfonamide, naphthyl-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

[Compounds having a thiourea structure] The thiourea structure is represented by the following formula (T-1). [Chemical Formula 66] In formula (T-1), ^R4 and ^R5 each independently represent a hydrogen atom or a monovalent organic group. ^R4 and ^R5 may bond to form a ring structure. ^R4 may bond to another structure to which * is bonded to form a ring structure. ^R5 may bond to another structure to which * is bonded to form a ring structure. * each independently represents a bonding site to another structure.

^R4 and ^R5 are preferably each independently a hydrogen atom. Examples of ^R4 and ^R5 include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a combination of two or more of these groups. Preferred alkyl groups include those with 1 to 10 carbon atoms, and more preferably those with 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl. Preferred cycloalkyl groups include those with 5 to 10 carbon atoms, and more preferably those with 6 to 10 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkoxy group include preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentoxy. Examples of the alkoxysilyl group include preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of the aryl group include preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include groups obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyrimidine ring, a piperidine ring, a piperidine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a trihydropyran ring. The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferred.

The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical Formula 67] In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, and at least two of R ⁴ to R ⁷ may be bonded to each other to form a ring structure.

In formula (T-2), ^R4 and ^R5 have the same meanings as ^R4 and ^R5 in formula (T-1), and preferred embodiments are also the same. In formula (T-2), ^R6 and ^R7 are each preferably independently a monovalent organic group. In formula (T-2), preferred monovalent organic groups for ^R6 and ^R7 are the same as preferred monovalent organic groups for ^R4 and R5 in formula (T- ¹ ).

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantylthiourea, N-benzoylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylenethiourea (2-imidazolinthione), carbimazole, and 1,3-dimethyl-2-thiohydantoin.

[Content] The combined content of the compound having a sulfonamide structure and the compound having a thiourea structure, relative to the total mass of the curable resin composition of the present invention, is preferably 0.05-10 mass%, more preferably 0.1-5 mass%, and even more preferably 0.2-3 mass%. The curable resin composition of the present invention may contain only one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more. When only one compound is contained, the content of the compound is preferably within the above range. When two or more compounds are contained, the combined content is preferably within the above range.

<Polymerization Inhibitor> The curable resin composition of the present invention preferably contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, p-tert-butyl-o-catechol (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) Phenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenanthridine, 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)-1-nitropropane -N-sulfopropylamino)phenol, N-nitrosophenylhydroxylamine first onium salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, N,N'-diphenyl-p-phenylenediamine, 2,4-di-tert-butylphenol, di-tert-butylhydroxytoluene, 1,4-naphthoquinone, 1,3,5-tris(4-tert-butyl-3-hydroxy- 2,6-dimethylbenzyl)-1,3,5-tris(II)-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl-1-oxyl free radical, phenanthridine, 1,1-diphenyl-2-pyrrolohydrazide, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. Furthermore, polymerization inhibitors described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of WO-2015/125469 can also be used.

In addition, the following compounds can be used (Me is a methyl group).

【Chemical formula 68】

When the curable resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the curable resin composition of the present invention can be, for example, 0.01 to 20.0 mass%, preferably 0.01 to 5 mass%, more preferably 0.02 to 3 mass%, and even more preferably 0.05 to 2.5 mass%.

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

<Metal Adhesion Improver> The curable 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 aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds with sulfonamide structures, compounds with thiourea structures, phosphoric acid derivatives, β-ketoester compounds, and amino compounds.

[Aluminum-based bonding agents] Examples of aluminum-based bonding agents include tris(ethyl acetoacetate)aluminum, tris(acetylacetonate)aluminum, and ethyl acetoacetate aluminum diisopropylate.

As metal adhesion improvers, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 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. When two or more types are used, their total content is preferably within the above range.

<Other Additives> The curable resin composition of the present invention may contain various additives, such as sensitizers, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, curing catalysts, fillers, antioxidants, UV absorbers, and anti-agglomeration agents, as needed, within the range that achieves the desired effects of the present invention. When such additives are added, their total amount is preferably no greater than 3% by weight of the solids content of the curable resin composition.

[Sensitizer] The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a heat-curing accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., causing electron transfer, energy transfer, and heat generation. This chemically changes the heat-curing accelerator, the thermal radical polymerization initiator, or the photoradical polymerization initiator, causing it to decompose and generate free radicals, acids, or bases. 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-Dimethylaminobenzylidenedihydroindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethyl Benzylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-benzoylbenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzyl Examples of the sensitizer include isoamyl benzoate, 2-benzylbenzimidazole, 1-phenyl-5-benzyltetrazole, 2-benzylbenzothiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Sensitizing dyes can also be used as sensitizers. 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 curable resin composition of the present invention 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 curable resin composition of the present invention. Sensitizers may be used singly or in combination.

[Chain Transfer Agent] The curable 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 Polymer Society, 2005), pages 683-684. Examples of chain transfer agents include compounds containing SH, PH, SiH, and GeH within their molecules. These compounds can generate free radicals by donating hydrogen to low-reactivity free radicals or by deprotonating them after oxidation. Thiol compounds are particularly preferred.

Furthermore, the chain transfer agent may also include the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219.

When the curable 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 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total solids content of the curable 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.

[Surfactant] From the perspective of further improving coating properties, a surfactant can be added to the curable resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, non-ionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. In addition, the following surfactants are also preferred. In the following formula, the parentheses representing the repeating units of the main chain represent the content (molar %) of each repeating unit, and the parentheses representing the repeating units of the side chains represent the number of repetitions of each repeating unit. [Chemical Formula 69] Furthermore, compounds described in paragraphs 0159-0165 of International Publication No. 2015/199219 can also be used as surfactants. Fluoropolymers containing ethylenically unsaturated groups in their side chains can also be used as fluorine-based surfactants. Specific examples include compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Laid-Open No. 2010-164965, such as 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 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 Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

Examples of hydrocarbon surfactants include PIONIN A-76, New Kalgen 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 nonionic surfactants include glycerin, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

Specific examples of cationic surfactants include organosiloxane polymer KP341 (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.).

When the curable resin composition of the present invention contains a surfactant, the surfactant content is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, relative to the total solids content of the curable resin composition of the present invention. The surfactant may be a single type or two or more types. When two or more types of surfactant are used, their total content is preferably within the above range.

[Higher Fatty Acid Derivatives] To prevent polymerization hindrance caused by oxygen, the curable resin composition of the present invention may contain a higher fatty acid derivative such as behenic acid or behenyl amide. This derivative can be unevenly distributed on the surface of the curable resin composition during the drying process after application.

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

When the curable resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solids content of the curable 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, their total content is preferably within the above range.

[Thermal Polymerization Initiator] The resin composition of the present invention may also 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 to initiate or accelerate the polymerization reaction of a polymerizable compound. The addition of a thermal free radical polymerization initiator further promotes the polymerization reaction between the resin and the polymerizable compound, thereby further improving solvent resistance.

Specific examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When a thermal polymerization initiator is included, its content is preferably 0.1-30 mass %, more preferably 0.1-20 mass %, and even more preferably 0.5-15 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, their 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. By including inorganic particles having this average particle size, both the mechanical properties of the cured film and the suppression of exposure light scattering can be achieved.

[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. 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, the aforementioned UV absorbers may be used singly or in combination. The composition of the present invention may or may not contain a UV absorber. However, when a UV absorber is contained, 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. By containing an organic titanium compound, the resin composition 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 or ionic bond. Specific examples of organic titanium compounds are shown in Sections I) to VII below: I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are particularly preferred, as they provide excellent storage stability of the negative photosensitive resin composition and yield a good cured pattern. Specific examples include titanium bis(triethanolamine)diisopropylate, titanium bis(n-butoxy)bis(2,4-glutarate), titanium diisopropoxybis(2,4-glutarate), titanium diisopropoxybis(tetramethylpimelate), and titanium diisopropoxybis(ethyl acetate). II) Tetraalkoxytitanium compounds: for example, tetrakis(n-butoxy)titanium, tetrakis(2-ethylhexyloxy)titanium, tetrakis(isobutoxy)titanium, tetrakis(isopropoxy)titanium, tetrakis(methanol)titanium, tetrakis(methoxypropoxy)titanium, tetrakis(methylphenoxy)titanium, tetrakis(n-nonoxy)titanium, tetrakis(n-propoxy)titanium, tetrastearyltitanium, tetrakis[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc. 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)isopropoxide and titanium tris(dodecylbenzenesulfonate)isopropoxide. V) Titanium oxide compounds: Examples include titanium bis(glutarate)oxide, titanium bis(tetramethylpimelate)oxide, and titanium phthalocyanine oxide. VI) Titanium tetraacetylacetonate compounds: Examples include titanium tetraacetylacetonate. VII) Titanium ester coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanium ester, etc.

Among these, from the perspective of exhibiting better drug resistance, 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. In particular, titanium bis(ethylacetoacetate)diisopropoxy, titanium tetra(n-butoxy), and titanium bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl) are preferred.

When an organic titanium compound is added, its amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the precursor of the cyclized 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 excellent.

[Antioxidant] The composition of the present invention may contain an antioxidant. By including an antioxidant as an additive, the ductility of the cured film and its adhesion to metal materials 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 the position adjacent to the phenolic hydroxyl group (at the 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]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and bis(2,4-di-tert-butyl-6-methylphenol)ethyl phosphite. Examples of commercially available antioxidants include ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO-80, and ADKSTAB 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. The composition of the present invention may contain a potential antioxidant, if desired. Potential antioxidants include compounds whose antioxidant-active sites are protected by protecting groups. These groups are released by heating at 100-250°C or at 80-200°C in the presence of an acid/base catalyst, allowing them to function as antioxidants. Examples of potential antioxidants include compounds described in International Publication Nos. 2014/021023, 2017/030005, and JP-A-2017-008219. Commercially available potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION). As examples of preferred antioxidants, there are 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and compounds represented by the general formula (3).

【Chemical formula 70】

In general formula (3), ^R₅ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, ^R₆ represents an alkylene group having 2 or more carbon atoms, ^R₇ represents an alkylene group having 2 or more 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 general formula (3) inhibits the oxidative degradation of aliphatic groups or phenolic hydroxyl groups in resins. Furthermore, it can inhibit metal oxidation by providing a rust-proofing effect on metal materials.

Because it can act simultaneously on 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. Of 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 through metal complex formation, -NH- is even more preferred.

The compounds represented by the following general formula (3) can be exemplified by the following compounds, but are not limited to the following structures.

【Chemical formula 71】

【Chemical formula 72】

【Chemical formula 73】

【Chemical formula 74】

The antioxidant addition amount is preferably 0.1-10 parts by weight relative to the resin, and more preferably 0.5-5 parts by weight. An amount less than 0.1 parts by weight may not improve the ductility after hardening or the adhesion to metals. Furthermore, an amount greater than 10 parts by weight may interact with the photosensitizer, potentially reducing the sensitivity of the resin composition. A single antioxidant may be used, or two or more may be used. When two or more antioxidants are used, the total amount is preferably within the above range.

<Regarding Restrictions on Other Substances> From the perspective of coating surface properties, the water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass. Methods for maintaining this water content include adjusting the humidity during storage and reducing the porosity of the container.

From the perspective of insulation, the metal content of the hardening 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, chromium, and nickel. When multiple metals are included, the total content of these metals is preferably within the above range.

Furthermore, methods for reducing the amount of metal impurities unintentionally contained in the hardening resin composition of the present invention include selecting raw materials with low metal content as the raw materials constituting the hardening resin composition of the present invention; filtering the raw materials constituting the hardening 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.

In the curable resin composition of the present invention, considering its use 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 content of chlorine atoms and bromine atoms, or the total content of chlorine and bromine ions, respectively, be 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 curable resin composition of the present invention. Furthermore, to prevent contaminants from entering the raw materials or curable resin composition, it is also preferable to use a multi-layer 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.

<Applications of the Curable Resin Composition> The curable resin composition of the present invention is preferably used to form interlayer insulating films for redistribution layers. In addition, it can also be used to form insulating films for semiconductor devices or stress buffer films.

<Preparation of Curable Resin Composition> The curable resin composition of the present invention can be prepared by mixing the aforementioned components. The mixing method is not particularly limited and can be performed using conventionally known methods.

Furthermore, in order to remove foreign matter such as dust and particles from the curable resin composition, it is preferred to filter using a filter. The pore size of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from a productivity perspective, 5 μm or less is preferred, 3 μm or less is more preferred, and 1 μm or less is even more preferred. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. The filter may be pre-cleaned with an organic solvent. In the filter filtration process, multiple filters may be connected in series or in parallel. When using multiple filter types, filters of different pore sizes or materials can be combined. Furthermore, various materials can be filtered multiple times. Multiple filtration cycles can be used for cyclic filtration. Furthermore, filtration can be performed using pressure. When filtration is performed using pressure, the pressure is preferably 0.05 MPa to 0.3 MPa. From a productivity perspective, a pressure of 0.01 MPa to 1.0 MPa is preferred, 0.03 MPa to 0.9 MPa is more preferred, and 0.05 MPa to 0.7 MPa is even more preferred. 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.

(Resin Film, Cured Film, Laminated Body, Semiconductor Device, and Methods for Manufacturing the Same) Next, the resin film, cured film, laminated body, semiconductor device, and methods for manufacturing the same are described.

The cured film of the present invention is formed by curing the curable resin composition or resin film of the present invention. The thickness of the cured film of the present invention can be, for example, 0.5 μm or greater, or 1 μm or greater. The upper limit can be 100 μm or less, or 30 μm or less.

The cured film of the present invention can be stacked in two or more layers, and further stacked in 3 to 7 layers, to form a laminate. The laminate of the present invention preferably includes two or more cured film layers and a metal layer between any of the cured films. For example, a preferred embodiment includes a laminate having a layered structure including at least three layers stacked in sequence: a first cured film, a metal layer, and a second cured film. The first and second cured films are both cured films of the present invention. As a preferred embodiment, for example, the first and second cured films are both films formed by curing the curable resin composition of the present invention. The curable resin composition of the present invention used to form the first cured film and the curable resin composition of the present invention used to form the second cured film may have the same composition or different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a redistribution layer.

Examples of applications for the cured film of the present invention include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, and stress buffering films. Other applications include patterning by etching on sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), and insulating films for packaging applications such as those described above. For information on these applications, see, for example, "Advanced Functionality and Application Technology of Polyimides" published by Science and Technology Co., Ltd. (April 2008), supervised by Masaaki Kakimoto; "Fundamentals and Development of Polyimide Materials" published by the CMC Technical Library (November 2011); and "Latest Polyimides: Fundamentals and Applications" published by the Japan Polyimide and Aromatic Polymer Research Association and edited by NTS Inc. (August 2010).

Furthermore, the cured film of the present invention can also be used in the production of printing plates such as offset printing plates and screen printing plates, in the etching of molded components, and in the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

The method for producing a cured film of the present invention (hereinafter simply referred to as the "production method of the present invention") preferably includes a film-forming process of applying the curable resin composition of the present invention to a substrate to form a film (resin film). The method for producing a cured film of the present invention preferably includes the film-forming process, an exposure process of exposing the film, and a development process of developing the film. Furthermore, the method for producing a cured film of the present invention preferably includes the film-forming process and, if necessary, the development process, and further includes a heating process of heating the film at 50 to 450°C. Specifically, the method preferably includes the following processes (a) to (d). (a) A film-forming process in which a curable resin composition is applied to a substrate to form a film (curable resin composition layer). (b) An exposure process in which the film is exposed to light after the film-forming process. (c) A development process in which the exposed film is developed. (d) A heating process in which the developed film is heated at 50-450°C. The heating in the heating process further hardens the resin layer already hardened by exposure. During this heating process, for example, the alkali generator decomposes, achieving sufficient hardness.

A preferred embodiment of the present invention includes a method for manufacturing a laminated body, including a method for manufacturing a cured film. The method for manufacturing a laminated body of the present embodiment further comprises forming a cured film according to the aforementioned method for manufacturing a cured film, and then performing process (a), processes (a) to (c), or processes (a) to (d). In particular, it is preferred to perform each of the aforementioned processes in sequence a plurality of times, for example, 2 to 5 times (i.e., 3 to 6 times in total). By laminating the cured film in this manner, a laminated body can be manufactured. In the present invention, it is particularly preferred to provide a metal layer on or between portions where the cured film is provided, or on and between portions where the cured film is provided. Furthermore, when manufacturing a laminate, it is not necessary to repeat all of the processes (a) to (d). As described above, a laminate of a cured film can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) a plurality of times.

<Film Formation Process (Layer Formation Process)> The manufacturing method of a preferred embodiment of the present invention includes a film formation process (layer formation process) in which a curable resin composition is applied to a substrate to form a film (layer).

The type of substrate can be appropriately selected depending on the intended use. 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; paper; SOG (Spin-On Glass); TFT (Thin Film Transistor) array substrates; and electrode plates for plasma display panels (PDPs). These substrates may also have a surface layer such as an adhesion layer or an oxide layer. In the present invention, semiconductor substrates are particularly preferred, with silicon substrates, Cu substrates, and mold substrates being even more preferred. Furthermore, these substrates may have a bonding layer or an oxide layer formed from, for example, hexamethyldisilazane (HMDS) on their surfaces. Also, a plate-shaped substrate (base plate) may be used as the substrate. The shape of the substrate is not particularly limited and may be circular or rectangular, but is preferably 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 shorter side of 100 to 1000 mm, preferably 200 to 700 mm.

Furthermore, when a hardening resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes a base material.

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

Specifically, applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the perspective of achieving uniform thickness of the curable resin composition layer, spin coating, slit coating, spray coating, and inkjet coating are more preferred. By appropriately adjusting the solids concentration and coating conditions depending on the method, a resin layer of 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. For spin coating, for example, a rotation speed of 500 to 2,000 rpm for approximately 10 seconds to 1 minute is suitable. Also, depending on the viscosity of the photosensitive resin composition or the desired film thickness, a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds is also preferred. Furthermore, to achieve uniform film thickness, a combination of multiple rotation speeds can be used for coating. Alternatively, a method can be applied in which a coating film previously applied and formed on a temporary support by the aforementioned application method is transferred to a substrate. Regarding the transfer method, the production methods described in paragraphs 0023 and 0036-0051 of Japanese Patent Application Publication No. 2006-023696 or paragraphs 0096-0108 of Japanese Patent Application Publication No. 2006-047592 can also be preferably used in the present invention. Also, a process can be performed to remove excess film from the edges of the substrate. Examples of such processes include edge bead rinsing (EBR), air knife, and back rinse. Alternatively, a pre-wetting process can be used: before applying the resin composition to the substrate, various solvents are applied to the substrate to increase the substrate's wettability before applying the resin composition.

<Drying Process> The manufacturing method of the present invention may include a drying process to remove the solvent after the film formation process (layer formation process). The drying temperature is preferably 50-150°C, more preferably 70-130°C, and even more preferably 90-110°C. The drying time can be, for example, 30 seconds to 20 minutes, preferably 1-10 minutes, and even more preferably 3-7 minutes.

<Exposure Process> The manufacturing method of the present invention may include an exposure process for exposing the film (hardening resin composition layer) to light. The exposure dose is not particularly limited as long as it cures the hardening resin composition. For example, an exposure energy of 100 to 10,000 mJ/ ^cm² at a wavelength of 365 nm is preferred, and 200 to 8,000 mJ/ ^cm² is more preferred.

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

If we explain the exposure wavelength in relation to the light source, we can cite (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic of YAG lasers is 532nm and the third harmonic is 355nm. The curable resin composition of the present invention is particularly preferably exposed using a high-pressure mercury lamp, with i-ray exposure being particularly preferred. This allows for particularly high exposure sensitivity. Also, from the perspectives of operability and productivity, a high-pressure mercury lamp with a broad wavelength (g, h, and i-rays) or a 405nm semiconductor laser are also preferred.

<Developing Process> The manufacturing method of the present invention may include a developing process for developing (developing) the exposed film (hardening resin composition layer). Unexposed portions (non-exposed areas) are removed by developing. The developing method is not particularly limited as long as the desired pattern can be formed. Examples include spraying developer from a nozzle, mist spraying, and immersing the substrate in the developer. Spraying from a nozzle is preferred. The developing process can include continuously supplying developer to the substrate, maintaining the developer in a substantially stationary state on the substrate, vibrating the developer using ultrasound or other methods, and combinations thereof.

Development is performed using a developer. The developer is not particularly limited; any known developer can be used, including one containing an organic solvent or an alkaline aqueous solution.

In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be calculated by inputting the structural formula into ChemBioDraw.

When the developer contains an organic solvent, the organic solvent may preferably be esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate), , ethyl ethoxylate, etc.)), 3-alkoxyalkyl propionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxyalkyl propionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.) Examples of the ethers include methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate, ethyl thiocyanate, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate, ethyl thiocyanate, diethylene glycol dimethyl ether, and ethers such as thiocyanate, thiocyanate, ethyl thiocyanate, thiocyanate, methyl thiocyanate, ethyl ... Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like; and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like are preferably exemplified; and, as cyclic hydrocarbons, for example, toluene, xylene, anisole, limonene, and the like are preferably exemplified; and, as sulfoxides, for example, dimethyl sulfoxide is preferably exemplified; and, mixtures of these organic solvents are also preferably exemplified.

When the developer contains an organic solvent, cyclopentanone and γ-butyrolactone are particularly preferred in the present invention, with cyclopentanone being even more preferred. Furthermore, when the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more.

When the developer 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. Alternatively, the developer may contain 100% by mass of the organic solvent.

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

When the developer is an alkaline aqueous solution, examples of alkaline compounds that can be contained in the alkaline aqueous solution include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), and sodium carbonate, with TMAH being 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.

[Developer Supply Method] The developer supply method is not particularly limited as long as the desired pattern can be formed. Examples include immersing the substrate in the developer, immersion development using a nozzle to supply the developer onto the substrate, and continuous developer supply. The nozzle type 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, methods using vertical nozzles or continuous spray nozzles are preferred. From the perspective of developer permeability to the image area, spray nozzles are even more preferred. Alternatively, a process can be employed in which developer solution is continuously supplied using a vertical nozzle, the substrate is rotated to remove the developer solution, and after spin drying, developer solution is continuously supplied using the vertical nozzle again, and the substrate is rotated to remove the developer solution. This process can be repeated multiple times. Furthermore, methods for supplying developer solution during the development process include continuously supplying developer solution to the substrate, maintaining the developer solution substantially stationary on the substrate, vibrating the developer solution on the substrate using ultrasound or other methods, and combinations of these.

The developing time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developer during development is not particularly specified, but it can generally be performed at 10 to 45°C, preferably 20 to 40°C.

After treatment with a developer, rinsing can be performed. Alternatively, a method can be employed, such as applying a rinse solution while the developer in contact with the pattern has not completely dried. Rinsing is preferably performed in a solvent different from the developer. For example, a solvent contained in the curable resin composition can be used for rinsing. When the developer contains an organic solvent, examples of the rinse solution include PGMEA (propylene glycol monoethyl ether acetate) and IPA (isopropyl alcohol), with PGMEA being preferred. Furthermore, water is a preferred rinse solution for development using a developer containing an aqueous alkaline solution. The optimal rinsing time is 10 seconds to 10 minutes, 20 seconds to 5 minutes is more preferred, and 5 seconds to 1 minute is even more preferred. The temperature of the rinse solution during rinsing is not specifically specified, but it is preferably between 10°C and 45°C, and more preferably between 18°C and 30°C.

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-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester), 2-alkoxypropionic acid alkyl esters (for example, 2-alkoxypropionic acid methyl ester, 2-alkoxypropionic acid ethyl ester, 2-alkoxypropionic acid propyl ester, etc. (for example, 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester), 2-alkoxy-2-methylpropionic acid methyl ester and 2-alkoxy-2-methylpropionic acid ethyl ester (for example, 2-methoxy-2- Examples of the ethers include methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate, ethyl thiocyanate, 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, and propylene glycol monopropyl ether acetate. Examples of the preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of the preferred aromatic hydrocarbons include toluene, xylene, anisole, and limonene; examples of the preferred sulfoxides include dimethyl sulfoxide; examples of the preferred alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbitol, and triethylene glycol; and examples of the preferred amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the rinse solution contains an organic solvent, one organic solvent or a mixture of two or more organic solvents can be used. 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 from a container, supplying the rinsing liquid to the substrate using a sprayer, and continuously supplying the rinsing liquid to the substrate using a mechanism such as a vertical nozzle. From the perspectives of rinse liquid penetration, removal of non-image areas, and manufacturing efficiency, the rinse liquid can be supplied using a shower nozzle, a vertical nozzle, or a mist nozzle. Continuous supply using a mist nozzle is preferred, and from the perspective of rinse liquid penetration into the image area, supply using a mist nozzle is even more preferred. The type of nozzle is not particularly limited; examples include vertical nozzles, shower nozzles, and mist nozzles. Specifically, the rinsing process preferably uses a vertical nozzle to supply or continuously supply the rinsing liquid to the exposed film, and more preferably uses a mist nozzle to supply the rinsing liquid. Additionally, the developer supply method during the rinsing process can include a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is held substantially stationary on the substrate, a process in which the rinsing liquid is vibrated on the substrate using ultrasound or other means, or a combination of these methods.

<Heating Process> The production method of the present invention preferably includes a step (heating process) of heating the developed film at 50-450°C. The heating process is preferably included after the film formation process (layer formation process), drying process, and development process. During the heating process, for example, the alkali generator decomposes to generate a base, which then undergoes a cyclization reaction as a precursor to the specific resin. Furthermore, the curable resin composition of the present invention may contain a radically polymerizable compound other than the precursor to the specific resin, and curing of any unreacted radically polymerizable compound other than the precursor to the specific resin can also occur during this process. The heating temperature (maximum heating temperature) of the layer during the heating process is preferably 50°C or higher, more preferably 80°C or higher, even more preferably 140°C or higher, even more preferably 150°C or higher, even more preferably 160°C or higher, and even more preferably 170°C or higher. As an upper limit, 500°C or lower is preferably, 450°C or lower is even more preferably, 350°C or lower is even more preferably, 250°C or lower is even more preferably, and 220°C or lower is even more preferably.

Heating is preferably performed at a rate of 1-12°C/minute, more preferably 2-10°C/minute, and even more preferably 3-10°C/minute, from the starting temperature to the maximum heating temperature. A rate of 1°C/minute or higher ensures productivity while preventing excessive amine volatilization. A rate of 12°C/minute or lower reduces residual stress in the cured film. Furthermore, in a fast-heating oven, a rate of 1-8°C/second, more preferably 2-7°C/second, and even more preferably 3-6°C/second, from the starting temperature to the maximum heating temperature is preferred.

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

The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.

In particular, when forming a multi-layer laminate, from the perspective of interlayer adhesion of the cured film, the heating temperature is preferably 180°C to 320°C, and more preferably 180°C to 260°C. Although the reason for this is unclear, it is believed that this temperature causes the acetylene groups of the specific resin between the layers to cross-link.

Heating can be performed in stages. For example, a pretreatment process can be performed as follows: heating from 25°C to 180°C at a rate of 3°C/minute, holding at 180°C for 60 minutes, then heating from 180°C to 200°C at a rate of 2°C/minute, and holding at 200°C for 120 minutes. The heating temperature for the pretreatment process is preferably 100-200°C, more preferably 110-190°C, and even more preferably 120-185°C. During this pretreatment process, it is also preferable to perform the treatment while irradiating with UV light, as described in U.S. Patent No. 9,159,547. This pretreatment process can improve membrane properties. The pretreatment process can be performed for a short time, from about 10 seconds to 2 hours, preferably from 15 seconds to 30 minutes. Pretreatment can also be performed in two or more stages, for example, pretreatment step 1 can be performed at a temperature between 100 and 150°C, followed by pretreatment step 2 at a temperature between 150 and 200°C.

It can be further heated and then cooled. The optimal cooling rate at this time is 1 to 5°C/minute.

To prevent the decomposition of certain resins, it is best to conduct the heating process in an atmosphere with a low oxygen concentration by flowing inert gases such as nitrogen, helium, and argon. 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 is not particularly limited; examples include a hot plate, infrared furnace, electric oven, and hot air oven.

<Metal Layer Formation Process> The manufacturing method of the present invention preferably includes a metal layer formation process in which a metal layer is formed on the surface of the developed film (hardening resin composition layer).

The metal layer is not particularly limited, and existing metals can be used. Examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper, aluminum, and alloys containing these metals 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, and Japanese Patent Application Publication No. 2004-101850 can be applied. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and combinations thereof are contemplated. More specifically, patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electrolytic plating can be cited.

The thickness of the metal layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and even more preferably 1 to 10 μm at the thickest wall portion.

<Lamination Process> The manufacturing method of the present invention preferably further includes a lamination process.

The lamination process refers to a series of processes that include, on the surface of a hardened film (resin layer) or metal layer, repeating (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) a heating process. However, it is also possible to repeat only the film formation process (a). Alternatively, it is also possible to perform the heating process (d) at the end or in the middle of the lamination process. In other words, it is possible to repeat the processes (a) to (c) a predetermined number of times, and then perform heating (d), thereby completely curing the accumulated layers of the hardening resin composition. Furthermore, the (e) metal layer formation process may be included after the (c) development process. In this case, the heating step (d) may be performed each time the layer is formed, or may be performed all at once after a predetermined number of layer formations. Of course, the layer formation process may further include the aforementioned drying process or heating process, as appropriate.

When a further layering process is performed after the layering process, a surface activation treatment process may be performed after the heating process, after the exposure process, or after the metal layer formation process. An example of the surface activation treatment is plasma treatment.

The above-described lamination process is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times. Furthermore, the layers in the lamination process may have the same composition, shape, thickness, etc., or may be different layers.

For example, a structure of resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably 3 or more and 7 or less resin layers, and more preferably 3 or more and 5 or less resin layers.

In the present invention, after providing the metal layer, it is particularly preferred to further form a hardened film (resin layer) of the hardening resin composition so as to cover the metal layer. Specifically, an embodiment can be exemplified by repeating the following steps: (a) film formation process, (b) exposure process, (c) development process, (e) metal layer formation process, and (d) heating process; or an embodiment can be exemplified by repeating the following steps: (a) film formation process, (b) exposure process, (c) development process, and (e) metal layer formation process, with (d) heating process being provided at the end or in the middle. By alternately performing the build-up process of the hardening resin composition layer (resin layer) and the metal layer forming process, the hardening resin composition layer (resin layer) and the metal layer can be alternately built up.

(Surface Activation Treatment Process) The method for manufacturing a laminate of the present invention may include a surface activation treatment process for performing a surface activation treatment on at least a portion of the metal layer and the photosensitive resin composition layer. The surface activation treatment process is typically performed after the metal layer formation process, but the metal layer formation process may also be performed after the exposure and development process. 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 photosensitive resin composition layer, or on at least a portion of both the metal layer and the exposed photosensitive 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 photosensitive resin composition layer is formed is surface-activated. By surface-activating the metal layer, adhesion to the resin layer disposed on the surface can be improved. Furthermore, preferably, a portion or all of the exposed photosensitive resin composition layer (resin layer) is also surface-activated. By surface-activating the photosensitive resin composition layer, adhesion to the metal layer or resin layer disposed on the surface-activated surface can be improved. 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 , and _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone, treatment by immersing in an aqueous hydrochloric acid solution to remove the oxide film followed by immersion in an organic surface treatment agent containing a compound having at least one of an amino group and a thiol group, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/ ^m2 , more preferably 1000-100,000 J/ ^m2 , and most preferably 10,000-50,000 J/ ^m2 .

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. Specific examples of semiconductor devices in which the curable resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Application Laid-Open No. 2016-027357, which are incorporated herein by reference. [Examples]

The present invention is further described below with reference to the following examples. The materials, amounts, ratios, processing details, and steps described in the following examples are subject to modification 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 weight standards.

<Synthesis Example B-1: Synthesis of Compound B-1> In a flask equipped with a stirrer and a condenser, 7.25 g (105 mmol) of 1,2,4-triazole (Tokyo Chemical Industry Co., Ltd.), 15.52 g (100 mmol) of Karenz MOI (SHOWA DENKO KK), and 0.01 g of Neostan U-600 (NITTO KASEI CO., LTD.) were dissolved in 70 mL of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) and stirred at 25°C for 1 hour. Subsequently, the mixture was stirred at 45°C for 2 hours, dissolved in 600 mL of ethyl acetate, and transferred to a separatory funnel. The product was then washed twice with 100 mL of water and twice with 150 mL of saturated sodium chloride solution, and dried over sodium sulfate. The product was filtered through filter paper and transferred to a flask. The solvent was removed using an evaporator to yield 18 g of B-1. The structure of B-1 was estimated to be represented by the following formula (B-1). ^1H -NMR spectroscopy confirmed its identity to be B-1. The ^1H -NMR data are shown below. ^1H -NMR data: (heavy dimethyl sulfoxide, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 1.85 (s, 3H), 3.54-3.58 (q, 2H), 4.24-4.26 (t, 2H), 5.66 (s, 1H), 6.03 (s, 1H), 8.27 (s, 1H), 8.86-8.90 (t, 1H), 9.16 (s, 1H) [Chemical formula 75]

<Synthesis Example B-2: Synthesis of Compound B-2> In a flask equipped with a stirrer and condenser, 15.2 g (0.22 mol) of 1,2,4-triazole and 150 mL of dichloromethane were mixed and cooled to below 10°C. Subsequently, 10.5 g (0.1 mol) of methacrylic acid chloride was added dropwise over 1 hour, and the temperature was raised to 20-25°C. After stirring at 20-25°C for 3 hours, 200 mL of dichloromethane was added, and the generated salt was filtered through filter paper, and the filtrate was recovered. The filtrate was transferred to a separatory funnel, washed twice with 50 mL of water and twice with 150 mL of saturated sodium chloride, and dried over sodium sulfate. While filtering through filter paper, the product was transferred to a single-necked flask and the solvent was removed using a distillation device to obtain 12 g of B-2. The structure of B-2 was estimated to be represented by the following formula (B-2). ^1H -NMR spectroscopy confirmed that it was B-2. ^1H -NMR data are shown below. ^1H -NMR data: (deuterated chloroform, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 2.17 (s, 3H), 6.09 (s, 1H), 6.44 (s, 1H), 8.06 (s, 1H), 8.95 (s, 1H) [Chemical formula 76]

<Synthesis Example B-3: Synthesis of Compound B-3> In a flask equipped with a stirrer and a condenser, 7.25 g (105 mmol) of 1,2,4-triazole (Tokyo Chemical Industry Co., Ltd.), 24.7 g (100 mmol) of 3-(triethoxysilyl)propyl isocyanate (Tokyo Chemical Industry Co., Ltd.), and 0.02 g of Neostan U-600 (NITTO KASEI CO., LTD.) were dissolved in 100 mL of tetrahydrofuran (Tokyo Chemical Industry Co., Ltd.) and stirred at 25°C for 1 hour. The mixture was then stirred at 45°C for 2 hours, dissolved in 800 mL of ethyl acetate, and transferred to a separatory funnel. The product was then washed twice with 100 mL of water and twice with 150 mL of saturated sodium chloride solution, and dried over sodium sulfate. The product was filtered through filter paper and transferred to a single-necked flask. The solvent was removed using an evaporator, yielding 26 g of B-3. The structure of B-3 was estimated to be represented by the following formula (B-3). ^1H -NMR spectroscopy confirmed its identity to be B-3. The ^1H -NMR data are shown below. ^1H -NMR data: (D-chloroform, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 0.67-0.72 (t, 2H), 1.21-1.25 (t, 9H), 1.74-1.82 (M, 2H), 3.43-3.48 (q, 2H), 3.81-3.86 (q, 6H), 7.19 (s, 1H), 7.97 (s, 1H), 8.86 (s, 1H) [Chemical formula 77]

<Synthesis Examples B-4 to B-10: Synthesis of Compounds B-4 to B-10> The following compounds B-4 to B-10 were synthesized using the same method as in Synthesis Examples B-1 to B-3. The estimated structures of B-4 to B-10 are shown in the following formulas (B-4) to (B-10), respectively. [Chemical Formula 78]

<Synthesis Example AP-1: Synthesis of Compound AP-1> 15 g of propylene glycol monomethyl ether was added to a flask, and the temperature was raised to 80°C while stirring under nitrogen. Next, 14.52 g (50 mmol) of 3-(triethoxysilyl)propyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.16 g (50 mmol) of the aforementioned B-4, 50 g of propylene glycol monomethyl ether, and 0.46 g of polymerization initiator V-601 (manufactured by Fujifilm Wako Pure Chemical Corporation) were added to the flask, dissolved, and added dropwise over 3 hours. The mixture was then heated to 85°C, stirred for 3 hours, and cooled to room temperature to obtain an AP-1 solution. The solid content concentration of the AP-1 solution (solid content/total solution mass × 100) is 24.1% by mass, and the weight-average molecular weight (Mw) of AP-1 is 12,500. [Chemical Formula 79]

<Synthesis Examples AP-2 to AP-4: Synthesis of Compounds AP-2 to AP-4> Compounds AP-2 to AP-4 were synthesized using the same method as Synthesis Example AP-1. The estimated structures of AP-2 to AP-4 are shown in the following formulas (AP-2) to (AP-4), respectively. In each structure, the subscripts in parentheses represent the molar ratio of each repeating unit. The Mw of AP-2 is 15,800, the Mw of AP-3 is 25,000, and the Mw of AP-4 is 8,500. [Chemical Formula 80]

<Synthesis Examples BP-1 and BP-2: Synthesis of Compounds BP-1 and BP-2> Compounds BP-1 and BP-2 were synthesized using the same method as Synthesis Example AP-1. The estimated structures of BP-1 and BP-2 are shown below in Formulas (BP-1) and (BP-2), respectively. In each structure, the subscripts in parentheses represent the molar ratio of each repeating unit. The Mw of BP-1 is 19,100, and the Mw of BP-2 is 32,800. [Chemical Formula 81]

<Synthesis Examples CP-1 to CP-3: Synthesis of Compounds CP-1 to CP-3> Compounds CP-1 to CP-3 were synthesized using the same method as Synthesis Example AP-1. The estimated structures of CP-1 to CP-3 are shown below in Formulas (CP-1) to (CP-3), respectively. In each structure, the subscripts in parentheses represent the molar ratio of each repeating unit. The Mw of CP-1 is 15,300, the Mw of CP-2 is 20,600, and the Mw of CP-3 is 28,700. [Chemical Formula 82]

<Synthesis Example A-1: Synthesis of Polybenzoxazole Precursor A-1 from 2,2'-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 4,4'-oxydiphenylformyl chloride> 28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 200 g of N-methylpyrrolidone. Next, 12.1 g (153 mmol) of pyridine was added. While maintaining the temperature between -10°C and 0°C, a solution of 20.7 g (70.1 mmol) of 4,4'-oxydiphenylformyl chloride dissolved in 75 g of N-methylpyrrolidone was added dropwise over 1 hour. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was stirred for a further 60 minutes. The polybenzoxazole pro-driver resin was then precipitated in 6 liters of water, and the water-polybenzoxazole pro-driver resin mixture was stirred at 500 rpm for 15 minutes. The polybenzoxazole pro-driver resin was filtered and removed, and the mixture was stirred again in 6 liters of water for 30 minutes and filtered again. The resulting polybenzoxazole pro-driver resin was then dried at 45°C under reduced pressure for 3 days to obtain polybenzoxazole pro-driver A-1. This polybenzoxazole pro-driver A-1 had an Mw = 21,500 and an Mn = 9,500. The structure of polybenzoxazole precursor A-1 is estimated to be represented by the following formula (A-1). [Chemical Formula 83]

<Synthesis Example A-2: Synthesis of a Polyimide Precursor from Pyromellitic Dianhydride, 4,4'-Diaminodiphenyl Ether, and 2-Hydroxyethyl Methacrylate (A-2: Polyimide Precursor Having a Free Radically Polymerizable Group)> 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-Hydroxyethyl Methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diethylene glycol dimethyl ether (DME) were mixed and stirred at 60°C for 18 hours to produce a diester of pyromellitic acid and 2-Hydroxyethyl Methacrylate. The resulting diester was then chlorinated with _SOCl₂ and converted to a polyimide precursor using 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-5. Polyimide precursor A-2 was obtained in the same manner as in Synthesis Example A-5. The weight-average molecular weight of polyimide precursor A-2 was 21,000. The structure of polyimide precursor A-2 is estimated to be represented by the following formula (A-2). [Chemical Formula 84]

Synthesis Example A-3: Synthesis of a Polyimide Precursor from 4,4'-oxydiphthalic Dianhydride, 4,4'-diaminodiphenyl ether, and 2-Hydroxyethyl Methacrylate (A-3: Polyimide Precursor with Free Radical Polymerization Group) 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with _SOCl₂ and converted to a polyimide precursor using 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example A-5. Polyimide precursor A-3 was obtained in the same manner as in Synthesis Example A-5. The weight-average molecular weight of polyimide precursor A-3 was 19,600. The structure of polyimide precursor A-3 is estimated to be represented by the following formula (A-3). [Chemical Formula 85]

<Synthesis Example A-4: Synthesis of a Polyimide Precursor from 4,4'-oxydiphthalic Dianhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (di-toluidine), and 2-hydroxyethyl methacrylate (A-4: Polyimide Precursor with Free Radical Polymerization Group)> 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with _SOCl₂ and converted to a polyimide precursor using 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example A-5. Polyimide precursor A-4 was obtained in the same manner as in Synthesis Example A-5. The weight-average molecular weight of polyimide precursor A-4 was 23,500. The structure of polyimide precursor A-4 is estimated to be represented by the following formula (A-4). [Chemical Formula 86]

[Synthesis Example A-5: Synthesis of Polyimide Precursor Resin A-5 from Oxydiphthalic Dianhydride, 4,4'-Diphthalic Acid Anhydrous, 2-Hydroxyethyl Methacrylate, and 4,4'-Diaminodiphenyl Ether] In a dry reactor equipped with a flat-bottomed joint equipped with a stirrer, a condenser, and an internal thermometer, 9.49 g (32.25 mmol) of 4,4'-Diphthalic Acid Anhydrous and 10.0 g (32.25 mmol) of oxydiphthalic dianhydride were suspended in 140 mL of diethylene glycol dimethyl ether while removing water. Next, 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water, and 10.7 g (135 mmol) of pyridine were added, and the mixture was stirred at 60°C for 18 hours. The mixture was then cooled to -20°C, and 16.1 g (135.5 mmol) of sulfinyl chloride was added dropwise over 90 minutes. This resulted in a white precipitate of pyridinium hydrochloride. The mixture was then warmed to room temperature and stirred for 2 hours. Then, 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added, resulting in a clear solution. Next, a solution of 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour to the resulting transparent liquid. Subsequently, 5.6 g (17.5 mmol) of methanol and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was filtered, stirred again in 4 liters of water for 30 minutes, and filtered again. The resulting polyimide precursor resin was then dried at 45°C under reduced pressure for three days to obtain polyimide precursor A-5. The resulting polyimide precursor A-5 had a weight average molecular weight of 23,800 and a number average molecular weight of 10,400. The structure of polyimide precursor A-5 is estimated to be represented by the following formula (A-5). [Chemical Formula 87]

<Synthesis Example A-6: Synthesis of Polyimide Precursor A-6 from 4,4'-Oxydiphthalic Dianhydride, 4,4'-Diaminodiphenyl Ether, and 2-Hydroxyethyl Methacrylate> 155.1 g of 4,4'-Oxydiphthalic Dianhydride (ODPA) was placed in a separable flask, followed by 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone. While stirring at room temperature, 79.1 g of pyridine was added to obtain a reaction mixture. After the exotherm due to the reaction subsided, the mixture was naturally cooled to room temperature and allowed to stand for 16 hours. Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension of 93.0 g of 4,4'-diaminodiphenyl ether in 350 mL of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 30 mL of ethanol was added and stirred for 1 hour. Then, 400 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to 3 liters of ethanol, yielding a precipitate consisting of a crude polymer. The resulting crude polymer was filtered and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer. The resulting precipitate was filtered and then vacuum-dried to obtain a powdered polyimide precursor A-6. The weight-average molecular weight (Mw) of the polyimide precursor A-6 was measured to be 24,000.

<Synthesis Example A-7: Synthesis of Polyimide Precursor A-7 from 3,3',4,4'-Biphenyltetracarboxylic Dianhydride, 4,4'-Diaminodiphenyl Ether, and 2-Hydroxyethyl Methacrylate> Polymer A-7 was obtained by the same method as described in Synthesis Example 6, except that 147.1 g of 3,3',4,4'-biphenyltetracarboxylic Dianhydride was used in place of 155.1 g of 4,4'-oxydiphthalic Dianhydride. The weight-average molecular weight (Mw) of this polymer A-7 was measured to be 22,900.

<Synthesis Example PBI-1: Synthesis of Polyimide PBI-1> In a flask equipped with a condenser and stirrer, while removing moisture, 22.2 g (50 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.02 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 100.0 g of N-methylpyrrolidone (NMP). Subsequently, 11.9 g (45 mmol) of the diamine (AA-1) described below was added, and the mixture was stirred at 25°C for 3 hours and then at 45°C for a further 3 hours. Next, 15.8 g (200 mmol) of pyridine, 12.8 g (125 mmol) of acetic anhydride, and 50 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80°C for 3 hours. Then, 50 g of N-methylpyrrolidone (NMP) was added to dilute the mixture. The reaction mixture was precipitated in 1 liter of methanol and stirred at 3000 rpm for 15 minutes. The resin was removed by filtration, and the mixture was stirred again in 1 liter of methanol for 30 minutes and filtered again. The resulting resin was dried at 40°C under reduced pressure for 1 day to obtain polyimide PBI-1. The molecular weight of PBI-1 was Mw = 19,000 and Mn = 8,100. The structure of polyimide PBI-1 is estimated to be represented by the following formula (PBI-1). [Chemical Formula 88]

<Synthesis Example AA-1: Synthesis of Diamine AA-1> In a flask equipped with a condenser and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Corporation) and 17.4 g (0.22 mol) of dehydrated pyridine (manufactured by Fujifilm Wako Pure Chemical Corporation) were dissolved in 78 g of ethyl acetate and cooled to below 5°C. Next, 48.4 g (0.21 mol) of 3,5-nitrobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate and added dropwise to the flask over 1 hour using a dropping funnel. After the addition was complete, the mixture was stirred at below 10°C for 30 minutes, then heated to 25°C and stirred for 3 hours. The reaction mixture was then diluted with 600 mL of ethyl acetate ( _CH₃COOEt ) and transferred to a separatory funnel. The mixture was then washed sequentially with 300 mL of water, 300 mL of saturated sodium bicarbonate (baking soda), 300 mL of dilute hydrochloric acid, and 300 mL of saturated sodium chloride. After separation and washing, the mixture was dried over 30 g of magnesium sulfate, concentrated in a distiller, and vacuum-dried to yield 61.0 g of the dinitro compound (A-1). Into a flask equipped with a condenser and a stirrer were weighed 27.9 g (500 mmol) of reduced iron (manufactured by FUJIFILM Wako Pure Chemical Corporation), 5.9 g (110 mmol) of ammonium chloride (manufactured by FUJIFILM Wako Pure Chemical Corporation), 3.0 g (50 mmol) of acetic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation), and 0.03 g of 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd.). 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred. Subsequently, 16.2 g of the dinitro compound (A-1) was added gradually over 1 hour, followed by stirring for 30 minutes. Next, the external temperature was raised to 85°C, stirred for 2 hours, and cooled to below 25°C. The mixture was then filtered using diatomaceous earth (registered trademark). The filtrate was concentrated using a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separatory funnel and washed twice with 300 mL of saturated sodium bicarbonate, followed by 300 mL of water and 300 mL of saturated sodium chloride solution. After separation and washing, the mixture was dried with 30 g of magnesium sulfate, concentrated using a evaporator, and vacuum dried to obtain 11.0 g of diamine (AA-1). [Chemical Formula 89]

<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 contents of the components listed in the table, excluding the solvent, are the amounts (parts by mass) listed in the "Amount Added" column of each table. In addition, for AP-1 to AP-4, BP-1 to BP-2, and CP-1 to CP-3, the solid content in the solution was the amount (parts by mass) listed in the "Amount Added" column of each table. The resulting curable resin composition and the comparative composition were pressure-filtered through a polytetrafluoroethylene filter with a pore width of 0.8 μm. In the table, "-" indicates that the composition does not contain the corresponding component.

【Table 1】 Resin Compound B Compound C Compound D Compound E Photopolymerization initiator polymerizable compounds polymerization inhibitors Alkali generators additives solvent Hardening temperature (°C) Adhesion when laminating multiple layers copper adhesion Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Embodiment 1 A-2 32 B-1 0.2 - 0 C-2 0.1 D-1 0.1 BP-1 0.12 E-1 0.1 OXE-01 1.2 A-DPH 6.0 F-1 0.08 I-1 0.1 - 0 DMSO/GBL 60 230 A A 2 A-3 32 B-2 0.2 - 0 C-2 0.1 D-1 0.1 BP-1 0.12 E-1 0.1 OXE-01 1.2 SR-209 6.0 F-3 0.08 I-2 0.1 - 0 DMSO/GBL 60 230 B A 3 A-4 32 B-3 0.2 - 0 C-2 0.1 D-1 0.1 BP-2 0.12 E-1 0.1 OXE-01 1.2 SR-209 6.0 F-2 0.08 I-3 0.1 - 0 DMSO/GBL 60 230 A A 4 A-5 32 B-4 0.2 - 0 C-4 0.1 D-1 0.1 BP-1 0.12 E-2 0.1 OXE-01 1.2 SR-209 6.0 F-2 0.08 I-1 0.1 - 0 DMSO/GBL 60 230 B A 5 A-6 32 B-5 0.2 - 0 C-3 0.1 D-1 0.1 BP-2 0.12 E-1 0.1 OXE-01 1.2 SR-209 6.0 F-2 0.08 I-2 0.1 - 0 DMSO/GBL 60 230 A B 6 A-7 32 B-6 0.2 - 0 C-1 0.1 D-1 0.1 - 0 E-1 0.1 OXE-01 1.2 SR-209 6.0 F-2 0.08 I-2 0.1 J-1 0.12 DMSO/GBL 60 230 B B 7 A-3 32 B-7 0.2 - 0 C-5 0.1 D-1 0.1 BP-2 0.12 E-1 0.1 OXE-01 1.2 SR-209 6.0 F-2 0.08 I-2 0.1 - 0 NMP 60 230 A A 8 A-3 32 B-8 0.2 CP-1 0.12 C-6 0.1 D-2 0.1 - 0 E-2 0.1 OXE-01 1.2 SR-209 6.0 F-2 0.08 I-4 0.1 - 0 DMSO/GBL 60 230 B B 9 A-3 32 B-9 0.2 CP-1 0.12 C-6 0.1 D-2 0.1 - 0 E-1 0.1 OXE-01 1.2 SR-209 6.0 F-2 0.08 I-4 0.1 - 0 DMSO/GBL 60 230 B B 10 A-3 32 B-1 0.2 CP-2 0.06 C-5 0.1 D-1 0.1 BP-1 0.06 E-1 0.1 OXE-02 1.2 SR-209 6.0 F-1 0.08 I-1 0.1 - 0 DMSO/GBL 60 230 A A 11 A-3 32 B-10 0.2 CP-3 0.06 C-7 0.1 D-3 0.1 BP-2 0.06 E-1 0.1 OXE-01 1.2 A-DPH 6.0 F-1 0.08 I-2 0.1 - 0 DMSO/GBL 60 230 A A 12 A-3 32 B-1 0.2 CP-1 0.1 C-2 0.1 - 0 BP-1 0.12 E-1 0.1 OXE-01 1.2 A-DPH 6.0 F-1 0.08 I-3 0.1 - 0 DMSO/GBL 60 230 A B 13 A-3 32 B-1 0.2 CP-2 0.17 - 0 D-5 0.1 BP-1 0.05 E-1 0.1 OXE-01 1.2 SR-231 6.0 F-1 0.08 I-2 0.1 - 0 DMSO/GBL 60 230 B B 14 A-1 32 B-1 0.32 - 0 C-6 0.1 - 0 - 0 E-1 0.2 OXE-01 1.2 SR-239 6.0 F-1 0.08 I-2 0.1 - 0 NMP 60 300 A B 15 A-3 32 B-1 0.32 - 0 - 0 - 0 - 0 E-1 0.3 OXE-01 1.2 SR-231 6.0 F-1 0.08 I-2 0.1 - 0 DMSO/GBL 60 230 B C 16 A-6/A-7 16/ 16 - 0 AP-1 0.3 C-2 0.1 D-1 0.12 - 0 E-1 0.1 OXE-01 1.2 A-DPH 6.0 F-1 0.08 I-1 0.1 - 0 DMSO/GBL 60 230 A B

【Table 2】 Resin Compound B Compound C Compound D Compound E Photopolymerization initiator polymerizable compounds polymerization inhibitors Alkali generators additives solvent Hardening temperature (°C) Adhesion when laminating multiple layers copper adhesion Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Kind Addition amount Embodiment 17 A-6/A-7 22/10 - 0 AP-2 0.3 C-2 0.1 D-4 0.12 - 0 E-3 0.1 OXE-01 1.2 SR-209 6.0 F-4 0.08 I-2 0.1 - 0 DMSO/GBL 60 230 B B 18 A-3 32 - 0 AP-3 0.3 C-2 0.1 D-6 0.12 - 0 E-3 0.1 OXE-01 1.2 SR-209 6.0 F-4 0.08 I-2 0.1 - 0 DMSO/GBL 60 230 B B 19 A-3 32 - 0 AP-4 0.3 C-2 0.1 D-1 0.12 - 0 E-1 0.1 OXE-01 1.2 SR-209 6.0 F-2 0.08 I-2 0.1 - 0 DMSO/GBL 60 230 A B 20 A-3 32 - 0 CP-1 0.3 C-2 0.1 D-1 0.12 - 0 E-1 0.1 OXE-01 1.2 SR-209 6.0 F-2 0.08 I-2 0.1 - 0 DMSO/GBL 60 230 A B twenty one PBI-1 30 B-1 0.2 CP-2 0.06 C-5 0.1 D-1 0.1 BP-1 0.06 E-1 0.1 OXE-02 1.2 SR-209 8.0 F-1 0.08 I-1 0.1 - 0 DMSO/GBL 60 230 A A Comparative example 1 A-6 32 - 0 - 0 C-2 0.2 - 0 - 0 E-2 0.3 OXE-02 1.2 A-DPH 6.0 F-1 0.08 I-2 0.1 J-1 0.12 DMSO/GBL 60 230 C D 2 A-1 32 - 0 - 0 C-2 0.2 - 0 - 0 E-2 0.3 OXE-02 1.2 SR-239 6.0 F-1 0.08 I-3 0.1 J-1 0.12 NMP 60 300 D E 3 PBI-1 30 - 0 - 0 C-2 0.2 - 0 - 0 E-2 0.3 OXE-02 1.2 SR-239 8.0 F-1 0.08 I-4 0.1 J-1 0.12 NMP 60 230 D C

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

[Resin] •A-1 to A-7, PBI-1: Polybenzoxazole precursor A-1 synthesized in the above synthesis example, polyimide precursors A-2 to A-7, polyimide PBI-1

[Compound B] •B-1 to B-10: B-1 to B-10 synthesized in the above-mentioned Synthesis Example •AP-1 to AP-4: AP-1 to AP-4 synthesized in the above-mentioned Synthesis Example •CP-1 to CP-3: CP-1 to CP-3 synthesized in the above-mentioned Synthesis Example B-1 to B-10 correspond to the above-mentioned Low Molecular Weight Compound B. AP-1 to AP-4 and CP-1 to CP-3 correspond to the above-mentioned Resin B.

[Compound C] •C-1 to C-7: Compounds represented by the following formulas (C-1) to (C-7) [Chemical Formula 90]

[Compound D] • D-1 to D-6: Compounds represented by the following formulas (D-1) to (D-6) • BP-1 to BP-2: BP-1 to BP-2 synthesized in the above synthesis example. D-1 to D-6 correspond to the above-mentioned low molecular weight compound D. BP-1 to BP-2 correspond to the above-mentioned resin D. [Chemical Formula 91]

[Compound E] •E-1 to E-3: Compounds represented by the following formulas (E-1) to (E-3) [Chemical Formula 92]

[Photopolymerization initiators (all trade names)] •OXE-01: IRGACURE OXE 01 (manufactured by BASF) •OXE-02: IRGACURE OXE 02 (manufactured by BASF)

[Polymerizable compounds (all trade names)] •SR-209: SR-209 (manufactured by Sartomer Company, Inc.) •SR-231: SR-231 (manufactured by Sartomer Company, Inc.) •SR-239: SR-239 (manufactured by Sartomer Company, Inc.) •A-DPH: Dipentatriol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Polymerization inhibitor] •F-1: 1,4-benzoquinone •F-2: 4-methoxyphenol •F-3: 1,4-dihydroxybenzene •F-4: Compound with the following structure [Chemical Formula 93]

[Alkali Generator] •I-1 to I-3: Compounds with the following structures •I-4: WPBG-27 (FUJIFILM Wako Pure Chemical Corporation) [Chemical Formula 94]

[Additives] •J-1: N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Solvent] •DMSO: Dimethyl sulfoxide •GBL: γ-Butyrolactone •NMP: N-Methylpyrrolidone In the table, "DMSO/GBL" indicates that a mixture of DMSO and GBL at a mass ratio of 80:20 was used.

<Evaluation> [Evaluation of Copper Adhesion] Each of the filtered curable resin compositions or the comparative composition was applied to a copper substrate in a layered manner using a spin coating method to form a curable resin composition layer. The copper substrate to which the curable resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes, forming a uniform curable resin composition layer with a thickness of 20 μm on the copper substrate. Using a stepper (Nikon NSR 2005 i9C), the curable resin composition layer on the copper substrate was exposed to light at an exposure energy of 500 mJ/ ^cm² using a mask with a 100 μm square unmasked area. The film was then developed with cyclopentanone for 60 seconds, resulting in a 100 μm square resin layer. The temperature was then increased at a rate of 10°C/min under a nitrogen atmosphere. After reaching the temperature listed in the "Curing Temperature (°C)" column in the table, the temperature was maintained for 3 hours, yielding Resin Film 2. In the example using I-4 as the base generator, after reaching the temperature listed in the "Curing Temperature (°C)" column, the entire pattern surface was exposed to i-rays at an exposure dose of 500 mJ/ ^cm² while maintaining that temperature for 3 hours. Shear force was measured on a 100μm square of resin film 2 on a copper substrate using an adhesion tester (CondorSigma, manufactured by XYZTEC) at 25°C and 65% relative humidity (RH). A greater shear force indicates greater adhesion, indicating excellent adhesion between the metal and the cured film, resulting in a better result. Evaluation was performed according to the following criteria, and the results are reported in the "Copper Adhesion" column in the table. Evaluation Criteria: A: Shear force exceeding 40 gf. B: Shear force exceeding 35 gf but less than 40 gf. C: Shear force exceeding 30 gf but less than 35 gf. D: Shear force exceeding 25 gf but less than 30 gf. E: Shear force less than 25 gf. 1 gf is 9.80665 × 10 ^-3 N.

[Evaluation of Adhesion in Multilayer Lamination] -Fabrication of Laminated Structures- Each curable resin composition or a comparative composition was applied in layers onto a silicon wafer by spin coating and dried using a hot plate at 100°C for 5 minutes to form a curable resin layer. The curable resin layer was then exposed using a stepper (Nikon NSR 2005 i9C) at an exposure energy of 500 mJ/ ^cm² through a mask with a 10μm diameter circular non-exposed area. The exposed curable resin layer was then developed with cyclopentanone for 60 seconds to form 10μm diameter holes. Next, the resin layer (pattern) was heated for three hours in a nitrogen atmosphere at the temperature listed in the "Curing Temperature (°C)" column to form a resin layer. In the example using I-4 as the base generator, after reaching the temperature listed in the "Curing Temperature (°C)" column, the entire surface of the pattern was exposed to i-rays at an exposure dose of 500 mJ/ ^cm² while maintaining that temperature for three hours. The heated resin layer (pattern) was then cooled to room temperature and copper-plated to form a 5μm-thick copper thin film on the resin layer, forming laminate 1. Next, the copper thin film of laminate 1 was irradiated with oxygen plasma, and then a curable resin composition was applied, exposed, developed, and heated, followed by copper plating. A 5-μm-thick copper thin film was formed on the resin layer, resulting in laminate 2. Next, the copper thin film of laminate 2 was irradiated with oxygen plasma, and then a curable resin composition was applied, exposed, developed, and heated, followed by copper plating. A 5-μm-thick copper thin film was formed on the resin layer, resulting in laminate 3. -Evaluation of peeling defects- The laminate 3 was cut vertically and a cross section with a width of 5 mm was observed to confirm the presence and number of peelings between resin layers/resin layers and between copper/resin layers. The less peeling occurs, the better the adhesion is when multiple layers are laminated, which is a better result. The evaluation was carried out according to the following evaluation standards, and the evaluation results are recorded in the "Adhesion in multiple layers" column in the table. -Evaluation standards- A: No peeling occurred B: 1 to 2 peelings occurred C: 3 to 5 peelings occurred D: 6 or more peelings occurred

<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 thereon by spin coating. The layer was dried at 100°C for 4 minutes to form a 20μm thick curable resin composition layer. The layer 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 layer was heated at 100°C for 4 minutes. Following heating, the layer 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 to 230°C. It was then maintained at 230°C for three hours to form an interlayer insulating film for the redistribution layer. This interlayer insulating film exhibited excellent insulating properties. Semiconductor devices were also fabricated using this interlayer insulating film for the redistribution layer, and their operation was confirmed to be flawless.

without.

Claims (23)

A curable resin composition comprises: at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole; and a compound B having a polymerizable group and an azole group, wherein the polymerizable group is a free radical polymerizable group, and the azole group in the compound B is a group represented by the following formula (B-1) or the following formula (B-2): In formula (B-1), ^RB1 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, ^ZB1 to ^ZB4 each independently represent = ^CRB7- or a nitrogen atom, ^RB7 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, and at least one of ^RB1 and ^RB7 included in formula (B-1) represents a bonding site with a structure having a polymerizable group; in formula (B-2), ^RB2 to ^RB6 each independently represent a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, ^ZB5 and ^ZB6 each independently represent = ^CRB8- or a nitrogen atom, ^RB8 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group having no polymerizable group, wherein at least one of ^RB2 to ^RB6 and ^RB8 included in formula (B-2) represents a bonding site to a structure having a polymerizable group. A curable resin composition comprising: at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide, and polybenzoxazole; and compound B, which is a compound having a polymerizable group and an azole group, wherein the polymerizable group is a free radical polymerizable group, and the resin has a polymerizable group on a side chain. A curable resin composition comprising: at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide, and polybenzoxazole; a compound B having a polymerizable group and an azole group; and a photopolymerization initiator or a thermal polymerization initiator, wherein the polymerizable group is a free radical polymerizable group. A curable resin composition comprising: at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide, and polybenzoxazole; and compound B having a polymerizable group and an azole group, wherein the polymerizable group is a free radical polymerizable group. The curable resin composition as described in claim 4, wherein the compound B comprises a compound B having a molecular weight of less than 2,000. The curable resin composition according to claim 4 or claim 5, wherein the compound B comprises, as the polymerizable group, at least one group selected from the group consisting of a free radical polymerizable group and an alkoxysilyl group. The curable resin composition according to any one of claims 2 to 4, wherein the azole group in the compound B is a group represented by the following formula (B-1) or the following formula (B-2); In formula (B-1), ^RB1 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, ^ZB1 to ^ZB4 each independently represent = ^CRB7- or a nitrogen atom, ^RB7 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, and at least one of ^RB1 and ^RB7 included in formula (B-1) represents a bonding site with a structure having a polymerizable group; in formula (B-2), ^RB2 to ^RB6 each independently represent a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group, ^ZB5 and ^ZB6 each independently represent = ^CRB8- or a nitrogen atom, and R ^B8 represents a bonding site with a structure having a polymerizable group, a hydrogen atom, or a monovalent organic group without a polymerizable group. At least one of ^RB2 to ^RB6 and ^RB8 included in formula (B-2) represents a bonding site with a structure having a polymerizable group. The curable resin composition as described in any one of claims 1 to 3, wherein the compound B comprises a compound B having a molecular weight of less than 2,000. The curable resin composition according to any one of claims 1 to 4 further comprises a compound C which is a compound having no polymerizable group but having an azole group. The curable resin composition according to claim 9, wherein the compound C is a compound represented by the following formula (C-1) or the following formula (C-2); In formula (C-1), Z ¹ to Z ⁴ each independently represent ═CR ⁷ - or a nitrogen atom, R ¹ represents a hydrogen atom or a monovalent organic group, R ⁷ represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (C-1) does not contain a polymerizable group. In formula (C-2), Z ⁵ to Z ⁶ each independently represent ═CR ⁸ - or a nitrogen atom, R ² to R ⁶ each independently represent a hydrogen atom or a monovalent organic group, R ⁸ represents a hydrogen atom or a monovalent organic group, and the structure represented by formula (C-2) does not contain a polymerizable group. The curable resin composition as described in any one of claim 1, claim 3, and claim 4, wherein at least one resin selected from the group consisting of the aforementioned polyimide precursor, polybenzoxazole precursor, polyimide, and polybenzoxazole has a polymerizable group capable of polymerizing with the polymerizable group in the aforementioned compound B. The curable resin composition according to any one of claims 1 to 4 further comprises a compound D as a silane coupling agent having a polymerizable group different from an alkoxysilyl group and not having an azole group. The curable resin composition as described in claim 12, wherein at least one resin selected from the group consisting of the aforementioned polyimide precursor, polybenzoxazole precursor, polyimide, and polybenzoxazole has a polymerizable group capable of polymerizing with the polymerizable group in the aforementioned compound D. The curable resin composition according to any one of claims 1 to 4 further comprises a compound E as a silane coupling agent having neither a polymerizable group different from an alkoxysilyl group nor an azole group. The curable resin composition according to any one of claims 1 to 4 is used for forming an interlayer insulating film for a redistribution layer. A cured film formed by curing the curable resin composition described in any one of claims 1 to 15. A laminate comprising two or more layers of the hardened film according to claim 16, wherein a metal layer is provided between any of the hardened films. A laminate comprising two or more cured films, with a metal layer between any of the cured films. Any of the cured films comprises a compound B comprising at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide, and polybenzoxazole, and having a polymerizable group and an azole group, wherein the polymerizable group is a free radical polymerizable group. The cured film is formed by curing the curable resin composition. A laminate comprising a cured film and a metal layer in contact with the cured film. The cured film is formed by curing a curable resin composition comprising at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimide, and polybenzoxazole, and comprising a compound B having a polymerizable group and an azole group, wherein the polymerizable group is a free radical polymerizable group. A method for producing a cured film includes a film-forming process comprising applying the curable resin composition described in any one of claims 1 to 15 to a substrate to form the film. The method for manufacturing a hardened film as described in claim 20 comprises: an exposure process for exposing the film; and a development process for developing the film. The method for manufacturing a hardened film as described in claim 20 or claim 21 includes a heating process of heating the film at 50-450°C. A method for producing a hardened film includes a film-forming process in which a hardening resin composition is applied to a substrate to form the film. The substrate is a semiconductor substrate such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, or amorphous silicon; quartz; an optical film; a ceramic material; a vapor-deposited film; a magnetic film; a reflective film; a metal substrate; paper; spin-on glass; a thin-film transistor array substrate; or an electrode plate for a plasma display panel. The hardening resin composition is a compound B selected from the group consisting of at least one resin selected from a polyimide precursor, a polybenzoxazole precursor, a polyimide, and a polybenzoxazole, and having a polymerizable group and an azole group, wherein the polymerizable group is a free radical polymerizable group.