Resin composition, cured material, laminate, method for manufacturing cured material, semiconductor device, and compound

Abstract

The present invention provides a resin composition, a cured product formed by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a semiconductor device containing the cured product or the laminate, and a novel compound, wherein the resin composition comprises a cyclized resin or a precursor thereof, and the content of carboxylic anhydride relative to the total mass of the resin composition is 0.5% by mass or less.

Description

[Technical Field]

[0001] This invention relates to a resin composition, a cured material, a laminate, a method for manufacturing the cured material, a semiconductor device, and a compound. [Previous Technology]

[0002] Cyclic resins such as polyimide have excellent heat resistance and insulation properties, and therefore can be used for a variety of applications. These applications are not particularly limited; for example, in the case of semiconductor devices used for actual installation, they can be used as insulating films, sealing materials, or protective films. Furthermore, they can also be used as base films or cover films for flexible substrates.

[0003] For example, in the above-described applications, cyclic resins such as polyimide are used in the form of a resin composition comprising at least one of a cyclic resin such as polyimide and a precursor of a cyclic resin. For example, such a resin composition is applied to a substrate by coating to form a photosensitive film, and then exposed, developed, heated, etc., as needed, thereby forming a cured material on the substrate. The precursor of the aforementioned cyclic resin, such as the polyimide precursor, is cyclized by heating to become a cyclic resin such as polyimide in the cured material. The resin composition can be applied by known coating methods, etc., therefore, it can be said that the design freedom of the applied resin composition, such as its shape, size, and application position, is high, and its manufacturing adaptability is excellent. Considering that in addition to the high performance of cyclic resins such as polyimide, such excellent manufacturing adaptability is also present, the expansion of industrial applications of the above-described resin composition is increasingly promising.

[0004] For example, Patent Document 1 describes a method for manufacturing a patterned hardening film, which includes: coating a photosensitive resin composition comprising (A) a polyimide precursor having polymerizable unsaturated bonds, (B) a polymerizable monomer, (C) a photopolymerization initiator, and (D) a thermal free radical generator onto a substrate and drying it to form a photosensitive resin film; exposing the photosensitive resin film to a pattern to obtain a resin film; developing the exposed resin film with an organic solvent to obtain a patterned resin film; and heat-treating the patterned resin film.

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2020-056934

[0006] In resin compositions used to obtain cured products, excellent storage stability of the resin composition is required. [Summary of the Invention]

[0007] The object of the present invention is to provide a resin composition with excellent preservation stability, a cured product formed by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a semiconductor device containing the cured product or the laminate, and a novel compound.

[0008] The following are examples of representative embodiments of the present invention. <1> A resin composition comprising a cyclized resin or a precursor thereof, wherein the content of carboxylic anhydride relative to the total mass of the resin composition is 0.5% by mass or less. <2> The resin composition as described in <1> comprises a silane coupling agent. <3> The resin composition as described in <2> comprises compound A as the silane coupling agent, wherein compound A has at least one group selected from the group consisting of hydroxyl, amino, and thiol groups, at least one group selected from amide and ester groups, and a group represented by the following formula (S-1). [Chemical Formula 1] In formula (S-1), R1 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms that can be substituted, R2 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms that can be substituted, x represents an integer of 1 to 3, and * represents a bonding site with other structures. <4> A resin composition comprising: a cyclized resin or a precursor thereof; and compound A having at least one group selected from the group consisting of hydroxyl, amino, and thiol groups, at least one group selected from acetaminophen and ester groups, and a group represented by the following formula (S-1). [Chemical Formula 2] In formula (S-1), R1 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms that can be substituted, R2 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms that can be substituted, x represents an integer of 1 to 3, and * represents a bonding site with other structures. <5> A resin composition as described in <3> or <4>, wherein the above-mentioned compound A is a compound represented by formula (1-1). [Chemical Formula 3] In Formula (1-1), R1 independently represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms that can be substituted, R2 independently represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms that can be substituted, L represents an m+n valence linkage containing an amino group or an ester group, x represents an integer of 1 or more and 3 or less, m represents an integer of 1 or more, and n represents an integer of 1 or more. <6> The resin composition as described in <5>, wherein the carbon atom containing L in Formula (1-1) and directly bonded to the hydroxyl group in Formula (1-1) is a carbon atom constituting an aliphatic hydrocarbon group. <7> The resin composition as described in any one of <3> to <6>, wherein the above-mentioned compound A is a compound represented by Formula (2-1). [Chemical Formula 4] In Formula (2-1), R1 independently represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms that can be substituted, R2 independently represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms that can be substituted, L1 represents a single bond or a divalent linkage, Z represents an amino group, the orientation of the amino group in Z is not particularly limited, L2 represents a single bond or a divalent linkage, Ar represents an aromatic group, X represents an alkyl group, and x represents an integer of 1 to 3. <8> A resin composition as described in any one of <3> to <7>, wherein the molecular weight of compound A is 300 to 1,000.<9> A resin composition as described in any one of <1> to <8>, comprising a photopolymerization initiator. <10> A resin composition as described in any one of <1> to <9>, comprising a polymerizable compound. <11> A resin composition as described in any one of <1> to <10>, comprising an alkali-generating agent. <12> A resin composition as described in any one of <1> to <11>, used for forming an interlayer insulating film for a rewiring layer. <13> A curable material formed by curing any one of the resin compositions described in <1> to <12>. <14> A laminate comprising two or more layers composed of the curable material described in <13>, wherein a metal layer is included between any of the layers composed of the curable material. <15> A method of manufacturing a curable material, comprising a film forming step of applying any one of the resin compositions described in <1> to <12> to form a film on a substrate. <16> A method for manufacturing a cured material as described in <15>, comprising an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern. <17> A method for manufacturing a cured material as described in <15> or <16>, comprising a heating step of heating the film at 50–450°C. <18> A semiconductor device comprising the cured material described in <13> or the laminate described in <14>. <19> A compound represented by formula (2-1), [Chemical Formula 5] In formula (2-1), R1 independently represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms that can be substituted, R2 independently represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms that can be substituted, L1 represents a single bond or a divalent linkage, Z represents an amino group, the orientation of the amino group in Z is not particularly limited, L2 represents a single bond or a divalent linkage, Ar represents an aromatic group, X represents an alkyl group, and x represents an integer of 1 to 3. [Effects of the Invention].

[0009] According to the present invention, a resin composition with excellent preservation stability is provided, a cured product formed by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a semiconductor device containing the cured product or the laminate, and a novel compound are provided.

Implementation Method

[0010] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments shown. In this specification, the numerical range indicated by the symbol “~” refers to the range including the values ​​before and after “~” as the lower limit and upper limit, respectively. In this specification, the term “step” means not only independent steps, but also steps that cannot be clearly distinguished from other steps as long as the intended function of the step can be achieved. In the marking of groups (atomic groups) in this specification, the markings without substituted and unsubstituted include both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, “alkyl” includes not only alkyl groups without substituents (unsubstituted alkyl) but also alkyl groups with substituents (substituted alkyl). 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. Furthermore, examples of light used for exposure include the bright-line spectrum of mercury lamps, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" refers to either "acrylate" or "methacrylate," "(meth)acrylic acid" refers to either "acrylic acid" or "methacrylic acid," and "(meth)acrylyl" refers to either "acrylyl" or "methacrylyl." In this specification, Me in the structural formula represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl. In this specification, total solids content refers to the total mass of all components of the composition excluding the solvent. Furthermore, in this specification, solids concentration is the mass percentage of components other than the solvent relative to the total mass of the composition. Unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in this specification are values ​​determined by gel permeation chromatography (GPC) and are defined as polystyrene conversion values. For example, this specification uses an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series as a column to determine the weight-average molecular weight (Mw) and number-average molecular weight (Mn). Unless otherwise specified, these molecular weights are determined using THF (tetrahydrofuran) as the eluent. When THF has low solubility or is unsuitable as the eluent, NMP (N-methyl-2-pyrrolidone) can be used instead.Furthermore, unless otherwise specified, the detection in GPC measurements uses a UV (ultraviolet) detector with a wavelength of 254 nm. In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," it is sufficient that other layers exist above or below the reference layer among the plurality of layers of interest. That is, a third layer or third element may be further sandwiched between the reference layer and the other layers, without the reference layer needing to be in contact with the other layers. Also, unless otherwise specified, the direction of the substrate stacked layers is referred to as "upper," or when a resin composition layer is present, the direction from the substrate towards the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." Furthermore, these vertical and horizontal directions are set for convenience in 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 included in the composition may contain two or more compounds belonging to that component. Furthermore, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds belonging to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, the combination of preferred samples is referred to as the more preferred sample.

[0011] (Resin Composition) The resin composition of the first state of the present invention comprises a cyclized resin or a precursor thereof, wherein the content of carboxylic anhydride relative to the total mass of the resin composition is 0.5% by mass or less. The resin composition of the second state of the present invention comprises a cyclized resin or a precursor thereof, and a compound A having at least one group selected from the group consisting of hydroxyl, amino, and thiol groups, at least one group selected from amide and ester groups, and a group represented by the following formula (S-1). Hereinafter, the resin composition of the first state and the resin composition of the second state are also collectively referred to as "resin composition".

[0012] The resin composition of the present invention is preferably used to form photosensitive films for exposure and development, and is preferably used to form films for exposure and development using a developer containing an organic solvent. The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for rewiring layers. Furthermore, the resin composition of the present invention can be used to form photosensitive films for positive development and also for negative development. In the present invention, in exposure and development, negative development refers to development that removes non-exposed portions, and positive development refers to development that removes exposed portions. As the above-described exposure method, developer, and development method, for example, the exposure method described in the exposure step of the description of the method for manufacturing a cured material described later, and the developer and development method described in the development step can be used.

[0013] The resin composition of the present invention exhibits excellent storage stability. The mechanism by which the above-mentioned effects are obtained is not yet clear, but it is speculated to be as follows.

[0014] Resin compositions containing cyclized resins or their precursors have been used in various fields. The inventors have discovered that a resin composition with excellent storage stability can be obtained by using a carboxylic anhydride content of 0.5% by mass or less relative to the total mass of the resin composition, or by using a compound A containing a cyclized resin or its precursor, and a group having at least one group selected from the group consisting of hydroxyl, amino, and thiol groups, at least one amide group, and an ester group, or a compound represented by formula (S-1), or by using a compound represented by formula (2-1). The mechanism by which the above-mentioned effect is obtained is not yet clear, but it is speculated that it is due to the following reasons: by using a carboxylic anhydride content of 0.5% by mass or less, the reaction between the carboxylic anhydride and other components such as the cyclized resin or its precursor is suppressed; furthermore, by using compound A or a compound represented by formula (2-1) as a silane coupling agent, the content of carboxylic anhydride introduced into the composition can be reduced. Furthermore, it is hypothesized that a hardened film with excellent adhesion to metal or silicon wafers can be obtained by a composition containing compound A or a compound represented by formula (2-1).

[0015] Herein, the content of carboxylic anhydride, compound A and the compound represented by formula (2-1) are not described in Patent Document 1.

[0016] Hereinafter, the components contained in the resin composition of the present invention and their physical properties will be described in detail. Hereinafter, cyclized resins and their precursors will also be referred to as "specific resins".

[0017] <Content of Carboxylic Anhydride> In the resin composition of the first state of the present invention, the content of carboxylic anhydride relative to the total mass of the resin composition is 0.5% by mass or less. Here, the content of carboxylic anhydride is determined by the method shown in the examples described later. It is preferable that the content is 0.3% by mass or less, more preferably 0.1% by mass or less, and more preferably 0.05% by mass or less. The lower limit of the above content is not particularly limited and can be 0% by mass. Furthermore, when the resin composition contains a silane coupling agent, it is preferable that the content of carboxylic anhydride relative to the total mass of the silane coupling agent is 0.3% by mass or less, more preferably 0.1% by mass or less, and more preferably 0.05% by mass or less. The lower limit of the above content is not particularly limited and can be 0% by mass. In the resin composition of the second state of the present invention, it is preferable that the content of carboxylic anhydride relative to the total mass of the resin composition is 0.5% by mass or less. The preferred ranges of the content of carboxylic anhydride relative to the total mass of the resin composition and the content of carboxylic anhydride relative to the total mass of the silane coupling agent in the resin composition of the second state of the present invention are the same as the preferred ranges of such contents in the resin composition of the first state of the present invention described above.

[0018] <Specific Resin> The resin composition of the present invention comprises at least one resin (specific resin) selected from the group consisting of cyclized resins and their precursors. The cyclized resin is preferably a resin whose main chain structure includes an imine ring structure or an oxazole ring structure. In the present invention, the main chain refers to the longest bonded chain in the resin molecule. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamide-imide. The precursor of the cyclized resin refers to a resin whose chemical structure changes due to external stimuli to become a cyclized resin; preferably, a resin whose chemical structure changes due to heat to become a cyclized resin; and more preferably, a resin that becomes a cyclized resin by forming a ring structure through a heat-induced ring-closing reaction. Examples of precursors of cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamide-imide precursors. That is, the resin composition of the present invention preferably includes at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide-imide, and polyamide-imide precursor as the specific resin. It is preferable that the resin composition of the present invention includes polyimide or a polyimide precursor as the specific resin. Furthermore, it is preferable that the specific resin has polymerizable groups, and it is even more preferable that it includes free radical polymerizable groups. When the specific resin has free radical polymerizable groups, it is preferable that the resin composition of the present invention includes the free radical polymerization initiator described later, and it is even more preferable that it includes both the free radical polymerization initiator described later and the free radical crosslinking agent described later. Sensitizers described later can be further included as needed. For example, a negative photosensitive film can be formed from such resin compositions of the present invention. Furthermore, the specific resin may have polar conversion groups such as acid-decomposing groups. When a particular resin has acid-degrading groups, it is preferable that the resin composition of the present invention includes the photoacid-generating agent described later. For example, such resin compositions of the present invention can be used to form chemically amplified positive or negative photosensitive films.

[0019] 〔Polyimine Precursor〕 The type of polyimine precursor used in this invention is not particularly limited, but it is preferable to include repeating units represented by the following formula (2). [Chemical Formula 6] In formula (2), A1 and A2 independently represent oxygen atoms or -NH-, R111 represents a divalent organic group, R115 represents a tetravalent organic group, and R113 and R114 independently represent hydrogen atoms or monovalent organic groups.

[0020] In formula (2), A1 and A2 independently represent oxygen atoms or -NH-, with oxygen atoms being preferred. In formula (2), R111 represents a divalent organic group. Examples of divalent organic groups include straight-chain or branched aliphatic groups, cyclic aliphatic groups, and groups containing aromatic groups. It is preferred to have straight-chain or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 3 to 20 carbon atoms, aromatic groups with 3 to 20 carbon atoms, or combinations thereof. It is even more preferred to have groups containing aromatic groups with 6 to 20 carbon atoms. The hydrocarbon group in the chain of the above-mentioned straight-chain or branched aliphatic group can be replaced by a group containing heteroatoms, and the hydrocarbon group in the ring members of the above-mentioned cyclic aliphatic group and aromatic group can be replaced by a group containing heteroatoms. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, with groups represented by -Ar-L-Ar- being particularly preferred. In this group, Ar is independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, or a group consisting of -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. The preferred ranges are as described above.

[0021] R111 is preferably derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include straight-chain or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, diamines containing a straight-chain or branched aliphatic group with 2 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 3 to 20 carbon atoms, or a combination thereof, are preferred; diamines containing an aromatic group with 6 to 20 carbon atoms are even more preferred. The hydrocarbon group in the chain of the aforementioned straight-chain or branched aliphatic group can be replaced by a group containing a heteroatom, and the hydrocarbon group in the ring members of the aforementioned cyclic aliphatic and aromatic groups can be replaced by a group containing a heteroatom. Examples of groups containing aromatic groups include the following groups.

[0022] [Chemical Formula 7] In the formula, A represents a single bond or a divalent linker. It is preferred that the single bond is a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or combinations thereof. It is even more preferred that the single bond is a group selected from alkyl groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO2-. -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2- are further preferred. In the formula, * indicates a bonding site with other structures.

[0023] Specifically, as a diamine, examples include those selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 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 isophorone diamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4 '- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane (Phenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl) guanidine, bis(4-amino-3-hydroxyphenyl) guanidine, 4,4'-diamino-p-terphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] guanidine, bis[4-(3-aminophenoxy)phenyl] guanidine, bis[4-(2-aminophenoxy)phenyl] guanidine, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenyl guanidine, 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)furan, 4,4'-dimethyl-3,3'-diaminodiphenyl ether, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-Diaminocumene, 2,5-Dimethyl-p-phenylenediamine, acetylguanidine, 2,3,5,6-Tetramethyl-p-phenylenediamine, 2,4,6-Trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-Diaminophen, 2,5-Diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoniline, esters of diaminobenzoic acid, 1,5-diamine Naphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane [4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]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)diphenyl At least one diamine selected from the following: 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylbenzene, 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'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

[0024] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0025] Alternatively, the diamine having two or more alkyl diol units on the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 may also be preferred.

[0026] From the viewpoint of the flexibility of the obtained organic membrane, R111 is preferably represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be substituted by a fluorine atom, or a group consisting of -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. Ar is preferably phenyl, and L is preferably an aliphatic hydrocarbon group with 1 or 2 carbon atoms that can be substituted by a fluorine atom, or a group consisting of -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably alkyl.

[0027] Furthermore, from the viewpoint of i-ray transmittance, it is preferable that R111 is a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, it is even more preferable that the divalent organic group represented by formula (61) is preferred. Formula (51) [Chemical Formula 8] 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 atom, or a trifluoromethyl atom, and * independently represents the bonding site with the nitrogen atom in formula (2). Examples of monovalent organic groups of R50 to R57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [Chemical Formula 9] In formula (61), R58 and R59 are independently fluorine atoms, methyl groups, or trifluoromethyl groups, respectively, and * independently represent bonding sites with nitrogen atoms in formula (2). Examples of diamines that impart 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. One or more of these may be used.

[0028] R115 in formula (2) represents a tetravalent organic group. As 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 even more preferred. In formula (5) or formula (6), * independently represents the bonding site with other structures. [Chemical Formula 10] In Formula (5), R112 is a single bond or a divalent linkage group. It is preferred that the single bond or a group selected from aliphatic hydrocarbon groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S-, -SO2- and -NHCO-, and combinations thereof. It is even more preferred that the single bond or a group selected from alkyl groups with 1 to 3 carbon atoms that can be replaced by fluorine atoms, -O-, -CO-, -S- and -SO2- is selected. It is even more preferred that a divalent group selected from the group including -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S- and -SO2- is selected.

[0029] Specifically, R115 can be a tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride. As a structure belonging to R115, the polyimide precursor may contain only one tetracarboxylic dianhydride residue, or it may contain two or more. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 11] In formula (O), R115 represents a tetravalent organic group. The preferred range of R115 is the same as the meaning of R115 in formula (2), and the preferred range is also the same.

[0030] Specific examples of tetracarboxylic dianhydrides include pyrocalcite dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide 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'-oxophthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl) Propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydride, 1,4,5,6-naphthalenetetracarboxylic acid dianhydride, 2,2',3,3'-diphenyltetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 1,2,4,5-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride, and alkyl and alkoxy derivatives thereof having 1 to 6 carbon atoms.

[0031] Furthermore, as a preferred example, one may also cite the tetracarboxylic dianhydride (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598.

[0032] In formula (2), at least one of R111 and R115 may have an OH group. More specifically, R111 may be a residue of a diaminophenol derivative.

[0033] In formula (2), R113 and R114 each independently represent a hydrogen atom or a monovalent organic group. As a monovalent organic group, it is preferable to include a straight-chain or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene group. Furthermore, it is preferable that at least one of R113 and R114 contains a polymerizable group, and it is even more preferable that both contain polymerizable groups. It is also preferable that at least one of R113 and R114 contains two or more polymerizable groups. As a polymerizable group, it is a group capable of cross-linking reactions by heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having vinyl unsaturated bonds, alkoxymethyl, hydroxymethyl, acetoxymethyl, epoxy, oxybutyl, benzo[a]azolyl, terminal isocyanate, and amino groups. As a free radical polymerizable group in a polyimide precursor, a group having vinyl unsaturated bonds is preferred. Examples of groups having vinyl unsaturated bonds include vinyl, allyl, isoallyl, 2-methylallyl, groups having an aromatic ring directly bonded to vinyl (e.g., vinylphenyl), (meth)acrylamide, (meth)acryloxy, and groups represented by formula (III) below, with groups represented by formula (III) below being preferred.

[0034] [Chemical Formula 12]

[0035] In formula (III), R200 represents a hydrogen atom, methyl, ethyl, or hydroxymethyl, with a hydrogen atom or methyl being preferred. In formula (III), * indicates a bonding site with other structures. In formula (III), R201 represents an alkyl group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, an cycloalkyl group, or a polyalkylene group. Preferred examples of R201 include alkyl groups such as vinyl, propenyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkylene groups; vinyl, propenyl, and other propenyl groups, -CH2CH(OH)CH2-, cyclohexyl, and polyalkylene groups are more preferred; vinyl, propenyl, and other propenyl groups or polyalkylene groups are even more preferred. In this invention, a polyalkylene group refers to a group with two or more propenylene groups directly bonded together. The alkyl groups in the plurality of alkyl groups contained in the polyalkylene group can be the same or different. When the polyalkylene group contains a plurality of alkyl groups with different alkyl groups, the arrangement of the alkyl groups in the polyalkylene group can be random, block-shaped, or alternating. It is preferred that the number of carbon atoms in the alkyl group (including the number of carbon atoms of the substituent when the alkyl group has substituents) is 2 or more, more preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the alkyl group can have substituents. Examples of preferred substituents include alkyl, aryl, and halogen atoms. Furthermore, it is preferred that the number of alkyl groups contained in the polyalkylene group (the number of repetitions of the polyalkylene group) is 2 to 20, more preferably 2 to 10, and further preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethethyleneoxy, or groups bonded by a plurality of ethyleneoxy and a plurality of propyleneoxy groups are preferred as polyvinyloxy groups, with polyvinyloxy or polypropyleneoxy being more preferred, and polyvinyloxy being even more preferred. Among the aforementioned groups bonded by a plurality of ethyleneoxy and a plurality of propyleneoxy groups, the ethyleneoxy and propyleneoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred state of the number of repetitions of the ethyleneoxy groups, etc., in these groups is as described above.

[0036] In formula (2), when R113 is a hydrogen atom or R114 is a hydrogen atom, the polyimide precursor can form a conjugated salt with a tertiary amine compound having an ethylene unsaturated bond. As an example of such a tertiary amine compound having an ethylene unsaturated bond, N,N-dimethylaminopropyl methacrylate can be cited.

[0037] In formula (2), at least one of R113 and R114 can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, it is not particularly limited as long as it decomposes by the action of acid to produce a base-soluble group such as a phenolic hydroxyl group or a carboxyl group. Acetal, ketal, silicone, silicone ether, and tertiary alkyl ester are preferred. From the viewpoint of exposure sensitivity, acetal or ketal is more preferred. Specific examples of acid-degradable groups include tertiary butoxycarbonyl, isopropoxycarbonyl, tetrahydropiperanyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tertiary butoxycarbonylmethyl, and trimethylsilyl ether. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

[0038] Furthermore, it is also preferable that the polyimide precursor has fluorine atoms in its structure. It is preferable that the fluorine atom content in the polyimide precursor is 10% by mass or more, and preferably 20% by mass or less.

[0039] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0040] It is preferable that the repeating unit represented by formula (2) is the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in this invention is a precursor having a repeating unit represented by formula (2-A). By including a repeating unit represented by formula (2-A) in the polyimide precursor, the range of exposure latitude can be further increased. Formula (2-A) [Chemical Formula 13] In formula (2-A), A1 and A2 represent oxygen atoms, R111 and R112 each independently represent divalent organic groups, R113 and R114 each independently represent hydrogen atoms or monovalent organic groups, and at least one of R113 and R114 is a group containing a polymerizable group, preferably both of which are groups containing polymerizable groups.

[0041] A1, A2, R111, R113 and R114 have the same meaning as A1, A2, R111, R113 and R114 in equation (2), and the preferred range is also the same. R112 has the same meaning as R112 in equation (5), and the preferred range is also the same.

[0042] The polyimide precursor may contain one repeating unit represented by formula (2), or it may contain two or more repeating units. It may also contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of formula (2) above, the polyimide precursor may obviously also contain other types of repeating units.

[0043] As one embodiment of the polyimide precursor of the present invention, an example is provided in which the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating unit. It is more preferable that the total content is 70 mol% or more, further preferred that it is 90 mol% or more, and especially preferred that it exceeds 90 mol%. There is no particular limitation on the upper limit of the total content, and all repeating units in the polyimide precursor except for the terminal units can be repeating units represented by formula (2).

[0044] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersion of the above-mentioned polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit to the molecular weight dispersion of the polyimide precursor; for example, 7.0 or lower is preferred, 6.5 or lower is more preferred, and 6.0 or lower is even more preferred. In this specification, the molecular weight dispersion is a value calculated by dividing the weight-average molecular weight by the number-average molecular weight. Furthermore, when the resin composition includes multiple polyimide precursors as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor are within the aforementioned ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated using the aforementioned multiple polyimide precursors as a single resin are each within the aforementioned ranges.

[0045] [Polyimide] The polyimide used in this invention may be an alkali-soluble polyimide or a polyimide soluble in a developer solution mainly composed of an organic solvent. In this specification, alkali-soluble polyimide refers to polyimide dissolved in 100g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C at a concentration of 0.1g or more. From the viewpoint of pattern formation, dissolving 0.5g or more of polyimide is preferred, and dissolving 1.0g or more of polyimide is further preferred. The upper limit of the above-mentioned dissolution amount is not particularly limited, but less than 100g is preferred. Furthermore, from the viewpoint of the film strength and insulation of the obtained organic film, polyimide having a plurality of polyimide structures in the main chain is preferred. In this specification, "main chain" refers to the longest bonded chain in the molecule of the polymer compound that constitutes the resin, and "side chain" refers to the bonded chain other than the main chain.

[0046] -Fluorine Atom- From the viewpoint of the membrane strength of the obtained organic membrane, it is preferable that the polyimide has fluorine atoms. It is preferable that the fluorine atom is contained in R132 or R131 in the repeating unit represented by the following formula (4), and it is even more preferable that it is contained as a fluorinated alkyl group in R132 or R131 in the repeating unit represented by the following formula (4). It is preferable that the amount of fluorine atoms relative to the total mass of the polyimide is 5% by mass or more, and preferably 20% by mass or less.

[0047] -Silicon Atoms- From the viewpoint of the strength of the obtained organic membrane, it is preferable that the polyimide contains silicon atoms. Silicon atoms are preferably contained, for example, in R131 of the repeating unit represented by the formula (4) described later, and even more preferably in R131 of the repeating unit represented by the formula (4) described later as an organic modified (poly)siloxane structure. Furthermore, the aforementioned silicon atoms or the aforementioned organic modified (poly)siloxane structure may be contained in the side chain of the polyimide, but it is preferable that they are contained in the main chain of the polyimide. It is preferable that the amount of silicon atoms relative to the total mass of the polyimide is 1% by mass or more, and even more preferably 20% by mass or less.

[0048] -Ethylene unsaturated bond- From the viewpoint of the membrane strength of the obtained organic membrane, it is preferable that the polyimide has an ethylene unsaturated bond. The polyimide may have an ethylene unsaturated bond at the end of the main chain or in the side chain, with the side chain having an ethylene unsaturated bond being preferable. It is preferable that the ethylene unsaturated bond has free radical polymerization properties. It is preferable that the ethylene unsaturated bond is contained in R132 or R131 in the repeating unit represented by the following formula (4), and it is even preferable that it is contained as a group having an ethylene unsaturated bond in R132 or R131 in the repeating unit represented by the following formula (4). In these cases, it is preferable that the vinyl unsaturated bond is contained in R131 of the repeating unit represented by the following formula (4), and it is even more preferable that R131 is contained in the repeating unit represented by the following formula (4) as a group having an vinyl unsaturated bond. Examples of groups having an vinyl unsaturated bond include vinyl, allyl, vinylphenyl and other substituted vinyl groups that are directly bonded to an aromatic ring, (meth)acrylamide, (meth)acryloxy, and groups represented by the following formula (IV).

[0049] [Chemical Formula 14]

[0050] In formula (IV), R20 represents a hydrogen atom, methyl, ethyl or hydroxymethyl, with hydrogen atom or methyl being preferred.

[0051] In formula (IV), R21 represents an alkyl group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene group having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms, more preferably 2 to 6, and especially preferably 2 or 3; preferably 1 to 12 repetitions, more preferably 1 to 6, and especially preferably 1 to 3), or a group formed by combining two or more of these. Furthermore, the alkyl group having 2 to 12 carbon atoms can be any of the following: linear, branched, cyclic, or a combination thereof. As the alkyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 8 carbon atoms is preferred, and an alkyl group having 2 to 4 carbon atoms is even more preferred.

[0052] In these formulations, it is preferable that R21 is a group represented by any one of the following formulas (R1) to (R3), and it is more preferable that the group is represented by formula (R1). [Chemical Formula 15] In formulas (R1) to (R3), L represents a single bond or an alkyl group having 2 to 12 carbon atoms, a (poly)alkylene group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these; X represents an oxygen atom or a sulfur atom; * represents a bonding site with other structures; and ● represents a bonding site with the oxygen atom bonded to R21 in formula (IV). In formulas (R1) to (R3), the preferred form of the alkyl group having 2 to 12 carbon atoms or the (poly)alkylene group having 2 to 30 carbon atoms in L is the same as the preferred form of the alkyl group having 2 to 12 carbon atoms or the (poly)alkylene group having 2 to 30 carbon atoms in R21. In formula (R1), it is preferable that X is an oxygen atom. In formulas (R1) to (R3), * has the same meaning as in formula (IV), and the preferred state is also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide with hydroxyl groups such as phenolic hydroxyl groups with a compound having isocyanate groups and vinyl unsaturated bonds (e.g., ethyl 2-isocyanate methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide with carboxyl groups with a compound having hydroxyl groups and vinyl unsaturated bonds (e.g., hydroxyethyl 2-methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide with hydroxyl groups such as phenolic hydroxyl groups with a compound having glycidyl groups and vinyl unsaturated bonds (e.g., glycidyl methacrylate).

[0053] In formula (IV), * indicates the bonding site with other structures, and the bonding site with the main chain of polyimide is preferred.

[0054] The amount of vinyl unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.0005 to 0.05 mol / g.

[0055] - Polymerizable groups other than those with vinyl unsaturated bonds- Polyimide may contain polymerizable groups other than those with vinyl unsaturated bonds. Examples of polymerizable groups other than those with vinyl unsaturated bonds include cyclic ether groups such as epoxy groups and cyclobutane groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups. For example, it is preferable that the polymerizable groups other than those with vinyl unsaturated bonds are included in R131 in the repeating unit represented by formula (4) described later. It is preferable that the amount of polymerizable groups other than those with vinyl unsaturated bonds relative to the total mass of polyimide is 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0056] -Polar conversion group- Polyimide may have polar conversion groups such as acid-degrading groups. The acid-degrading groups in polyimide are the same as those described in R113 and R114 of the above formula (2), and the preferred form is also the same. Polar conversion groups are included, for example, in R131, R132, the end of polyimide, etc., in the repeating unit represented by the following formula (4).

[0057] -Acid Value- When polyimide is used for alkaline development, from the viewpoint of improving developability, an acid value of 30 mg KOH / g or higher is preferred, 50 mg KOH / g or higher is more preferred, and 70 mg KOH / g or higher is even more preferred. Furthermore, an acid value of 500 mg KOH / g or lower is preferred, 400 mg KOH / g or lower is more preferred, and 200 mg KOH / g or lower is even more preferred. Also, when polyimide is used in development with a developer primarily composed of organic solvents (e.g., "solvent development" described below), an acid value of 1 to 35 mg KOH / g is preferred, 2 to 30 mg KOH / g is more preferred, and 5 to 20 mg KOH / g is even more preferred. The above acid values ​​are determined by known methods, for example, by the method described in JIS K 0070:1992. Furthermore, considering both storage stability and developability, acid groups included in polyimide preferably have a pKa of 0 to 10, and more preferably 3 to 8. pKa is the equilibrium constant Ka, expressed as the negative logarithm of the dissociation reaction of the acid releasing hydrogen ions. In this specification, unless otherwise specified, pKa is set to a value calculated based on ACD / ChemSketch (registered trademark). Alternatively, the values ​​described in the "5th Revised Edition of the Chemical Handbook: Basic Chemicals" compiled by the Chemical Society of Japan can be consulted. Also, when the acid group is, for example, a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant. As such acid groups, polyimide preferably contains at least one group selected from the group including carboxyl and phenolic hydroxyl groups, and more preferably contains phenolic hydroxyl groups.

[0058] -Phenolic hydroxyl group- From the viewpoint of achieving an appropriate development speed based on alkaline developer, it is preferable that the polyimide has phenolic hydroxyl groups. The polyimide may have phenolic hydroxyl groups at the end of the main chain or in the side chain. It is preferable that the phenolic hydroxyl groups are contained, for example, in R132 or R131 in the repeating unit represented by formula (4) described later. It is preferable that the amount of phenolic hydroxyl groups relative to the total mass of the polyimide is 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0059] The polyimide used in this invention is not particularly limited as long as it is a polymer compound having a polyimide structure, but it is preferred to include repeating units represented by the following formula (4). [Chemical Formula 16] In formula (4), R131 represents a divalent organic group and R132 represents a tetravalent organic group. When a polymerizable group is present, the polymerizable group may be located on at least one of R131 and R132, or it may be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below. Formula (4-1) [Chemical Formula 17] In formula (4-1), R133 is a polymerizable group, and the other groups have the same meaning as in formula (4). Formula (4-2) [Chemical Formula 18] At least one of R134 and R135 is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other groups have the same meaning as in formula (4).

[0060] As a polymerizable group, examples can be groups containing the aforementioned vinyl unsaturated bonds or crosslinking groups other than groups containing the aforementioned vinyl unsaturated bonds. R131 represents a divalent organic group. Examples of divalent organic groups can be the same as R111 in formula (2), and the preferred range is also the same. Furthermore, as R131, examples can be diamine residues remaining after removing the amino group of a diamine. Examples of diamines can be aliphatic, cyclic aliphatic, or aromatic diamines. As a specific example, examples can be R111 in formula (2) of polyimide precursors.

[0061] From the viewpoint of more effectively suppressing warping during firing, R131 is preferably a diamine residue having at least two alkyl diol units in the main chain. More preferably, it is a diamine containing a total of two or more ethylene glycol chains, propylene glycol chains, or both in a molecule; even more preferably, it is the above-mentioned diamine without containing aromatic ring diamine residues.

[0062] As a diamine containing a total of two or more ethylene glycol chains or propylene glycol chains in one molecule, examples include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, etc., but not limited to these.

[0063] R132 represents a tetravalent organic group. As a tetravalent organic group, it can be exemplified as the same as R115 in formula (2), and the preferred range is also the same. For example, the four bonds of the tetravalent organic group exemplified as R115 are bonded to the four -C (=O)- portions in the above formula (4) to form a condensation ring.

[0064] Furthermore, R132 can be a tetracarboxylic acid residue remaining after the anhydride group is removed from a tetracarboxylic acid dianhydride. As a specific example, R115 in formula (2) of a polyimide precursor can be cited. From the viewpoint of the strength of the organic film, R132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

[0065] It is also preferable that at least one of R131 and R132 has an OH group. More specifically, as R131, 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) are preferred examples, and as R132, the above-mentioned (DAA-1) to (DAA-5) are more preferred examples.

[0066] Furthermore, it is also preferable that the polyimide has fluorine atoms in its structure. It is preferable that the fluorine atom content in the polyimide precursor is 10% by mass or more, and preferably 20% by mass or less.

[0067] Furthermore, in order 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.

[0068] Furthermore, in order to improve the storage stability of the resin composition, it is preferable to end-cap the main chain of the polyimide with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monochloro compounds, and active monoester compounds. Among these, monoamines are preferred, and preferred compounds for monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy-5-aminonaphthalene. Examples of amino acids include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminobenzenethiophenol, 3-aminobenzenethiophenol, and 4-aminobenzenethiophenol. Two or more of these can be used, or multiple different end groups can be introduced by reacting multiple end-capping agents.

[0069] - Acrylimization Rate (Ring-Closed Rate)- From the perspective of the obtained organic film's strength and insulation properties, a acetilimization rate (also known as "ring-closed rate") of 70% or higher for polyimide is preferred, 80% or higher is even better, and 90% or higher is even better. There is no specific upper limit to the above acetilimization rate; 100% or lower is acceptable. For example, the above acetilimization rate can be determined by the following method: Measure the infrared absorption spectrum of the polyimide and determine the peak intensity P1 near the absorption peak originating from the acetilimide structure, i.e., around 1377 cm⁻¹. Next, after heat-treating the polyimide at 350°C for 1 hour, measure the infrared absorption spectrum again and determine the peak intensity P2 near 1377 cm⁻¹. Using the obtained peak intensities P1 and P2, the acetilimization rate of the polyimide can be determined according to the following formula. Acrylimide content (%) = (peak intensity P1 / peak intensity P2) × 100

[0070] Polyimide may have repeating units represented by the above formula (4) which includes only one type of R131 or R132, or it may have repeating units represented by the above formula (4) which includes two or more different types of R131 or R132. In addition to repeating units represented by the above formula (4), polyimide may also include other types of repeating units. For example, repeating units represented by the above formula (2) can be cited as other types of repeating units.

[0071] For example, polyimide can be produced by reacting tetracarboxylic dianhydride with diamine (with a portion replaced by a monoamine, i.e., a capping agent) at low temperature; by reacting tetracarboxylic dianhydride (with a portion replaced by an anhydride, a monochloro compound, or an active monoester compound, i.e., a capping agent) with diamine at low temperature; by obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting it in the presence of diamine (with a portion replaced by a monoamine, i.e., a capping agent) and a condensing agent; by using tetracarboxylic dianhydride... Polyamide precursors are obtained by methods such as esterification of dianhydrides and alcohols, followed by acetylation of the remaining dicarboxylic acid and reaction with a diamine (partially replaced by a monoamine, i.e., a capping agent). These precursors are then synthesized using conventional acetylation reactions, either by complete acetylation or by stopping the acetylation reaction midway and introducing a partial acetylation structure, followed by further mixing the fully acetylated polymer and its polyamide precursor to introduce a partial acetylation structure. Other known methods for synthesizing polyamides are also applicable.

[0072] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. For obtaining an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or more is particularly preferred. Furthermore, the number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersion of the above-mentioned polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit to the molecular weight dispersion of the polyimide precursor; for example, 7.0 or less is preferred, 6.5 or less is even more preferred, and 6.0 or less is further preferred. Furthermore, when the resin composition contains multiple polyimides as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyimide are within the above-mentioned ranges. Also, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion calculated when the multiple polyimides are used as a single resin are each within the above-mentioned ranges.

[0073] 〔Polybenzoxazole precursor〕 The structure of the polybenzoxazole precursor used in this invention is not particularly limited, but it is preferred to contain repeating units represented by the following formula (3). [Chemical Formula 19] In formula (3), R121 represents a divalent organic group, R122 represents a tetravalent organic group, and R123 and R124 each independently represent a hydrogen atom or a monovalent organic group.

[0074] In formula (3), R123 and R124 have the same meaning as R113 in formula (2), and the preferred range is also the same. That is, it is preferred that at least one is a polymerizable group. In formula (3), R121 represents a divalent organic group. As a divalent organic group, it is preferred that the group includes at least one of an aliphatic group and an aromatic group. As an aliphatic group, a straight-chain aliphatic group is preferred. It is preferred that R121 is a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or more than two types may be used.

[0075] As a dicarboxylic acid residue, dicarboxylic acid residues containing an aliphatic group and dicarboxylic acid residues containing an aromatic group are preferred, with dicarboxylic acid residues containing an aromatic group being more preferred. As a dicarboxylic acid containing an aliphatic group, dicarboxylic acid containing a straight-chain or branched (preferably straight-chain) aliphatic group is preferred, and dicarboxylic acid composed of a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH groups is more preferred. The number of carbon atoms in the straight-chain or branched (preferably straight-chain) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The straight-chain aliphatic group is preferably an alkyl group. Examples of dicarboxylic acids containing straight-chain aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, and 2,2,6,6-tetramethylhimelic acid. Diacid, 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, hexadecanedioic acid Acid, behenedioic acid, triacontanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid, and dicarboxylic acid represented by the following formula, etc.

[0076] [Chemical Formula 20] (where Z is a hydrocarbon group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0077] As a dicarboxylic acid containing an aromatic group, it is preferable to have a dicarboxylic acid having the following aromatic group, and it is even more preferable to have a dicarboxylic acid consisting only of a group having the following aromatic group and 2 -COOH groups.

[0078] [Chemical Formula 21] In the formula, A represents a divalent group selected from the group including -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2- and -C(CH3)2-, and * represents the bonding site with other structures independently.

[0079] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid and 4,4'-dicarboxylic diphenyl ether and terephthalic acid.

[0080] In formula (3), R122 represents a tetravalent organic group. As a tetravalent organic group, it has the same meaning as R115 in formula (2) above, and the preferred range is also the same. Furthermore, it is preferable that R122 is a group derived from a diaminophenol derivative. Examples of groups derived from diaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfonate, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfonate, 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 diaminophenols can be used alone or in combination.

[0081] Among the diaminophenol derivatives, diaminophenol derivatives having the following aromatic groups are preferred.

[0082] [Chemical Formula 22] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, -NHCO-, and * and # represent the bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and even more preferably a hydrogen atom or an alkyl group. Furthermore, R122 is also preferred for the structure represented by the above formula. When R122 is the structure represented by the above formula, it is preferable that any two of the four asterisks and # are bonded to the nitrogen atom of R122 in formula (3) and the other two are bonded to the oxygen atom of R122 in formula (3). It is even better that two asterisks are bonded to the oxygen atom of R122 in formula (3) and two # are bonded to the nitrogen atom of R122 in formula (3) or two asterisks are bonded to the nitrogen atom of R122 in formula (3) and two # are bonded to the oxygen atom of R122 in formula (3). It is even more preferable that two asterisks are bonded to the oxygen atom of R122 in formula (3) and two # are bonded to the nitrogen atom of R122 in formula (3).

[0083] Diaminophenol derivatives represented by formula (As) are also preferred. [Chemical Formula 23]

[0084] In formula (As), R1 is an organic group selected from the group consisting of hydrogen atom, alkyl group, substituted alkyl group, -O-, -S-, -SO2-, -CO-, -NHCO-, single bond, or the following formulas (A-sc). R2 is any one of hydrogen atom, alkyl group, alkoxy group, acetoxy group, or cyclic alkyl group, which may be the same or different. R3 is any one of hydrogen atom, straight-chain or branched alkyl group, alkoxy group, acetoxy group, or cyclic alkyl group, which may be the same or different.

[0085] [Chemical Formula 24] (In formula (A-sc), * indicates an aromatic ring bond with the aminophenol group of the diaminophenol derivative represented by formula (As) above.)

[0086] It is believed that in the above formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, that is, at R3, will make the carbonyl carbon of the amide bond closer to the hydroxyl group, and is particularly good from the perspective of further improving the effect of increasing the cyclization rate during hardening at low temperature.

[0087] Furthermore, in the above formula (As), it is preferable that R2 is an alkyl group and R3 is an alkyl group, which can maintain the effect of high transparency to i-rays and high cyclization rate when hardening at low temperature.

[0088] Furthermore, in the above formula (As), it is even more preferable that R1 is an alkylene group or a substituted alkylene group. Specific examples of alkylene groups and substituted alkylene groups related to R1 include straight-chain or branched alkyl groups having 1 to 8 carbon atoms. Among these, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferable, considering both maintaining high transparency to i-rays and high cyclization rate during low-temperature curing, while also possessing sufficient solubility in solvents and being able to obtain a well-balanced polybenzoxazole precursor.

[0089] As a method for manufacturing the diaminophenol derivative represented by the above formula (As), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, the contents of which are incorporated herein by reference.

[0090] As a specific example of the structure of a diaminophenol derivative represented by the above formula (As), the contents described in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506 are provided, and such contents are incorporated herein by reference. Of course, it is not limited to such contents.

[0091] In addition to the repeating unit of formula (3) above, the polybenzoxazole precursor may also contain other types of repeating units. From the viewpoint of being able to suppress the warping that accompanies the ring closure, it is preferable that the polybenzoxazole precursor contains a diamine residue represented by the following formula (SL) as another type of repeating unit.

[0092] [Chemical Formula 25] In formula (SL), Z has an a structure and a b structure, R1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R2s is a hydrocarbon group having 1 to 10 carbon atoms, at least one of R3s, R4s, R5s, and R6s is an aromatic group, and the remaining part is a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure can be block polymerization or random polymerization. Regarding the molar percentage of the Z part, the a structure is 5 to 95 molars, the b structure is 95 to 5 molars, and a+b is 100 molars.

[0093] In formula (SL), as a preferred embodiment, R5s and R6s in structure b can be phenyl. Furthermore, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced more effectively, while simultaneously achieving the effects of suppressing warpage and improving solvent solubility.

[0094] When a diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferable to further include a tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride as a repeating unit. As an example of such a tetracarboxylic acid residue, R115 in formula (2) can be cited.

[0095] For example, 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 dispersion of the above-mentioned polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. There is no particular upper limit to the molecular weight dispersion of the polybenzo[a]azole precursor. For example, 2.6 or less is preferred, 2.5 or less is even better, 2.4 or less is further preferred, 2.3 or less is even more preferred, and 2.2 or less is still even more preferred. Furthermore, when the resin composition includes multiple polybenzo[a]azole precursors as a specific resin, it is preferred that the weight average molecular weight, number average molecular weight, and dispersion of at least one polybenzo[a]azole precursor are within the above-mentioned ranges. Also, it is preferred that the weight average molecular weight, number average molecular weight, and dispersion calculated using the multiple polybenzo[a]azole precursors as a single resin are each within the above-mentioned ranges.

[0096] 〔Polybenzoxazole〕 As for polybenzoxazole, there is no particular limitation as long as it is a polymeric compound having a benzoxazole ring. Compounds represented by the following formula (X) are preferred, and compounds represented by the following formula (X) and having a polymerizable group are even more preferred. As the aforementioned polymerizable group, a free radical polymerizable group is preferred. Also, it can be a compound represented by the following formula (X) and having a polar conversion group such as an acid-decomposing group. [Chemical Formula 26] In formula (X), R133 represents a divalent organic group, and R134 represents a tetravalent organic group. When it has a polymerizable group or an acid-decomposing group, the polymerizable group or the acid-decomposing group can be located on at least one of R133 and R134, or it can be located at the end of the polybenzoxazole as shown in formula (X-1) or formula (X-2) below. Formula (X-1) [Chemical Formula 27] In Formula (X-1), at least one of R135 and R136 is a polymerizable or acid-degradable polar conversion group, or an organic group if it is not a polymerizable or acid-degradable polar conversion group. The other groups have the same meaning as in Formula (X). Formula (X-2) [Chemical Formula 28] In Formula (X-2), R137 is a polymerizable or acid-degradable polar conversion group, and the rest are substituents. The other groups have the same meaning as in Formula (X).

[0097] The polar conversion groups such as polymerizable groups or acid-degradable groups have the same meaning as the polymerizable groups described in the polymerizable groups polymerized in the above-mentioned polyimide precursors.

[0098] R133 represents a divalent organic group. Examples of divalent organic groups include aliphatic or aromatic groups. As a specific example, R121 in formula (3) of polybenzoxazole precursor can be cited. Furthermore, the preferred example has the same meaning as R121.

[0099] R134 represents a tetravalent organic group. An example of a tetravalent organic group is R122 in formula (3) of a polybenzoxazole precursor. Furthermore, a preferred example has the same meaning as R122. For example, the four bonds of the tetravalent organic group exemplified by R122 bond with the nitrogen and oxygen atoms in formula (X) above to form a condensation ring. For example, when R134 is an organic group, the following structure is formed. In the following structure, * indicates the bonding site with the nitrogen or oxygen atom in formula (X), respectively. [Chemical Formula 29]

[0100] An acezolation rate of 85% or higher for polybenzo[a]azole is preferred, and 90% or higher is even better. There is no specific upper limit; it can be 100%. With an acezolation rate of 85% or higher, the film shrinkage caused by ring closure during heating during acezolation is reduced, and warpage can be effectively suppressed. For example, the aforementioned acezolation rate can be determined by the following method: The infrared absorption spectrum of polybenzo[a]azole is measured, and the peak intensity Q1 of the absorption peak near 1650 cm⁻¹ derived from the amide structure of the precursor is determined. Then, the absorption intensity of the aromatic ring observed near 1490 cm⁻¹ is normalized. After heat-treating the polybenzo[a]azole precursor at 350°C for 1 hour, the infrared absorption spectrum is measured again, and the peak intensity Q2 near 1650 cm⁻¹ is determined, and normalized using the absorption intensity of the aromatic ring observed near 1490 cm⁻¹. The azoleization rate of polybenzoxazole can be calculated using the obtained peak intensity specifications Q1 and Q2 according to the following formula: Alzolization rate (%) = (Specification value of peak intensity Q1 / Specification value of peak intensity Q2) × 100

[0101] Polybenzoxazole may have repeating units comprising all of one type of R131 or R132 as described above, or it may have repeating units comprising two or more different types of R131 or R132 as described above. Furthermore, in addition to repeating units comprising the above-described formula (X), polybenzoxazole may also contain other types of repeating units.

[0102] For example, a polybenzoxazole precursor is obtained by reacting a diaminophenol derivative with a dicarboxylic acid containing R133 or a dicarboxylic acid dichloride or dicarboxylic acid derivative selected from the above dicarboxylic acids. The precursor is then acetazoleized using a conventional acetazoleization reaction method, thereby obtaining polybenzoxazole. Furthermore, in the case of dicarboxylic acids, in order to improve the reaction yield, an active ester-type dicarboxylic acid derivative, such as 1-hydroxy-1,2,3-benzotriazole, can be used as a pre-reacted derivative to enhance the reaction yield.

[0103] The weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or higher, the bending resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, a weight average molecular weight of 20,000 or higher is particularly preferred. Furthermore, when two or more polybenzoxazoles are contained, it is preferable that the weight average molecular weight of at least one polybenzoxazole is within the above range. Furthermore, the number average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. It is preferable that the molecular weight dispersion of the aforementioned polybenzo[a]azole is 1.4 or higher, more preferably 1.5 or higher, and further preferably 1.6 or higher. There is no particular upper limit to the molecular weight dispersion of the polybenzo[a]azole; for example, 2.6 or lower is preferable, 2.5 or lower is more preferable, 2.4 or lower is further preferable, 2.3 or lower is even more preferable, and 2.2 or lower is still even more preferable. Furthermore, when the resin composition includes multiple types of polybenzo[a]azole as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion of at least one type of polybenzo[a]azole are within the aforementioned ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersion calculated when the aforementioned multiple types of polybenzo[a]azole are used as a single resin are each within the aforementioned ranges.

[0104] 〔Polyamide-imide precursor〕 It is preferable that the polyamide-imide precursor contains a repeating unit represented by the following formula (PAI-2). [Chemical Formula 30] In formula (PAI-2), R117 represents a trivalent organic group, R111 represents a divalent organic group, A2 represents an oxygen atom or -NH-, and R113 represents a hydrogen atom or a monovalent organic group.

[0105] In formula (PAI-2), R117 may be an example of a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group formed by linking two or more of these groups by a single bond or a linking group. It is preferred that a straight-chain aliphatic group with 2 to 20 carbons, a branched aliphatic group with 3 to 20 carbons, a cyclic aliphatic group with 3 to 20 carbons, an aromatic group with 6 to 20 carbons, or a group formed by combining two or more of these groups by a single bond or a linking group. It is even more preferred that an aromatic group with 6 to 20 carbons, or a group formed by combining two or more aromatic groups with 6 to 20 carbons by a single bond or a linking group, is formed. As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halogenate, arylene, or a linking group formed by combining two or more of these bonds is preferred; -O-, -S-, alkylene, alkyl halogenate, arylene, or a linking group formed by combining two or more of these bonds is even more preferred. As the alkylene group mentioned above, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is even more preferred, and an alkylene group having 1 to 4 carbon atoms is even more preferred. As the alkyl halogenate mentioned above, an alkyl halogenate having 1 to 20 carbon atoms is preferred, an alkyl halogenate having 1 to 10 carbon atoms is even more preferred, and an alkyl halogenate having 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the alkyl halogenate include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. The aforementioned alkyl halides may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, but replacement of all hydrogen atoms by halogen atoms is preferred. Examples of preferred alkyl halides include (di-trifluoromethyl)methylene. As for the aforementioned aryl groups, phenyl or naphthyl groups are preferred, phenyl groups are more preferred, and 1,3-phenyl or 1,4-phenyl groups are even more preferred.

[0106] Furthermore, R117 is preferably derived from a tricarboxylic acid compound with at least one carboxyl group that can be halogenated. Chlorination is preferred as the halogenation method. In this invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups in the aforementioned tricarboxylic acid compound can be anhydride-substituted. Examples of halogenable tricarboxylic acid compounds for manufacturing polyamide imine precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. Only one type of such tricarboxylic acid compound may be used, or two or more types may be used.

[0107] Specifically, as a tricarboxylic acid compound, a tricarboxylic acid compound comprising a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by a single bond or a linking group, is preferred. A tricarboxylic acid compound comprising an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group, is even more preferred.

[0108] Furthermore, specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride), and benzoic acid linked by a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or an extended phenyl group. These compounds can be compounds formed by anhydridating two carboxyl groups (e.g., trimellitic anhydride) or compounds formed by halogenating at least one carboxyl group (e.g., trimellitic anhydride chloride).

[0109] In formula (PAI-2), R111, A2, and R113 have the same meaning as R111, A2, and R113 in formula (2) above, and the better state is also the same.

[0110] The polyamide imide precursor may further include other repeating units. Examples of other repeating units include repeating units represented by formula (2) above, repeating units represented by formula (PAI-1) below, etc. [Chemical Formula 31]

[0111] In formula (PAI-1), R116 represents a divalent organic group, and R111 represents a divalent organic group. In formula (PAI-1), R116 may represent a straight-chain or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group formed by linking two or more of these groups by single bonds or linking groups. It is preferred that a straight-chain aliphatic group with 2 to 20 carbon atoms, a branched aliphatic group with 3 to 20 carbon atoms, a cyclic aliphatic group with 3 to 20 carbon atoms, an aromatic group with 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by single bonds or linking groups. It is even more preferred that an aromatic group with 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups with 6 to 20 carbon atoms by single bonds or linking groups, is formed. As the linking group mentioned above, -O-, -S-, -C(=O)-, -S(=O)2-, alkylene, alkyl halogenate, arylene, or a linking group formed by combining two or more of these bonds is preferred; -O-, -S-, alkylene, alkyl halogenate, arylene, or a linking group formed by combining two or more of these bonds is even more preferred. As the alkylene group mentioned above, an alkylene group having 1 to 20 carbon atoms is preferred, an alkylene group having 1 to 10 carbon atoms is even more preferred, and an alkylene group having 1 to 4 carbon atoms is even more preferred. As the alkyl halogenate mentioned above, an alkyl halogenate having 1 to 20 carbon atoms is preferred, an alkyl halogenate having 1 to 10 carbon atoms is even more preferred, and an alkyl halogenate having 1 to 4 carbon atoms is even more preferred. Furthermore, examples of halogen atoms in the alkyl halogenate include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred. The aforementioned alkyl halides may have hydrogen atoms, or all hydrogen atoms may be replaced by halogen atoms, but replacement of all hydrogen atoms by halogen atoms is preferred. Examples of preferred alkyl halides include (di-trifluoromethyl)methylene. As for the aforementioned aryl groups, phenyl or naphthyl groups are preferred, phenyl groups are more preferred, and 1,3-phenyl or 1,4-phenyl groups are even more preferred.

[0112] Furthermore, R116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In this invention, a compound having two carboxyl groups is called a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is called a dicarboxylic acid dihalide compound. The carboxyl groups in the dicarboxylic acid dihalide compound can be halogenated, for example, chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of halogenable dicarboxylic acid compounds or dicarboxylic acid dihalides that can be used as precursors for manufacturing polyamide imide include linear or branched aliphatic, cyclic aliphatic, or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalides. Only one of these dicarboxylic acid compounds or dicarboxylic acid dihalides may be used, or two or more may be used.

[0113] Specifically, as a dicarboxylic acid compound or a dicarboxylic acid dihalide compound, it is preferable that the dicarboxylic acid compound or dicarboxylic acid dihalide compound contains a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups by a single bond or a linking group. It is even more preferable that the dicarboxylic acid compound or dicarboxylic acid dihalide compound contains an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms by a single bond or a linking group.

[0114] Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, octanoic acid, dodecafluorooctanoic acid, azelaic acid, sebacic acid. Examples of dicarboxylic acid dihalides include hexafluorodecanedioic acid, 1,9-azelaic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanedioic acid, octadecanoic acid, nonadecanedioic acid, eicosanoic acid, icosanoic acid, docosanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanedioic acid, octadecanoic acid, nonadecanedioic acid, triadecanoic acid, triadecanoic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, etc. Specific examples of dicarboxylic acid dihalides include compounds with structures where two carboxyl groups are halogenated.

[0115] In formula (PAI-1), R111 has the same meaning as R111 in formula (2) above, and the better state is also the same.

[0116] Furthermore, it is also preferable that the polyamide imide precursor has fluorine atoms in its structure. It is preferable that the fluorine atom content in the polyamide imide precursor is 10% by mass or more, and preferably 20% by mass or less.

[0117] Furthermore, to improve adhesion to the substrate, the polyamide imine precursor can be copolymerized with an aliphatic group having a silicate structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0118] As one embodiment of the polyamide imide precursor of the present invention, an embodiment in which the total content of the repeating unit represented by formula (PAI-2), the repeating unit represented by formula (PAI-1), and the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units. It is more preferable that the total content is 70 mol% or more, more preferably 90 mol% or more, and especially preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyamide imide precursor except for the terminal can be any one of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2). Furthermore, as another embodiment of the polyamide-imide precursor of the present invention, an example is provided in which the total content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or more of the total repeating units. It is more preferable that the total content is 70 mol% or more, further preferable that it is 90 mol% or more, and particularly preferable that it exceeds 90 mol%. The upper limit of the total content is not particularly limited; all repeating units in the polyamide-imide precursor, except for the terminal units, can be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

[0119] The weight average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The molecular weight dispersion of the polyamide-imide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit to the molecular weight dispersion of the polyamide-imide precursor; for example, 7.0 or lower is preferred, 6.5 or lower is more preferably, and 6.0 or lower is even more preferably. Furthermore, when the resin composition includes multiple polyamide-imide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one polyamide-imide precursor are within the aforementioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated using the aforementioned multiple polyamide-imide precursors as a single resin are each within the aforementioned ranges.

[0120] [Polyamide-Imine] The polyamide-imide used in this invention may be an alkali-soluble polyamide-imide or a polyamide-imide soluble in a developer solution mainly composed of an organic solvent. In this specification, alkali-soluble polyamide-imide refers to polyamide-imide dissolved in 100g of a 2.38% by mass tetramethylammonium aqueous solution at 23°C at a concentration of 0.1g or more. From the viewpoint of pattern formation, dissolving 0.5g or more of polyamide-imide is preferred, and dissolving 1.0g or more of polyamide-imide is further preferred. The upper limit of the above-mentioned dissolution amount is not particularly limited, but less than 100g is preferred. Furthermore, from the viewpoint of the strength and insulation of the obtained organic membrane, polyamide-amide is preferred if it has a plurality of amide bonds and a plurality of amide structures in the main chain.

[0121] -Fluorine Atom- From the viewpoint of the strength of the obtained organic membrane, it is preferable that the polyamide imide has fluorine atoms. It is preferable that the fluorine atom is contained, for example, in R117 or R111 of the repeating unit represented by the following formula (PAI-3), and even more preferably, it is contained as a fluorinated alkyl group in the repeating unit represented by the following formula (PAI-3). It is preferable that the amount of fluorine atoms relative to the total mass of the polyamide imide is 5% by mass or more, and preferably 20% by mass or less.

[0122] -Ethylene Unsaturated Bond- From the viewpoint of the membrane strength of the obtained organic membrane, polyamide imide can have ethylene unsaturated bonds. Polyamide imide can have ethylene unsaturated bonds at the end of the main chain or in the side chain, with the latter being more preferred. The aforementioned ethylene unsaturated bonds are preferably free radical polymerizable. It is preferable that the ethylene unsaturated bonds are contained in R117 or R111 in the repeating unit represented by the following formula (PAI-3), and it is even more preferable that they are contained in R117 or R111 in the repeating unit represented by the following formula (PAI-3) as groups having ethylene unsaturated bonds. The preferred state of the groups having ethylene unsaturated bonds is the same as the preferred state of the groups having ethylene unsaturated bonds in the polyamide described above.

[0123] The amount of vinyl unsaturated bonds relative to the total mass of polyamide imine is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0124] - Polymerizable groups other than vinyl unsaturated bonds - Polyamide imides may have polymerizable groups other than vinyl unsaturated bonds. Examples of polymerizable groups other than vinyl unsaturated bonds in polyamide imides include groups identical to those in the polyamide imides described above. For example, it is preferable that the polymerizable group other than vinyl unsaturated bonds is included in R111 of the repeating unit represented by formula (PAI-3) described later. The amount of polymerizable groups other than vinyl unsaturated bonds relative to the total mass of the polyamide imide is preferably 0.05 to 10 mol / g, and more preferably 0.1 to 5 mol / g.

[0125] -Polar conversion group- Polyamide imide may have polar conversion groups such as acid-degrading groups. The acid-degrading groups in polyamide imide are the same as those described in R113 and R114 of the above formula (2), and the preferred state is also the same.

[0126] -Acid Value- When polyamide-imide is used for alkaline development, from the viewpoint of improving developability, an acid value of 30 mg KOH / g or higher is preferred, 50 mg KOH / g or higher is more preferred, and 70 mg KOH / g or higher is even more preferred. Furthermore, an acid value of 500 mg KOH / g or lower is preferred, 400 mg KOH / g or lower is more preferred, and 200 mg KOH / g or lower is even more preferred. Moreover, when polyamide-imide is used in development with a developer primarily composed of organic solvents (e.g., "solvent development" described below), an acid value of 2–35 mg KOH / g is preferred, 3–30 mg KOH / g is more preferred, and 5–20 mg KOH / g is even more preferred. The acid value described above is determined by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, as an acid group contained in polyamide imide, groups identical to the acid groups in the aforementioned polyamide imide can be cited, and the preferred sample is also the same.

[0127] -Phenolic hydroxyl group- From the viewpoint of achieving an appropriate development speed based on alkaline developer, it is preferable that the polyamide imide has a phenolic hydroxyl group. The polyamide imide may have a phenolic hydroxyl group at the end of the main chain or in the side chain. It is preferable that the phenolic hydroxyl group is contained, for example, in R117 or R111 in the repeating unit represented by the formula (PAI-3) described later. It is preferable that the amount of phenolic hydroxyl group relative to the total mass of the polyamide imide is 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0128] The polyamide amide used in this invention is not particularly limited as long as it is a polymer compound having an amide structure and amide bonds, but it is preferred to include repeating units represented by the following formula (PAI-3). [Chemical Formula 32] In formula (PAI-3), R111 and R117 have the same meaning as R111 and R117 in formula (PAI-2), and the preferred state is also the same. When it has a polymerizable group, the polymerizable group can be located on at least one of R111 and R117, or it can be located at the end of the polyamide amide.

[0129] Furthermore, in order to improve the storage stability of the resin composition, it is preferable to seal the main chain ends of the polyamide amide with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monochlorodimethylamine compounds, or active monoester compounds. The preferred state of the end-capping agent is the same as that of the end-capping agent in the polyamide described above.

[0130] - Acrylimization Rate (Ring-Closed Rate)- From the perspective of the obtained organic membrane's strength and insulation properties, a acetilimide ...

[0131] Polyamide imide may have repeating units represented by the above formula (PAI-3) comprising only one type of R111 or R117, or it may have repeating units represented by the above formula (PAI-3) comprising two or more different types of R131 or R132. Furthermore, polyamide imide may contain repeating units of other types besides those represented by the above formula (PAI-3). Examples of other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0132] Polyamide imide can be synthesized, for example, by means of: obtaining a polyamide imide precursor by a known method, fully amide imidizing it using a conventional amide imidization reaction, or stopping the amide imidization reaction midway and introducing a partial amide structure, or introducing a partial amide structure by further mixing the fully amide imidized polymer with the polyamide imide precursor.

[0133] The weight average molecular weight (Mw) of the polyamide imide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or higher, the bending resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, a weight average molecular weight of 20,000 or higher is particularly preferred. Furthermore, the number average molecular weight (Mn) of the polyamide imide is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The molecular weight dispersion of the polyamide imide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit to the molecular weight dispersion of polyamide imides; for example, 7.0 or less is preferred, 6.5 or less is even more preferred, and 6.0 or less is further preferred. Furthermore, when the resin composition includes multiple polyamide imides as a specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersion of at least one polyamide imide are within the above-mentioned ranges. Moreover, it is also preferable that the weight average molecular weight, number average molecular weight, and dispersion calculated when the multiple polyamide imides are used as a single resin are each within the above-mentioned ranges.

[0134] [Manufacturing Method of Polyimide Precursors, etc.] For example, polyimide precursors, etc., can be obtained by the following methods: a method of reacting tetracarboxylic dianhydride with diamine at low temperature; a method of obtaining polyamide by reacting tetracarboxylic dianhydride with diamine at low temperature and then esterifying it with a condensing agent or an alkylating agent; a method of obtaining a diester by tetracarboxylic dianhydride and alcohol and then reacting it in the presence of diamine and a condensing agent; a method of obtaining a diester by tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with diamine, etc. Of the above manufacturing methods, the method of obtaining a diester by tetracarboxylic dianhydride and alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and then reacting it with diamine is more preferred. Examples of condensing agents include dicyclohexanediimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of alkylating agents include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of halogenating agents include thionyl chloride, oxalyl chloride, and phosphatidyl chloride. In the method for manufacturing polyimide precursors, etc., it is preferable to use an organic solvent during the reaction. One or more organic solvents may be used. As an organic solvent, it can be appropriately determined according to the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, γ-butyrolactone, etc. In the manufacturing method of polyimide precursors, it is preferable to add a basic compound during the reaction. The basic compound can be one type or two or more types. The basic compound can be appropriately determined according to the raw materials, and examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diacrylbicyclo[5.4.0]undecyl-7-ene, N,N-dimethyl-4-aminepyridine, etc.

[0135] -End-capping agent- In the manufacture of polyimide precursors, etc., it is preferable to block the carboxylic anhydride, anhydride derivatives, or amine groups remaining at the resin ends of the polyimide precursor, etc., in order to further improve storage stability. When blocking the carboxylic anhydride and anhydride derivatives remaining at the resin ends, monools, phenols, thiols, benzenethiophenols, monoamines, etc. can be used as end-capping agents. Considering reactivity and film stability, monools, phenols, and monoamines are preferred. Preferred compounds as monools include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol and other primary alcohols, isopropanol, 2-butanol, cyclohexanol, cyclopentanol, 1-methoxy-2-propanol and other secondary alcohols, tertiary alcohols such as butanol and adamantanol. Preferred compounds among phenols include phenol, methoxyphenol, methylphenol, naphth-1-ol, naphth-2-ol, and hydroxystyrene. Preferred compounds among monoamines 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, and 2-carboxy-7-aminonaphthalene. -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-Aminobenzenethiophenol, 3-Aminobenzenethiophenol, 4-Aminobenzenethiophenol, etc. Two or more of these can be used, and multiple different end groups can be introduced by reacting multiple end-capping agents. Furthermore, when blocking the amino groups at the resin ends, compounds with functional groups that can react with amino groups can be used for blocking. Preferred end-capping agents for the amino group include carboxylic anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic anhydrides, with carboxylic anhydrides and carboxylic acid chlorides being more preferred. Preferred compounds for carboxylic anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norcamphen-2,3-dicarboxylic anhydride. Preferred compounds for carboxylic acid chlorides include acetic acid chloride, acrylonitrile chloride, propionic acid chloride, methacrylic acid chloride, neopentyl chloride, cyclohexanemethyl chloride, 2-ethylhexyl chloride, cinnamon chloride, 1-adamantanemethyl chloride, heptafluorobutyl chloride, stearyl chloride, and benzoyl chloride.

[0136] - Solid Precipitation - When manufacturing polyimide precursors, a solid precipitation step may be included. Specifically, after filtering out the water-absorbing byproducts of the dehydrating condensing agent coexisting in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, aliphatic lower alcohols, or mixtures thereof, and the polymer component is precipitated, thereby precipitating it as a solid and drying it to obtain the polyimide precursor, etc. To improve the purification degree, the polyimide precursor, etc., may be repeatedly subjected to operations such as re-dissolving, re-precipitating, and drying. A step of removing ionic impurities using an ion exchange resin may also be included.

[0137] [Content] The content of the specific resin in the resin composition of the present invention, relative to the total solid content of the resin composition, is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, the content of the resin in the resin composition of the present invention, relative to the total solid content of the resin composition, is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less. The resin composition of the present invention may contain only one specific resin, or it may contain two or more. When containing two or more, it is preferable that the total amount is within the above-mentioned range.

[0138] Furthermore, it is preferable that the resin composition of the present invention contains at least two types of resins. Specifically, the resin composition of the present invention may contain two or more types of specific resins and other resins described below, or it may contain two or more types of specific resins, and it is preferable that it contains two or more types of specific resins. When the resin composition of the present invention contains two or more types of specific resins, it is preferable that it contains, for example, two or more polyimide precursors with different structures derived from dianhydrides (R115 in formula (2) above).

[0139] <Other Resins> The resin composition of the present invention may include the specific resin described above and other resins different from the specific resin (hereinafter also simply referred to as "other resins"). Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylic amide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, polyester resins, etc. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can also be obtained. For example, by adding (meth)acrylic resin to the resin composition to replace the polymerizable compound described later, or by adding (meth)acrylic resin in addition to the polymerizable compound described later, the coatability of the resin composition, the solvent resistance of the pattern (cured product), etc., can be improved. The (meth)acrylic resin has a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, the content of polymerizable groups in 1g of resin is 1×10-3 moles / g or more).

[0140] When the resin composition of the present invention contains other resins, the content of the other resins relative to the total solid content of the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more. Furthermore, the content of other resins in the resin composition of the present invention relative to the total solid content of the resin composition is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less. Also, as a preferred embodiment of the resin composition of the present invention, it is also possible to provide an embodiment with a low content of other resins. In the above-described samples, the content of other resins relative to the total solids content of the resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, further 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; 0% by mass or more is acceptable. The resin composition of the present invention may contain only one type of other resin, or it may contain two or more types. When containing two or more types, it is preferable that the total amount is within the above-described range.

[0141] <Silane Coupling Agent> It is preferable that the resin composition of the first state sample of the present invention contains a silane coupling agent.

[0142] As a silane coupling agent, there is no particular limitation, but it is preferable to include compound A having at least one group selected from the group consisting of hydroxyl, amino, and thiol groups, at least one group consisting of amide and ester groups, and a group represented by formula (S-1). Furthermore, from the viewpoint of close contact with the silicon wafer, it is preferable that compound A contains an aromatic group. When compound A contains an aromatic group, it is preferable that the aromatic group exists between at least one group selected from the group consisting of hydroxyl, amino, and thiol groups and at least one group consisting of amide and ester groups. The aromatic group can be any of an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. Among the aromatic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 20 carbon atoms are preferred, and benzene ring groups are more preferred. [Chemical Formula 33] In Formula (S-1), R1 independently represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms that can be substituted, R2 independently represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms that can be substituted, x represents an integer of 1 to 3, and * represents a bonding site with other structures. One or both of the two hydrogen atoms in the amine group contained in the silane coupling agent can be substituted by a substituent. Examples of substituents include hydrocarbon groups or heterocyclic groups, preferably alkyl or aryl groups. Examples of heteroatoms in the heterocycle include oxygen, sulfur, and nitrogen atoms. Furthermore, the amine group in the silane coupling agent being an unsubstituted amine group is also one of the preferred embodiments of the present invention. It is preferable that the hydroxyl group contained in the silane coupling agent is directly bonded to an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and more preferably directly bonded to an aliphatic hydrocarbon group. In silane coupling agents, it is preferable that the thiol group is directly bonded to an aromatic or aliphatic hydrocarbon group, with direct bonding to an aliphatic hydrocarbon group being more preferred. Similarly, it is preferable that the amine group in the silane coupling agent is directly bonded to an aromatic or aliphatic hydrocarbon group, with direct bonding to an aromatic hydrocarbon group being more preferred. The amide group refers to a group represented by -C(=O)NRN-. The orientation of the amide group is not particularly limited, but it is preferable that carbon atoms are bonded to both ends of the amide group. RN represents a hydrogen atom or a monovalent substituent; a hydrogen atom or a hydrocarbon group is preferred, with hydrogen, alkyl, or aromatic hydrocarbon groups being more preferred, and hydrogen being particularly preferred. The ester group refers to a group represented by -C(=O)O-. The orientation of the ester group is not particularly limited, but it is preferable that carbon atoms are bonded to both ends of the ester group.

[0143] In formula (S-1), R1 is preferably a substituted hydrocarbon group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, further preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, especially preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably methyl or ethyl, with ethyl being the most preferred. In formula (S-1), R2 is preferably a substituted hydrocarbon group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 30 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, further preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, especially preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably methyl or ethyl, with ethyl being the most preferred. In formula (S-1), x is preferably 2 or 3, with 3 being more preferred. The group represented by formula (S-1) is preferably an alkoxysilyl group. The alkoxysilyl group can be any one of monoalkoxysilyl, dialkoxysilyl, or trialkoxysilyl, with dialkoxysilyl or trialkoxysilyl being preferred, and trialkoxysilyl being even more preferred. There is no particular limitation on the alkoxy group, but alkoxy groups with 1 to 10 carbon atoms are preferred, alkoxy groups with 1 to 4 carbon atoms are even more preferred, methoxy or ethoxy groups are further preferred, and ethoxy groups are particularly preferred. Furthermore, the plurality of alkoxy groups in the dialkoxysilyl or trialkoxysilyl group can be the same or different.

[0144] Compound A may have a plurality of at least one group selected from the group consisting of hydroxyl, amino, and thiol groups, or may have only one. When it has a plurality of groups, it may include hydroxyl and amino groups, which contain a plurality of groups. It is preferred that the total number of at least one group selected from the group consisting of hydroxyl, amino, and thiol groups in Compound A is 1 to 4, more preferably 1 or 2, and 1 is even more preferred. Compound A may have a plurality of at least one group selected from amide and ester groups, or may have only one. When it has a plurality of groups, it may include amide and ester groups, which contain a plurality of groups. It is preferred that the total number of at least one group selected from amide and ester groups in Compound A is 1 to 4, more preferably 1 or 2, and 1 is even more preferred. Compound A may contain two or more groups represented by formula (S-1). It is preferred that the number of groups represented by formula (S-1) in compound A is 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0145] Compound A is preferably a compound having at least one group selected from hydroxyl, amide, and ester, or a group represented by formula (S-1). Furthermore, it is preferable that compound A is a compound having at least one group selected from the group consisting of hydroxyl, amide, and thiol, or an amide group, or a group represented by formula (S-1). Of these, compound A is more preferably a compound having hydroxyl, amide, or a group represented by formula (S-1).

[0146] The resin composition of the second state of the present invention comprises a compound A having at least one group selected from the group consisting of hydroxyl, amino, and thiol groups, at least one group selected from amide and ester groups, and a group represented by formula (S-1). The compound A in the resin composition of the second state has the same meaning as the compound A in the resin composition of the first state, and also the same in the preferred state.

[0147] Compound A is preferably a compound represented by formula (1-1). [Chemical Formula 34] In formula (1-1), R1 independently represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms that can be substituted, R2 independently represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms that can be substituted, L represents an m+n valence linkage containing an amino group or an ester group, x represents an integer of 1 or more and 3 or less, m represents an integer of 1 or more, and n represents an integer of 1 or more.

[0148] In formula (1-1), R1, R2 and x have the same meaning as R1, R2 and x in formula (S-1), and the better state is also the same.

[0149] In formula (1-1), the orientation of the amide or ester group in L is not particularly limited. In formula (1-1), it is preferable that L is an m+n linking group containing an amide group. Furthermore, it is preferable that L is an m+n linking group containing an amide or ester group and a hydrocarbon group, and it is preferable that the group is represented by a combination of an amide or ester group and a hydrocarbon group or a group represented by a combination of an amide or ester group and a heterocyclic group -O-, -CO-, -S-, -SO2- or -NRN-. RN is as described above. As a heterocyclic group, a heteroaromatic ring group is preferred. As a heteroatom in the heterocyclic group, examples include oxygen atom, sulfur atom or nitrogen atom. As the aforementioned hydrocarbon group, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof is preferred; a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof is even more preferred; an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof is further preferred; and a group represented by a combination of an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms is particularly preferred. Furthermore, from the viewpoint of close contact with the silicon wafer, L preferably contains an aromatic group. When compound A contains an aromatic group, it is preferable that the aromatic group exists between at least one group selected from the group consisting of hydroxyl, amino, and thiol groups and at least one group selected from amide and ester groups. The aforementioned aromatic group can be any of an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. As for the aforementioned aromatic hydrocarbon group, an aromatic hydrocarbon group with 6 to 20 carbon atoms is preferred, and a benzene ring group is even more preferred. Furthermore, it is preferred that the carbon atom of L in formula (1-1) that is directly bonded to the hydroxyl group in formula (1-1) is a carbon atom constituting an aliphatic hydrocarbon group; that is, it is preferred that the bonding site between L and the hydroxyl group in formula (1-1) is an aliphatic hydrocarbon group.

[0150] Specific examples of preferred forms of L in formula (1-1) are described below, but the present invention is not limited thereto. In the following specific examples, * indicates a bonding site with the Si atom in formula (1-1), and # indicates a bonding site with the hydroxyl group in formula (1-1). [Chemical Formula 35]

[0151] In formula (1-1), x represents an integer greater than or equal to 1 and less than or equal to 3, with 2 or 3 being preferred and 3 being even better. In formula (1-1), m is a preferred integer from 1 to 4, with 1 or 2 being even better and 1 being even better. n is a preferred integer from 1 to 4, with 1 or 2 being even better and 1 being even better.

[0152] Compound A is preferably a compound represented by formula (2-1). [Chemical Formula 36] In formula (2-1), R1 independently represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms that can be substituted, R2 independently represents a hydrogen atom or a hydrocarbon group with 1 to 30 carbon atoms that can be substituted, L1 represents a single bond or a divalent linkage, Z represents a amide group, the orientation of the amide group in Z is not particularly limited, L2 represents a single bond or a divalent linkage, Ar represents an aromatic group, X represents an alkyl group, and x represents an integer of 1 or more and 3 or less.

[0153] In equation (2-1), R1, R2 and x have the same meaning as R1, R2 and x in equation (1-1), and the better state is also the same.

[0154] In formula (2-1), L1 is preferably a single bond or a hydrocarbon group, or a group represented by a combination of a hydrocarbon group and -O-, -CO-, -S-, -SO2- or -NRN-, and more preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-, and even more preferably a hydrocarbon group. As the above-mentioned hydrocarbon group, alkyl, phenyl, or a combination thereof is preferred, and alkyl is even more preferred. As the above-mentioned alkyl group, alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 4 carbon atoms are even more preferred.

[0155] In formula (2-1), Z represents a amide group, which can be a substituted amide group or an unsubstituted amide group, with an unsubstituted amide group being preferred. The orientation of the amide group is not particularly limited. For example, the nitrogen atom of the amide group at the bonding site with L2 is also one of the preferred states of the present invention.

[0156] In formula (2-1), L2 represents a single bond or a divalent linkage. A single bond or a hydrocarbon group, or a group represented by a combination of a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O)2-, or -NRN-, is preferred. A hydrocarbon group, or a group represented by a combination of a hydrocarbon group and -C(=O)O- or -C(=O)NRN-, is even more preferred. A hydrocarbon group is further preferred. As the aforementioned hydrocarbon group, an alkyl group, an phenyl group, or a combination thereof is preferred, and an alkyl group is even more preferred. As the aforementioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is even more preferred.

[0157] In formula (2-1), Ar is preferably an aromatic hydrocarbon group, and phenyl is even more preferred. Ar can be an aromatic heterocyclic group, or an aromatic hydrocarbon group that forms a heterocycle with a heterocyclic group or a hydrocarbon group. Examples of heteroatoms in the above-mentioned aromatic heterocyclic group or heterocyclic group include oxygen atoms, sulfur atoms, nitrogen atoms, etc.

[0158] In formula (2-1), X is preferably an alkyl group with 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms, and methylene is particularly preferred.

[0159] 〔Molecular weight〕 It is preferred that the molecular weight of compound A is 200 to 1,000, more preferably 300 to 900, and even more preferably 300 to 800.

[0160] [Synthetic Method] For example, compound A can be synthesized by the method described in the synthesis examples in the following embodiments. Alternatively, it can be synthesized by other known synthetic methods; there are no particular limitations on the synthetic method.

[0161] As a specific example of compound A, there is no particular limitation, but C-1 to C-23 used in the examples can be cited.

[0162] [Other silane coupling agents] The resin composition of the present invention may contain other silane coupling agents different from compound A described above. There are no particular limitations on other silane coupling agents; silane coupling agents known in the art can be used. For example, compounds described in International Publication No. 2015 / 199219, paragraph 0167; compounds described in Japanese Patent Application Publication No. 2014-191002, paragraphs 0062-0073; compounds described in International Publication No. 2011 / 080992, paragraphs 0063-0071; and compounds described in Japanese Patent Application Publication No. 2014-191002, paragraphs 0062-0073. The compounds described in paragraphs 0060-0061 of Japanese Patent Application Publication No. 2014-191252, paragraphs 0045-0052 of Japanese Patent Application Publication No. 2014-041264, paragraph 0055 of International Patent Application Publication No. 2014 / 097594, and paragraphs 0067-0078 of Japanese Patent Application Publication No. 2018-173573 are incorporated herein by reference. Furthermore, as described in paragraphs 0050-0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. Additionally, it is preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents methyl and Et represents ethyl.

[0163] [Chemical Formula 37]

[0164] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3- Acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureapropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[0165] The content of the silane coupling agent relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 20% by mass. A lower limit of 0.5% by mass or more is more preferred, and 1.0% by mass or more is further preferred. An upper limit of 10% by mass or less is more preferred, and 5% by mass or less is further preferred. One type of silane coupling agent may be used alone, or two or more may be used in combination. When two or more are used simultaneously, the total amount is preferably within the above-mentioned range. The content of compound A relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 20% by mass. A lower limit of 0.5% by mass or more is more preferred, and 1.0% by mass or more is further preferred. An upper limit of 10% by mass or less is more preferred, and 5% by mass or less is further preferred. One type of compound A may be used alone, or two or more may be used in combination. When two or more are used simultaneously, the total amount is preferably within the above-mentioned range. In this invention, it is also possible to configure a state in which there is substantially no other silane coupling agent different from compound A. Specifically, it is preferable that the content of other silane coupling agents relative to the total solids content of the resin composition is 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less. The lower limit is not particularly limited and can be 0% by mass. In this invention, it is also possible to configure a state in which there is substantially no silane coupling agent different from the compound represented by formula (2-1). Specifically, it is preferable that the content of silane coupling agents relative to the total solids content of the resin composition in this invention is 1% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less. The lower limit is not particularly limited and can be 0% by mass.

[0166] <Organometallic Complexes> From the viewpoint of drug resistance, the resin composition of the present invention may contain organometallic complexes. Organometallic complexes are any organic complex compounds containing metal atoms; complex compounds containing metal atoms and organic groups are preferred; compounds in which the organic group is coordinated with the metal atom are more preferred; and metallocene compounds are even more preferred. In the present invention, a metallocene compound refers to an organometallic complex containing two cyclopentadienyl anionic derivatives that may have substituents as n5-ligands. The organic group is not particularly limited; a hydrocarbon group or a group composed of a hydrocarbon group and a heteroatom is preferred. As heteroatoms, oxygen, sulfur, and nitrogen atoms are preferred. In the present invention, at least one of the organic groups is preferably a cyclic group, and at least two are more preferred. The cyclic group is preferably selected from 5-membered and 6-membered cyclic groups, with 5-membered cyclic groups being more preferred. The aforementioned cyclic group can be a hydrocarbon ring or a heterocycle, with a hydrocarbon ring being preferred. As a 5-membered ring cyclic group, a cyclopentadienyl group is preferred. Furthermore, the organometallic complex used in this invention preferably contains 2 to 4 cyclic groups per molecule.

[0167] The metal contained in the organometallic complex is not particularly limited, but it is preferred to be a metal belonging to Group 4 elements, more preferably to be selected from at least one metal from the group including titanium, zirconium and hafnium, further preferably to be selected from at least one metal from the group including titanium and zirconium, and titanium is particularly preferred.

[0168] Organometallic complexes may contain two or more metal atoms, or they may contain only one metal atom, but it is preferred that they contain only one metal atom. When organometallic complexes contain two or more metal atoms, they may contain only one type of metal atom or they may contain two or more types of metal atoms.

[0169] The organometallic complex is preferably a ferrocene compound, a titanium diacene compound, a zirconium diacene compound, or a hafnium diacene compound, more preferably a titanium diacene compound, a zirconium diacene compound, or a hafnium diacene compound, further preferably a titanium diacene compound or a zirconium diacene compound, and especially preferably a titanium diacene compound.

[0170] An organometallic complex possessing photoradical polymerization initiation capability is also a preferred embodiment of the present invention. In the present invention, photoradical polymerization initiation capability refers to the ability to generate free radicals capable of initiating free radical polymerization upon irradiation with light. For example, when a composition containing a free radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength region where the organometallic complex absorbs light and the free radical crosslinking agent does not absorb light, the presence or absence of photoradical polymerization initiation capability can be confirmed by checking whether the free radical crosslinking agent disappears. When confirming whether it has disappeared, an appropriate method can be selected according to the type of free radical crosslinking agent, such as IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography). When the organometallic complex possesses photoradical polymerization initiation capability, a metallocene compound is preferred, followed by a titanocene compound, a zirconium diacene compound, or a hafnium diacene compound; a titanocene compound or a zirconium diacene compound is further preferred, and a titanocene compound is particularly preferred. When the organometallic complex does not possess photoradical polymerization initiation ability, it is preferable that the organometallic complex is selected from at least one compound from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, acetylated titanium compounds, chelated titanium compounds, zirconium diacene compounds, and hafnium diacene compounds; it is even more preferable that the compound is selected from at least one compound from the group consisting of titanocene compounds and zirconium diacene compounds; it is further preferable that the compound is selected from at least one compound from the group consisting of titanocene compounds and zirconium diacene compounds; and titanocene compounds are particularly preferred.

[0171] The molecular weight of the organometallic complex is preferably 50 to 2,000, and even more preferably 100 to 1,000.

[0172] As organometallic complexes, compounds represented by the following formula (P) are preferably exemplified. [Chemical Formula 38] In formula (P), M is a metal atom, and R are each independently a substituent. It is preferred that R are each independently selected from aromatic groups, alkyl groups, halogen atoms, and alkylsulfonyloxy groups.

[0173] In formula (P), iron, titanium, zirconium, or hafnium atoms are preferred as the metal atom represented by M; titanium, zirconium, or hafnium atoms are more preferred; titanium or zirconium atoms are even more preferred; and titanium atoms are particularly preferred. As the aromatic group in R of formula (P), aromatic groups having 6 to 20 carbon atoms are preferred, and aromatic hydrocarbon groups having 6 to 20 carbon atoms are preferred, such as phenyl, 1-naphthyl, or 2-naphthyl. As the alkyl group in R of formula (P), alkyl groups having 1 to 20 carbon atoms are preferred, and alkyl groups having 1 to 10 carbon atoms are more preferred, such as methyl, ethyl, propyl, octyl, isopropyl, tributyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, and cyclopentyl. As the halogen atom in the above-mentioned R, F, Cl, Br, and I are examples. As the alkyl group constituting the alkyl sulfonyloxy group in the above-mentioned R, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred. Examples include methyl, ethyl, propyl, octyl, isopropyl, tributyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. The above-mentioned R may further have substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acetyl, alkoxycarbonyl, aryloxycarbonyl, acetyloxy, monoalkylamino, dialkylamino, monoarylamino, and diarylamino.

[0174] Specific examples of organometallic complexes are not particularly limited, but may include tetraisopropoxy titanium, tetra(2-ethylhexyloxy) titanium, diisopropoxybis(ethyl acetate) titanium, diisopropoxybis(acetyl acetone) titanium, bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl) titanium, pentamethylcyclopentadientrimethoxy titanium, bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl) titanium, and the following compounds. [Chemical Formula 39]

[0175] In addition, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018 / 025738 may also be used, but are not limited thereto.

[0176] The content of the organometallic complex relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass. A lower limit of 1.0% by mass or more is more preferred, 1.5% by mass or more is further preferred, and 3.0% by mass or more is particularly preferred. An upper limit of 25% by mass or less is more preferred. One or more organometallic complexes can be used. When two or more are used, the total amount within the above-mentioned range is preferred.

[0177] <Polymerizable Compound> It is preferable that the resin composition of the present invention contains a polymerizable compound. Examples of polymerizable compounds include free radical crosslinking agents or other crosslinking agents.

[0178] [Free Radical Crosslinking Agent] It is preferable that the resin composition of the present invention includes a free radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As a free radical polymerizable group, it is preferable that it includes a group having an ethylene unsaturated bond. Examples of groups having an ethylene unsaturated bond include vinyl, allyl, vinylphenyl, (meth)acrylyl, maleicadiimino, (meth)acrylamide, etc. Among these, (meth)acrylyl, (meth)acrylamide, and vinylphenyl are preferred as groups having an ethylene unsaturated bond, and (meth)acrylyl is more preferred from the viewpoint of reactivity.

[0179] It is preferable that the free radical crosslinking agent is a compound having one or more ethylene unsaturated bonds, and even more preferable that it is a compound having two or more ethylene unsaturated bonds. The free radical crosslinking agent may have three or more ethylene unsaturated bonds. As a compound having two or more of the above-mentioned ethylene unsaturated bonds, a compound having 2 to 15 ethylene unsaturated bonds is preferable, a compound having 2 to 10 ethylene unsaturated bonds is more preferable, and a compound having 2 to 6 ethylene unsaturated bonds is even more preferable. Furthermore, from the viewpoint of the film strength of the obtained pattern (cured material), it is also preferable that the resin composition of the present invention includes compounds having two ethylene unsaturated bonds and compounds having three or more of the above-mentioned ethylene unsaturated bonds.

[0180] It is preferable that the molecular weight of the free radical crosslinking agent is 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. It is preferable that the lower limit of the molecular weight of the free radical crosslinking agent is 100 or more.

[0181] Specific examples of free radical polymerizable compounds include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl, amino, or hydrogen sulfide groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids are also preferred. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are preferred, as are substitution reactions of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or toluenesulfonyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. Additionally, as another example, compounds substituted with unsaturated phosphonic acids, styrene, vinylbenzene derivatives, vinyl ethers, or allyl ethers can be used instead of the aforementioned unsaturated carboxylic acids. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0182] Furthermore, it is preferable that the free radical crosslinking agent is a compound having a boiling point of 100°C or higher at normal pressure. Examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl tetramethylolethane tri(meth)acrylate, neopentyl tetramethylolethane tetra(meth)acrylate, dinepentyl tetramethylolethane penta(meth)acrylate, dinepentyl tetramethylolethane hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerol, or trimethylolethane, which are added to a polyfunctional alcohol and then subjected to (meth)acrylate reaction with ethylene oxide or propylene oxide. Esterified compounds, urethane (meth)acrylates described in Japanese Patent Application Publications Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates described in Japanese Patent Application Publications Nos. 48-064183, 49-043191, and 52-030490, multifunctional acrylates or methacrylates such as epoxy acrylates as products of the reaction of epoxy resin and (meth)acrylic acid; and mixtures thereof. Furthermore, compounds described in paragraphs 0254 to 0257 of Japanese Patent Application Publication No. 2008-292970 are also preferred. Furthermore, examples include polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds such as glycidyl (meth)acrylate that have cyclic ether groups and vinyl unsaturated bonds.

[0183] Furthermore, as a preferred free radical crosslinking agent other than those mentioned above, compounds having a cycloid and having two or more groups having ethylene unsaturated bonds, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, as well as cardo resins, can also be used.

[0184] Furthermore, as other examples, specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, and vinylphosphonic acid compounds described in Japanese Patent Application Publication No. 02-025493, etc., can also be used. Furthermore, compounds containing perfluoroalkyl groups described in Japanese Patent Application Publication No. 61-022048 can also be used. Furthermore, those introduced as photopolymerizable monomers and oligomers in the "Journal of the Adhesion Society of Japan" vol. 20, No. 7, pp. 300-308 (1984) can also be used.

[0185] In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015 / 199219 are also preferably used, and such contents are incorporated in this specification.

[0186] Furthermore, the compounds described in Japanese Patent Application Publication No. 10-062986 as formulas (1) and (2) together with their specific examples can also be used as free radical crosslinking agents. These compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then esterifying it with (meth)acrylate.

[0187] Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Publication No. 2015-187211 can also be used as free radical crosslinking agents, and such contents are incorporated in this specification.

[0188] As a free radical crosslinking agent, dinepentylenetetroxide triacrylate (commercially available as KAYARAD D-330 (Nippon Kayaku Co., Ltd.)), dinepentylenetetroxide tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku Co., Ltd.)), A-TMMT (Shin-Nakamura Chemical Co., Ltd.), dinepentylenetetroxide penta(meth)acrylate (commercially available as KAYARAD D-310 (Nippon Kayaku Co., Ltd.)), dinepentylenetetroxide hexa(meth)acrylate (commercially available as KAYARAD DPHA (Nippon Kayaku Co., Ltd.)), A-DPH (Shin-Nakamura Chemical Co., Ltd.), and structures in which the (meth)acrylic acid group is bonded via ethylene glycol residues or propylene glycol residues are preferred. Oligopolymer types such as these can also be used.

[0189] Commercially available free radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethoxy groups manufactured by Sartomer Company, Inc.; SR-209, 231, and 239, a difunctional methacrylate with four ethoxy groups manufactured by Sartomer Company, Inc.; DPCA-60, a hexafunctional acrylate with six pentyloyl groups manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutyloyl groups manufactured by Nippon Kayaku Co., Ltd.; UAS-10 and UAB-140, carbamate oligomers manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.; NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.); and DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.). Products manufactured by Kayaku Co., Ltd., including UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and BLEMMER PME400 (manufactured by NOF CORPORATION.).

[0190] As free radical crosslinking agents, urethane ester acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and urethane ester compounds having an ethylene oxide backbone described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. Furthermore, as a free radical crosslinking agent, compounds with an amino group structure or a thioether structure described in Japanese Patent Application Publication No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. 01-105238 can also be used.

[0191] The free radical crosslinking agent can be a free radical crosslinking agent having acid groups such as carboxyl groups and phosphate groups. It is preferable that the free radical crosslinking agent having acid groups is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and even more preferable is a free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Particularly preferred are compounds in which the aliphatic polyhydroxy compound is neopentyl tetrol or dinepentyl tetrol in the free radical crosslinking agent that reacts the unreacted hydroxyl groups of the aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride to give it acid groups. Commercially available examples include, for instance, polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO.,LTD.

[0192] The preferred acid value of the free radical crosslinking agent containing acid groups is 0.1 to 300 mg KOH / g, and particularly preferably 1 to 100 mg KOH / g. When the acid value of the free radical crosslinking agent is within the above range, it exhibits excellent manufacturability and, consequently, excellent developability. Furthermore, it demonstrates good polymerizability. The above acid value was determined according to the description in JIS K 0070:1992.

[0193] From the viewpoint of pattern resolution and film elasticity, it is preferable to use difunctional methacrylates or acrylates as the resin composition. Specific compounds that can be used include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol diacrylate. Dimethacrylates, dimethyloltricyclodecane diacrylates, dimethyloltricyclodecane dimethacrylates, ethylene oxide (EO) adduct diacrylates of bisphenol A, EO adduct dimethacrylates of bisphenol A, PO adduct diacrylates of bisphenol A, PO adduct dimethacrylates of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylates, EO-modified diacrylates of isocyanuric acid, isocyanuric acid-modified dimethacrylates, other difunctional acrylates having urethane bonds, and difunctional methacrylates having urethane bonds. Two or more of these can be mixed as needed. Furthermore, for example, PEG200 diacrylate refers to polyethylene glycol diacrylates with a molecular weight of approximately 200. From the viewpoint of suppressing warping caused by controlling the elastic modulus of the accompanying pattern (cured material), the resin composition of the present invention preferably uses a monofunctional free radical crosslinking agent as a free radical crosslinking agent. As monofunctional free radical crosslinking agents, the following are preferred: n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, butoxyethyl methacrylate, carbitol methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, N-hydroxymethyl (meth)acrylamide, glycidyl methacrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-vinylpyrrolidone, N-vinylcaprolactone, and allyl glycidyl ether. For monofunctional free radical crosslinking agents, compounds with a boiling point of 100°C or higher at ambient pressure are also preferred to suppress pre-exposure volatilization. Furthermore, as multifunctional or higher free radical crosslinking agents, allyl compounds such as diallyl phthalate and triallyl trimellitate are also suitable.

[0194] When a free radical crosslinking agent is contained, it is preferable that its content relative to the total solids content of the resin composition of the present invention is more than 0% by mass and less than 60% by mass. A lower limit of 5% by mass or more is more preferred. An upper limit of 50% by mass or less is more preferred, and 30% by mass or less is further preferred.

[0195] A single free radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more are used simultaneously, it is preferable that their total dosage be within the range mentioned above.

[0196] [Other Crosslinking Agents] It is preferable that the resin composition of the present invention includes other crosslinking agents different from the free radical crosslinking agents described above. In the present invention, other crosslinking agents refer to crosslinking agents other than the free radical crosslinking agents described above. It is preferable that the compound has a plurality of groups within the molecule that promote the reaction (forming covalent bonds between the compound and other compounds in the composition or their reaction products) by photosensitive acid generators or photobase generators. It is even preferable that the compound has a plurality of groups within the molecule that promote the reaction (forming covalent bonds between the compound and other compounds in the composition or their reaction products) by the action of acids or bases. It is preferable that the acid or base described above is an acid or base generated from the photosensitive acid generator or photobase generator during the exposure step. As other crosslinking agents, it is preferable that the compound has at least one group selected from the group consisting of acetoxymethyl, hydroxymethyl and alkoxymethyl, and it is even preferable that the compound has a structure in which at least one group selected from the group consisting of acetoxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom. Other crosslinking agents include, for example, compounds having the following structure: a structure in which an amine-containing compound such as melamine, acetylenurea, urea, alkylurea, or benzoguanidine is reacted with formaldehyde, or formaldehyde is reacted with an alcohol, and the hydrogen atoms of the aforementioned amine groups are replaced with acetoxymethyl, hydroxymethyl, or alkoxymethyl groups. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Furthermore, it can be an oligomer formed by the self-condensation of the hydroxymethyl groups of these compounds. As the aforementioned amine-containing compounds, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using acetylenurea, urea, or alkylurea are called urea-based crosslinking agents, crosslinking agents using alkylurea are called alkylurea-based crosslinking agents, and crosslinking agents using benzoguanidine are called benzoguanidine-based crosslinking agents. In these embodiments, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and it is even more preferable that it contains at least one compound selected from the group consisting of acetylene urea-based crosslinking agents and melamine-based crosslinking agents described below.

[0197] As a compound containing at least one of alkoxymethyl and acetoxymethyl groups in the present invention, examples of compounds in which the alkoxymethyl or acetoxymethyl group is directly substituted on the nitrogen atom or trimethylol group of the aromatic group or the urea structure described below are provided as structural examples. Regarding the alkoxymethyl or acetoxymethyl group in the above-mentioned compound, it is preferred that the number of carbon atoms is 2 to 5, preferably 2 or 3, and more preferably 2. It is preferred that the total number of alkoxymethyl and acetoxymethyl groups in the above-mentioned compound is 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. It is preferred that the molecular weight of the above-mentioned compound is 1500 or less, and preferably 180 to 1200.

[0198] [Chemical Formula 40]

[0199] R100 represents an alkyl or acetyl group. R101 and R102 each independently represent a monovalent organic group that can bond with each other to form a ring.

[0200] As compounds in which alkoxymethyl or acetomethyl groups are directly substituted on an aromatic group, examples include compounds of the following general formula.

[0201] [Chemical Formula 41]

[0202] In the formula, X represents a single bond or a divalent organic group, each R104 independently represents an alkyl or acetyl group, and R103 represents a hydrogen atom, alkyl, alkenyl, aryl, aralkyl, or a group that decomposes under the action of an acid to generate a base-soluble group (e.g., a group that is released by the action of an acid, or a group represented by -C(R4)2COOR5 (R4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R5 represents a group that is released by the action of an acid.)). Each R105 independently represents an alkyl or alkenyl group, a, b, and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3, a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less. Regarding groups that decompose under the action of acid to generate base-soluble groups, groups that are released under the action of acid, and R5 in groups represented by -C(R4)2COOR5, examples include -C(R36)(R37)(R38), -C(R36)(R37)(OR39), and -C(R01)(R02)(OR39). In these formulas, R36 to R39 independently represent alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups. R36 and R37 can be bonded together to form a ring. Alkyl groups with 1 to 10 carbon atoms are preferred, and alkyl groups with 1 to 5 carbon atoms are more preferred. The alkyl groups can be either straight-chain or branched. Cycloalkyl groups with 3 to 12 carbon atoms are preferred, and cycloalkyl groups with 3 to 8 carbon atoms are more preferred. The cycloalkyl groups can be monocyclic or polycyclic structures such as condensed rings. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and phenyl is more preferred. As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferred, and an alkyl group having 7 to 16 carbon atoms is more preferred. The aralkyl group refers to an aryl group substituted with an alkyl group, and the preferred states of these alkyl and aryl groups are the same as those of the alkyl and aryl groups mentioned above. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and an alkenyl group having 3 to 16 carbon atoms is more preferred. Furthermore, these groups may further have known substituents within the scope of obtaining the effects of the present invention.

[0203] R01 and R02 independently represent hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl or alkenyl.

[0204] The group that decomposes and generates a base-soluble group by the action of an acid, or that is removed by the action of an acid, is preferably a trialkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. More preferably a trialkyl ester group or an acetal group.

[0205] Specific examples of compounds having an alkoxymethyl group include the following structures. Examples of compounds having an acetoxymethyl group include compounds in which the alkoxymethyl group of the following compounds is replaced with an acetoxymethyl group. Examples of compounds having an alkoxymethyl group or an acetoxymethyl group within the molecule include the following compounds, but are not limited to these.

[0206] [Chemical Formula 42]

[0207] [Chemical Formula 43]

[0208] Compounds containing at least one of alkoxymethyl and acetoxymethyl can be commercially available or synthesized by known methods. From the viewpoint of heat resistance, compounds in which the alkoxymethyl or acetoxymethyl is directly substituted on the aromatic ring or trihalomethane ring are preferred.

[0209] Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

[0210] Specific examples of urea-based crosslinking agents include, for instance, monohydroxymethylated acetylenide, dihydroxymethylated acetylenide, trihydroxymethylated acetylenide, tetrahydroxymethylated acetylenide, monomethoxymethylated acetylenide, dimethoxymethylated acetylenide, trimethoxymethylated acetylenide, tetramethoxymethylated acetylenide, monoethoxymethylated acetylenide, diethoxymethylated acetylenide, triethoxymethylated acetylenide, tetraethoxymethylated acetylenide, monopropoxymethylated acetylenide, dipropoxymethylated acetylenide, tripropoxymethylated acetylenide, tetrapropoxymethylated acetylenide, monobutoxymethylated acetylenide, dibutoxymethylated acetylenide, tributoxymethylated acetylenide, or tetrabutoxymethylated acetylenide, etc.; urea-based crosslinking agents such as dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea, etc. Vinylurea crosslinking agents such as monohydroxymethylated vinylurea or dihydroxymethylated vinylurea, monomethoxymethylated vinylurea, dimethoxymethylated vinylurea, monoethoxymethylated vinylurea, diethoxymethylated vinylurea, monopropoxymethylated vinylurea, dipropoxymethylated vinylurea, monobutoxymethylated vinylurea or dibutoxymethylated vinylurea, etc.; propylene urea 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, etc.; 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidineone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidineone, etc.

[0211] Specific examples of benzoguanidine-based crosslinking agents include, for example, monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monoethoxymethylated benzoguanidine, diethoxymethylated benzoguanidine, triethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, tetrabutoxymethylated benzoguanidine, etc.

[0212] Furthermore, as a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl, a compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl directly bonded to an aromatic ring (preferably a benzene ring) may also be preferred. Specific examples of such compounds include benzene glycol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzoic acid hydroxymethylbenzene, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenylbenzene Ketones, methoxymethylbenzoic acid, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetra(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

[0213] As other crosslinking agents, commercially available products can 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, DMLBisOC-P, DMOM-PC, 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.), NIKALAC (registered trademark, same below) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all manufactured by SANWA CHEMICAL CO.,LTD), etc.

[0214] Furthermore, it is preferable that the resin composition of the present invention contains at least one compound selected from the group consisting of epoxy compounds, cyclobutane compounds and benzo[a] compounds as other crosslinking agents.

[0215] -Epoxy compound (a compound having epoxy groups)- As an epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. Epoxy groups undergo cross-linking reactions below 200°C and do not trigger dehydration reactions due to cross-linking, thus minimizing the risk of film shrinkage. Therefore, by containing an epoxy compound, low-temperature curing and warping of the resin composition of the present invention can be effectively suppressed.

[0216] It is preferable that the epoxy compound contains polyethylene oxide. This further reduces the elastic modulus and suppresses warping. Polyethylene oxide refers to ethylene oxide with 2 or more repeating units, preferably 2 to 15 repeating units.

[0217] Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and polysiloxanes containing epoxy groups such as polymethyl (epoxypropoxypropyl)siloxane, but are not limited to these.Specifically, examples include EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, 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, and EPICLON (registered trademark) N-740 (these are product names, DIC). (Manufactured by Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are trade names, manufactured by Daicel) (Manufactured by Nippon Kayaku Co., Ltd.), 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 (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc. Furthermore, the following compounds may also be used preferentially.

[0218] [Chemical Formula 44]

[0219] In the formula, n is an integer from 1 to 5, and m is an integer from 1 to 20.

[0220] In the above structure, considering both heat resistance and improved elongation, n of 1 to 2 and m of 3 to 7 are preferred.

[0221] -Oxycyclobutane compounds (compounds having an oxycyclobutane ring)- Examples of oxycyclobutane compounds include compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethyloxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutane)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, and 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxycyclobutane)methyl] ester. Specifically, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO.,LTD. is preferred; these can be used alone or in mixtures of two or more.

[0222] -Benzozoline compounds (compounds with benzozoline groups)-Benzozoline compounds are preferred because the cross-linking reaction caused by the ring-opening addition reaction does not cause degassing during hardening, thereby reducing thermal shrinkage and inhibiting warping.

[0223] Preferred examples of benzo[a]benzyl compounds include Pd-type benzo[a]benzyl, Fa-type benzo[a]benzyl (trade names, manufactured by Shikoku Chemicals Corporation), benzo[a]benzyl adducts of polyhydroxystyrene resins, and phenolic varnish-type dihydrobenzo[a]benzyl compounds. These can be used alone or in combination of two or more.

[0224] The content of other crosslinking agents relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and especially preferably 1.0 to 10% by mass. The other crosslinking agents may be only one type or may contain two or more types. When two or more other thermal crosslinking agents are contained, it is preferable that their total content is within the above-mentioned range.

[0225] [Polymerization Initiator] It is preferable that the resin composition of the present invention contains a polymerization initiator capable of initiating polymerization by light and / or heat. In particular, it is preferable that it contains a photopolymerization initiator. It is preferable that 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, it is preferable that the photoradical polymerization initiator is photosensitive to light in the ultraviolet to visible regions. In addition, it can be an active agent that interacts with the photoexcited sensitizer and generates active free radicals.

[0226] The photoradical polymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 L·mol⁻¹·cm⁻¹ in the wavelength range of about 240–800 nm (preferably 330–500 nm). The molar absorptivity of the compound can be determined using known methods. For example, it is preferable to determine it using an ethyl acetate solvent at a concentration of 0.01 g / L with a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer).

[0227] As a photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds with a trimethylolamine skeleton, compounds with a diazole skeleton, compounds with a trihalomethyl skeleton, etc.), acetylphosphine compounds such as acetylphosphine oxide, hexaaryl diimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-amino ketone compounds such as aminoacetophenone, α-hydroxy ketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron aromatic complexes, etc. For details regarding these compounds, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Application Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Application Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Application Publication No. 2019-167313, all of which are incorporated herein by reference.

[0228] As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference. KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used in commercially available products.

[0229] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and amide phosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Publication No. 10-291969 and amide phosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, as described herein.

[0230] As an α-hydroxy ketone initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), 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.

[0231] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369 and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0232] As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, which have a maximum absorption wavelength that matches a light source of wavelengths such as 365 nm or 405 nm, can also be used, and this content is included in this specification.

[0233] Examples of phosphine oxide initiators include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. Additionally, Omnirad 819, Omnirad TPO (both manufactured by IGM Resins BV), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF) can also be used.

[0234] Examples of metallocene compounds include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem Co., Ltd.).

[0235] Oxime compounds are even better examples of photoradical polymerization initiators. By using oxime compounds, exposure latitude can be further improved more effectively. Oxime compounds have a wider exposure latitude (exposure margin) and also act as photocuring accelerators, making them particularly advantageous.

[0236] Specific examples of oxime compounds include compounds described in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in the Journal of Photopolymer Science and... The compounds described in Technology (1995, pp. 202-232), Japanese Patent Application Publication No. 2000-066385, Japanese Patent Application Publication No. 2004-534797, Japanese Patent Application Publication No. 2017-019766, Japanese Patent No. 6065596, International Publication No. 2015 / 152153, International Publication No. 2017 / 051680, Japanese Patent Application Publication No. 2017-198865, International Publication No. 2017 / 164127 (paragraphs 0025-0038), and International Publication No. 2013 / 167515 are included in this specification.

[0237] Examples of preferred oxime compounds include compounds with the following structures: 3-(benzoxyloxy(imino))but-2-one, 3-(acetoxy(imino))but-2-one, 3-(propoxy(imino))but-2-one, 2-(acetoxy(imino))pent-3-one, 2-(acetoxy(imino))-1-phenylprop-1-one, 2-(benzoxyloxy(imino))-1-phenylprop-1-one, 3-((4-toluenesulfonoxy(imino))but-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylprop-1-one. In the resin composition of the present invention, it is particularly preferred to use oxime compounds (oxime-based photoradical polymerization initiators) as photoradical polymerization initiators. Oxime-based photoradical polymerization initiators have an intramolecular linker >C=NOC(=O)-.

[0238] [Chemical Formula 45]

[0239] 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, the photoradical polymerization initiator 2 described in Japanese Patent Application Publication No. 2012-014052) are also suitable. Furthermore, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) are also suitable. Additionally, DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) are also suitable. Furthermore, oxime compounds with the following structure can also be used. [Chemical Formula 46]

[0240] Oxime compounds having a cyclohexane ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a cyclohexane ring include the compounds described in Japanese Patent Application Publication No. 2014-137466 and the compounds described in Japanese Patent No. 06636081, the contents of which are incorporated herein by reference.

[0241] As a photoradical polymerization initiator, oxime compounds having at least one benzene ring having a carbazole ring as the backbone of a naphthalene ring can also be used. Specific examples of such oxime compounds include the compound described in International Publication No. 2013 / 083505, the contents of which are incorporated herein by reference.

[0242] Oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471, the contents of which are incorporated herein by reference.

[0243] Oxime compounds containing nitro groups can be used as photopolymerization initiators. It is also preferable that the oxime compound containing nitro groups is a dimer. Specific examples of oxime compounds containing nitro groups include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007 to 0025 of Japanese Patent Application Publication No. 4223071, the contents of which are incorporated herein by reference. Furthermore, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION) is also an example of an oxime compound containing nitro groups.

[0244] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75 as described in International Publication No. 2015 / 036910.

[0245] Oxime compounds with hydroxyl substituents bonded to the carbazole backbone can also be used as photoradical polymerization initiators. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019 / 088055, the contents of which are incorporated herein by reference.

[0246] As a photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic cyclic group ArOX1 with an electron-withdrawing group introduced into the aromatic ring can also be used. Examples of electron-withdrawing groups in the aforementioned aromatic cyclic ArOX1 include acetyl, nitro, trifluoromethyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, and cyano. Acetyl and nitro are preferred, and acetyl is more preferred from the perspective of easily forming a film with excellent lightfastness, while benzoyl is further preferred. Benzyl may have substituents. As substituents, halogen atoms, cyano, nitro, hydroxyl, alkyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkenyl, alkyl hydrogen sulfide, aryl hydrogen sulfide, acetyl or amino are preferred, alkyl, alkoxy, aryl, aryloxy, heterocyclic, alkyl hydrogen sulfide, aryl hydrogen sulfide or amino are even more preferred, and alkoxy, alkyl hydrogen sulfide or amino are further preferred.

[0247] The oxime compound OX is preferably selected from at least one of the compounds represented by formula (OX1) and the compounds represented by formula (OX2), with the compound represented by formula (OX2) being more preferred. [Chemical Formula 47] In this formula, RX1 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylhydrothio, arylhydrothio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetyl, acetoxy, amino, phosphinyl, aminomethyl, or aminosulfonyl; RX2 represents alkyl, alkenyl, alkoxy, aryl, aryloxy, heterocyclic, heterocyclic, alkylhydrothio, arylhydrothio, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, acetoxy, or amino; and RX3 to RX14 each independently represent a hydrogen atom or a substituent. At least one of RX10 to RX14 is an electron-withdrawing group.

[0248] In the above formula, RX12 is an electron-withdrawing group, and RX10, RX11, RX13 and RX14 are preferably hydrogen atoms.

[0249] As a specific example of an oxime compound OX, the compound described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600 is cited, the contents of which are incorporated herein by reference.

[0250] Examples of preferred oxime compounds include those with specific substituents shown in Japanese Patent Application Publication No. 2007-269779 and those with thioaryl groups shown in Japanese Patent Application Publication No. 2009-191061, the contents of which are incorporated herein by reference.

[0251] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethane trihalomethane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acetylsinyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazolium dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethyl diazole compounds, and 3-aryl substituted coumarin compounds.

[0252] It is even more preferable that the free radical polymerization initiator is a trihalomethane trihalomethane compound, an α-aminoketone compound, an acetophosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazolium dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound, and is selected from at least one compound in the group including trihalomethane trihalomethane compound, α-aminoketone compound, metallocene compound, oxime compound, triarylimidazolium dimer, and benzophenone compound, and is even more preferable to use a metallocene compound or an oxime compound.

[0253] Furthermore, the photoradical polymerization initiator can also be benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone) and other N,N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-aminolinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-aminolinyl-acetone-1 and other aromatic ketones, alkyl anthraquinones and other quinones formed by cyclization with aromatic rings, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. Also, compounds represented by the following formula (I) can be used.

[0254] [Chemical Formula 48]

[0255] In formula (I), RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms, and is a phenyl or biphenyl group, RI01 is a group represented by formula (II) or a group identical to RI00, and RI02 to RI04 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.

[0256] [Chemical Formula 49]

[0257] In the formula, RI05~RI07 are the same as RI02~RI04 in the above formula (I).

[0258] Furthermore, the photoradical polymerization initiator may also be the compound described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469, which is incorporated herein by reference.

[0259] As a photoradical polymerization initiator, a photoradical polymerization initiator with two or more functionalities can be used. By using such a photoradical polymerization initiator, two or more free radicals are generated from one molecule of the photoradical polymerization initiator, thus obtaining good sensitivity. Furthermore, when a compound with an asymmetric structure is used, the crystallinity decreases while the solubility in solvents increases, making it less prone to precipitation over time, thereby improving the long-term stability of the resin composition. Specific examples of photoradical polymerization initiators with two or more functionalities include dimers of oxime compounds described in Japanese Patent Application Publication Nos. 2010-527339, 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of Japanese Patent Application Publication No. 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680; and compounds (E) and compounds described in Japanese Patent Application Publication No. 2013-522445. (G) Cmpd1 to 7 as described in International Publication No. 2016 / 034963, oxime ester photoinitiators as described in paragraph 0007 of Japanese Patent Application Publication No. 2017-523465, photoinitiators as described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators as described in paragraphs 0017 to 0026 of Japanese Patent Application Publication No. 2017-151342 (A), and oxime ester photoinitiators as described in Japanese Patent Application Publication No. 6469669, etc., are included in this specification.

[0260] When a photopolymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are included, the total amount within the above range is preferred. Furthermore, sometimes the photopolymerization initiator also functions as a thermal polymerization initiator; therefore, heating by an oven, heating plate, etc., can sometimes further promote crosslinking based on the photopolymerization initiator.

[0261] 〔Senser〕 The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. The sensitizer in the electronically excited state comes into contact with thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., and produces electron transfer, energy transfer, heating, etc. As a result, the thermal free radical polymerization initiator and photofree radical polymerization initiator undergo chemical changes and decompose, generating free radicals, acids, or bases. As usable sensitizers, compounds such as benzophenone, milchnerone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthraquinone, benzene, oxacyanine, pyrazolotriazole azo, pyridone azo, anthocyanin, phenanthrene, pyrrolopyrazolomethene, phthalocyanine, benzo[a]piperanone, and indigo compounds can be used. Examples of sensitizers include milchnerone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallyl dihydroindone, and p-dimethylaminophenylallyl dihydroindone. Methylaminophenylmethylene dihydroindone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)isonaphthiazole, 1,3-bis(4'-dimethylaminobenzyl)acetone, 1,3-bis(4'-diethylaminobenzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetylated-7-dimethylaminocoumarin, 3- Ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-hydroxylinylbenzophenone, isoamyl dimethylaminobenzoate The following pigments are used: isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyrene)benzo[a]azole, 2-(p-dimethylaminostyrene)benzo[a]thiazole, 2-(p-dimethylaminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzo[a]aniline, N-methylacetamide, 3',4'-dimethylacetamide, etc. Other sensitizing pigments may also be used. For detailed information on sensitizing pigments, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

[0262] When the resin composition contains a sensitizer, the content of the sensitizer relative to the total solid content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 0.5 to 10% by mass. A single sensitizer may be used alone, or two or more may be used simultaneously.

[0263] [Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds having intramolecularly -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH groups, as well as dithiobenzoate, trithiocarbonate, dithiocarbamate, and xanthate compounds having thiocarbonyl sulfhydryl groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. Thiol compounds are particularly preferred.

[0264] Furthermore, the chain transfer agent may also be the compound described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0265] When the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solids content of the resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and further preferably 0.5 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, it is preferable that their total content is within the above-mentioned range.

[0266] <Alkali Generating Agent> The resin composition of the present invention may contain an alkali generating agent. Here, an alkali generating agent refers to a compound capable of generating an alkali through physical or chemical action. Examples of preferred alkali generating agents for the resin composition of the present invention include thermal alkali generating agents and photo-alkali generating agents. In particular, it is preferable that the resin composition contains an alkali generating agent when it contains a precursor of a cyclized resin. By containing a thermal alkali generating agent in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, resulting in improved mechanical properties and chemical resistance of the cured product, for example, improved performance as an interlayer insulating film for a rewiring layer included in a semiconductor package. The alkali generating agent can be either an ionic or a nonionic type. Examples of alkalis generated from the alkali generating agent include, for example, secondary amines and tertiary amines. The alkali generating agent of the present invention is not particularly limited, and known alkali generating agents can be used. Commonly known base-generating agents include, for example, aminomethyloxime compounds, aminomethylhydroxylamine compounds, carbamic acid compounds, methylamine compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimine compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimine compounds, phthalimine derivative compounds, and aceoxyimine compounds. Specific compounds representing nonionic base-generating agents include those represented by formulas (B1), (B2), or (B3). [Chemical Formula 50]

[0267] In formulas (B1) and (B2), Rb1, Rb2, and Rb3 are independently an organic group, a halogen atom, or a hydrogen atom that does not have a tertiary amine structure. Rb1 and Rb2 do not simultaneously become hydrogen atoms. Furthermore, Rb1, Rb2, and Rb3 do not have a carboxyl group. In addition, in this specification, a tertiary amine structure refers to a structure in which all three bonds of the trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, it is not limited to this when the bonded carbon atoms are carbon atoms forming a carbonyl group, that is, when they form an amide group together with the nitrogen atom.

[0268] In formulas (B1) and (B2), it is preferable that at least one of Rb1, Rb2, and Rb3 contains a cyclic structure, and it is even more preferable that at least two of them contain a cyclic structure. The cyclic structure can be any of a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring formed by the condensation of two monocyclic rings. It is preferable that the monocyclic ring is a 5-membered or 6-membered ring, with a 6-membered ring being more preferred. It is preferable that the monocyclic ring is a cyclohexane ring or a benzene ring, with a cyclohexane ring being more preferred.

[0269] More specifically, Rb1 and Rb2 are preferably hydrogen atoms, alkyl groups (preferably with 1 to 24 carbon atoms, more preferably with 2 to 18 carbon atoms, and further preferably with 3 to 12 carbon atoms), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably with 2 to 18 carbon atoms, and further preferably with 3 to 12 carbon atoms), aryl groups (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18 carbon atoms, and further preferably with 6 to 10 carbon atoms), or aralkyl groups (preferably with 7 to 25 carbon atoms, more preferably with 7 to 19 carbon atoms, and further preferably with 7 to 12 carbon atoms). These groups may have substituents within the range that enables the effects of the present invention. Rb1 and Rb2 may be bonded to each other to form a ring. As the formed ring, a nitrogen-containing heterocycle with 4 to 7 members is preferred. In particular, Rb1 and Rb2 are preferably straight-chain, branched or cyclic alkyl groups with substituents (preferably 1 to 24 carbons, more preferably 2 to 18 carbons, and even more preferably 3 to 12 carbons), preferably cycloalkyl groups with substituents (preferably 3 to 24 carbons, more preferably 3 to 18 carbons, and even more preferably 3 to 12 carbons), and preferably cyclohexyl groups with substituents.

[0270] As Rb3, examples include alkyl groups (preferably with 1 to 24 carbons, more preferably with 2 to 18, and further preferably with 3 to 12), aryl groups (preferably with 6 to 22 carbons, more preferably with 6 to 18, and further preferably with 6 to 10), alkenyl groups (preferably with 2 to 24 carbons, more preferably with 2 to 12, and further preferably with 2 to 6), and aralkyl groups (preferably with 7 to 23 carbons, more preferably with 7 to 19, and further preferably with 7 to 12). The preferred substituents are alkyl (preferably 8-24 carbons, more preferably 8-20, and further preferably 8-16 carbons), alkoxy (preferably 1-24 carbons, more preferably 2-18, and further preferably 3-12 carbons), aryloxy (preferably 6-22 carbons, more preferably 6-18, and further preferably 6-12 carbons), or arylalkoxy (preferably 7-23 carbons, more preferably 7-19, and further preferably 7-12 carbons). Cycloalkyl (preferably 3-24 carbons, more preferably 3-18, and further preferably 3-12 carbons), aryl, and arylalkoxy are preferred. Rb3 may further have substituents within the scope of achieving the effects of this invention.

[0271] The compound represented by formula (B1) is preferably represented by formula (B1-1) or formula (B1-2) below. [Chemical Formula 51]

[0272] In the formula, Rb11 and Rb12, and Rb31 and Rb32 have the same meaning as Rb1 and Rb2 in formula (B1), respectively. Rb13 is an alkyl group (preferably with 1 to 24 carbons, more preferably with 2 to 18 carbons, and further preferably with 3 to 12 carbons), an alkenyl group (preferably with 2 to 24 carbons, more preferably with 2 to 18 carbons, and further preferably with 3 to 12 carbons), an aryl group (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and further preferably with 6 to 12 carbons), or an aralkyl group (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and further preferably with 7 to 12 carbons), and may have substituents within the range of exerting the effects of the present invention. Among them, it is preferred that Rb13 is an aralkyl group.

[0273] Rb33 and Rb34 are each independently a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably with 1 to 8 carbon atoms, and even more preferably with 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 8 carbon atoms, and even more preferably with 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18 carbon atoms, and even more preferably with 6 to 10 carbon atoms), an aralkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19 carbon atoms, and even more preferably with 7 to 11 carbon atoms), and a hydrogen atom is preferred.

[0274] Rb35 is an alkyl group (preferably with 1 to 24 carbons, more preferably with 1 to 12 carbons, and even more preferably with 3 to 8 carbons), an alkenyl group (preferably with 2 to 12 carbons, more preferably with 2 to 10 carbons, and even more preferably with 3 to 8 carbons), an aryl group (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 12 carbons), an aralkyl group (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 12 carbons), with an aryl group being preferred.

[0275] The compound represented by formula (B1-1) is preferred over the compound represented by formula (B1-1a). [Chemical Formula 52]

[0276] Rb11 and Rb12 have the same meaning as Rb11 and Rb12 in formula (B1-1). Rb15 and Rb16 are hydrogen atoms, alkyl (preferably 1-12 carbons, more preferably 1-6 carbons, and even more preferably 1-3 carbons), alkenyl (preferably 2-12 carbons, more preferably 2-6 carbons, and even more preferably 2-3 carbons), aryl (preferably 6-22 carbons, more preferably 6-18 carbons, and even more preferably 6-10 carbons), aralkyl (preferably 7-23 carbons, more preferably 7-19 carbons, and even more preferably 7-11 carbons), hydrogen atoms, or methyl groups are preferred. Rb17 is an alkyl group (preferably with 1 to 24 carbons, more preferably with 1 to 12 carbons, and even more preferably with 3 to 8 carbons), an alkenyl group (preferably with 2 to 12 carbons, more preferably with 2 to 10 carbons, and even more preferably with 3 to 8 carbons), an aryl group (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 12 carbons), or an aralkyl group (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 12 carbons), wherein an aryl group is preferred.

[0277] [Chemical Formula 53]

[0278] In formula (B3), L is a divalent hydrocarbon group with a saturated hydrocarbon group in the path of the linking chain connecting adjacent oxygen atoms and carbon atoms, indicating a hydrocarbon group with 3 or more atoms in the path of the linking chain. Also, RN1 and RN2 each independently represent a monovalent organic group.

[0279] In this specification, "linking chain" refers to an atomic chain that connects two atoms or groups of atoms along a path connecting the linked objects with the shortest (smallest number of atoms) distance. For example, in a compound represented by the following formula, L is composed of styrene, has a vinyl group as a saturated hydrocarbon group, the linking chain is composed of 4 carbon atoms, and the number of atoms along the path of the linking chain (that is, the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "linking chain length") is 4. [Chemical Formula 54]

[0280] It is preferable that the number of carbon atoms in L of formula (B3) (including carbon atoms other than those in the linking chain) is 3 to 24. An upper limit of 12 or less is more preferable, 10 or less is even more preferable, and 8 or less is particularly preferable. A lower limit of 4 or more is more preferable. From the viewpoint of facilitating the above-mentioned intramolecular cyclization reaction, an upper limit of 12 or less of the linking chain length of L is preferable, 8 or less is more preferable, 6 or less is even more preferable, and 5 or less is particularly preferable. In particular, a linking chain length of 4 or 5 is preferable, with 4 being optimal. Specific examples of preferred compounds as base-generating agents include, for example, compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0281] Furthermore, it is preferable that the alkali-generating agent comprises a compound represented by the following formula (N1). [Chemical Formula 55]

[0282] In formula (N1), RN1 and RN2 independently represent monovalent organic groups, RC1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0283] L is a divalent linker, preferably a divalent organic group. A linker chain length of 1 or more is preferred, and 2 or more is even more preferred. As an upper limit, 12 or less is preferred, 8 or less is even more preferred, and 5 or less is even more preferred. The linker chain length refers to the number of atoms present in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

[0284] In formula (N1), RN1 and RN2 are each independently a monovalent organic group (preferably with 1 to 24 carbons, more preferably with 2 to 18 carbons, and further preferably with 3 to 12 carbons), or a hydrocarbon group (preferably with 1 to 24 carbons, more preferably with 1 to 12 carbons, and further preferably with 1 to 10 carbons). Specifically, aliphatic hydrocarbon groups (preferably with 1 to 24 carbons, more preferably with 1 to 12 carbons, and further preferably with 1 to 10 carbons) or aromatic hydrocarbon groups (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and further preferably with 6 to 10 carbons) are preferred. Aliphatic hydrocarbon groups are preferred. If aliphatic hydrocarbon groups are used as RN1 and RN2, the resulting base has higher basicity. Furthermore, aliphatic hydrocarbon groups and aromatic hydrocarbon groups can have substituents, and aliphatic hydrocarbon groups and aromatic hydrocarbon groups can also have oxygen atoms in the aliphatic hydrocarbon chain, the aromatic ring, or the substituents. In particular, examples can be given of aliphatic hydrocarbon groups having oxygen atoms in the hydrocarbon chain.

[0285] Examples of aliphatic hydrocarbon groups constituting RN1 and RN2 include straight-chain or branched chain alkyl groups, cyclic alkyl groups, groups combining chain alkyl groups and cyclic alkyl groups, and alkyl groups having oxygen atoms in the chain. It is preferred that the number of carbon atoms in the straight-chain or branched chain alkyl group is 1 to 24, more preferably 2 to 18, and further preferably 3 to 12. Examples of straight-chain or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, isohexyl, etc. It is preferred that the number of carbon atoms in the cyclic alkyl group is 3 to 12, and more preferably 3 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc. The carbon number of the group relating to the combination of chain alkyl and cyclic alkyl groups is preferably 4 to 24, more preferably 4 to 18, and further preferably 4 to 12. Examples of the groups relating to the combination of chain alkyl and cyclic alkyl groups include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl. The carbon number of the alkyl group containing an oxygen atom in the chain is preferably 2 to 12, more preferably 2 to 6, and further preferably 2 to 4. The alkyl group containing an oxygen atom in the chain can be chain-like or cyclic, and can be straight-chain or branched. From the viewpoint of increasing the boiling point of the decomposition to form a base as described later, RN1 and RN2 are preferably alkyl groups with 5 to 12 carbons. In formulations where adhesion to metals (e.g., copper) is important, alkyl groups containing cyclic alkyl groups and having 1 to 8 carbons are preferred.

[0286] RN1 and RN2 can be linked together to form a ring structure. When forming a ring structure, oxygen atoms, etc., can be present in the chain. Furthermore, the ring structure formed by RN1 and RN2 can be a monocyclic ring or a condensed ring, with a monocyclic ring being preferred. As the formed ring structure, a 5-membered or 6-membered ring containing the nitrogen atom in formula (N1) is preferred. Examples include pyrrole rings, imidazole rings, pyrazole rings, pyrrolidine rings, imidazoleidine rings, pyrazoleidine rings, piperidine rings, piperidine rings, and sulfoline rings. Pyrroleline rings, pyrrolidine rings, piperidine rings, piperidine rings, and sulfoline rings are preferred.

[0287] RC1 represents a hydrogen atom or a protecting group, with hydrogen atom being preferred.

[0288] As a protecting group, a protecting group that decomposes by the action of an acid or a base is preferred, and a protecting group that decomposes by an acid can be cited as an example.

[0289] Specific examples of protecting groups include chain-like or cyclic alkyl groups or chain-like or cyclic alkyl groups having oxygen atoms in the chain. Examples of chain-like or cyclic alkyl groups include methyl, ethyl, isopropyl, tributyl, cyclohexyl, etc. Examples of chain-like alkyl groups having oxygen atoms in the chain include alkoxyalkyl groups, and more specifically, methoxymethyl (MOM), ethoxyethyl (EE), etc. Examples of cyclic alkyl groups having oxygen atoms in the chain include epoxy, glycidyl, oxycyclobutyl, tetrahydrofuranyl, tetrahydropiperanyl (THP), etc.

[0290] The divalent linker constituting L is not particularly limited, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is even more preferred. The hydrocarbon group may have substituents, and may also have atoms other than carbon atoms in the hydrocarbon chain. More specifically, a divalent hydrocarbon linker having an oxygen atom in the chain is preferred, and a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group having an oxygen atom in the chain is even more preferred, and a divalent aliphatic hydrocarbon group having an oxygen atom in the chain is even more preferred. It is preferred that these groups do not have an oxygen atom. It is preferred that the number of carbon atoms in the divalent hydrocarbon linker is 1 to 24, more preferably 2 to 12, and even more preferably 2 to 6. It is preferred that the number of carbon atoms in the divalent aliphatic hydrocarbon group is 1 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. The number of carbon atoms in the group relating to the combination of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group (e.g., arylalkyl) is preferably 7 to 22, more preferably 7 to 18, and even more preferably 7 to 10.

[0291] Specifically, as the linking group L, linear or branched chain-like alkylene groups, cyclic alkylene groups, groups relating to combinations of chain-like and cyclic alkylene groups, alkylene groups having oxygen atoms in the chain, linear or branched chain-like alkenyl groups, cyclic alkenyl groups, aryl groups, and arylalkylene groups are preferred. The number of carbon atoms in the linear or branched chain-like alkylene groups is preferably 1 to 12, more preferably 2 to 6, and further preferably 2 to 4. The number of carbon atoms in the cyclic alkylene groups is preferably 3 to 12, and more preferably 3 to 6. The number of carbon atoms in the groups relating to combinations of chain-like and cyclic alkylene groups is preferably 4 to 24, more preferably 4 to 12, and further preferably 4 to 6. The alkylene groups having oxygen atoms in the chain can be chain-like or cyclic, and can be linear or branched. It is preferred that the number of carbon atoms in the alkyl group containing oxygen atoms in the chain is 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.

[0292] The linear or branched chain alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched chain alkenyl group preferably has 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenyl group preferably has 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2. The aryl group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The arylalkyl group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among them, chain-like alkylene, cyclic alkylene, alkylene with oxygen atoms in the chain, chain-like alkenyl, aryl, and arylalkylene are preferred, and 1,2-vinyl, propanediyl (especially 1,3-propanediyl), cyclohexanediyl (especially 1,2-cyclohexanediyl), vinylene (especially cis vinylene), phenylene (1,2-phenylene), phenylenemethylene (especially 1,2-phenylenemethylene), and vinylethoxyethylene (especially 1,2-vinylethoxy-1,2-vinyl) are even more preferred.

[0293] Examples of alkali-generating agents can be given below, but the present invention should not be interpreted as limiting.

[0294] [Chemical Formula 56]

[0295] It is preferable that the molecular weight of the nonionic alkali generator is below 800, more preferably below 600, and further preferably below 500. As a lower limit, it is preferable that the molecular weight is above 100, more preferably above 200, and further preferably above 300.

[0296] Specific examples of preferred compounds as ionic base generating agents include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0297] Specific examples of ammonium salts include the following compounds, but the present invention is not limited to these. [Chemical Formula 57]

[0298] Specific examples of imine salts include the following compounds, but the present invention is not limited to these. [Chemical Formula 58]

[0299] When the resin composition of the present invention contains an alkali-generating agent, the content of the alkali-generating agent is preferably 0.1 to 50 parts by weight relative to 100 parts by weight of resin in the resin composition of the present invention. A lower limit of 0.3 parts by weight or more is more preferred, and 0.5 parts by weight or more is further preferred. An upper limit of 30 parts by weight or less is more preferred, 20 parts by weight or less is further preferred, 10 parts by weight or less is even more preferred, and it can be 5 parts by weight or less, or 4 parts by weight or less. One or more alkali-generating agents can be used. When two or more are used, the total amount is preferably within the above-mentioned range.

[0300] <Solvent> It is preferable that the resin composition of the present invention contains a solvent. Any known solvent may be used. The solvent is preferably an organic solvent. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, sulfides, amides, ureas, alcohols, and other compounds.

[0301] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionate esters (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-ethoxypropionate, alkyl 3-alkoxypropionate). Ethyl propionate, etc.), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

[0302] As ethers, examples of preferred alternatives include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celusone acetate, ethyl celusone acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0303] As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, etc. are preferred.

[0304] As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred examples.

[0305] As a sulfide, dimethyl sulfide is a preferred example.

[0306] Among amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, N-methoxycarbamate, and N-acetylcarbamate are preferred.

[0307] Among ureas, N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone are preferred.

[0308] As alcohols, examples 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, etc.

[0309] Regarding solvents, from the perspective of improving the properties of the coating surface, it is better to mix two or more forms.

[0310] In this invention, a solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celecoxib acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, L-glucanone, and dihydro-L-glucanone, or a mixture of two or more solvents, is preferred. The simultaneous use of dimethyl sulfoxide and γ-butyrolactone, or the simultaneous use of N-methyl-2-pyrrolidone and ethyl lactate, is particularly preferred.

[0311] Regarding the solvent content, from the viewpoint of coatability, it is preferable that the total solids concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, further preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the required thickness of the coating and the coating method.

[0312] The resin composition of the present invention may contain only one solvent or may contain two or more solvents. When containing two or more solvents, it is preferable that their total amount is within the above-mentioned range.

[0313] <Metal Adhesion Modifier> It is preferable that the resin composition of the present invention includes a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring, etc. Examples of metal adhesion modifiers include aluminum-based adhesives, titanium-based adhesives, compounds having a sulfonylurea structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0314] 〔Aluminum-based adhesive aid〕 Examples of aluminum-based adhesive aids include tri(acetyl ethyl acetate) aluminum, tri(acetyl acetone) aluminum, and acetyl ethyl acetate diisopropyl aluminum.

[0315] Furthermore, as other metal adhesion modifiers, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 may also be used, and such contents are incorporated in this specification.

[0316] The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting it to the lower limit or above, the adhesion between the pattern and the metal layer becomes better; by setting it to the upper limit or below, the heat resistance and mechanical properties of the pattern become better. There may be only one type of metal adhesion modifier, or there may be two or more types. When two or more types are used, it is preferable that their total content is within the above range.

[0317] <Migration Inhibitor> It is preferable that the resin composition of the present invention further includes a migration inhibitor. By including a migration inhibitor, the migration of metal ions originating from the metal layer (metal wiring) into the membrane can be effectively inhibited.

[0318] As a migration inhibitor, there are no particular limitations, and examples include compounds with heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, succinazole ring, thiazole ring, pyrazole ring, isosuccinazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyrazine ring, pyridine ring, piperidine ring, piperidine ring, piperidine ring, 2H-piperanium ring and 6H-piperanium ring, triazine ring), compounds with thiourea and hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and acehydrazine derivative compounds. In particular, it is possible to use triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, as well as tetraazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole.

[0319] Alternatively, ion trapping agents that capture anions such as halide ions can also be used.

[0320] Other migration inhibitors may include the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, etc., which are incorporated herein by reference.

[0321] The following compounds can be cited as specific examples of migration inhibitors.

[0322] [Chemical Formula 59]

[0323] When the resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.

[0324] There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is preferable that their total number is within the above range.

[0325] <Polymerization Inhibitor> It is preferable that the resin composition of the present invention contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxygen radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0326] Specific compounds used as polymerization inhibitors may preferably include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tertiary butyl-p-cresol, gallnutol, p-tertiary butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxyamino cerium salt, N-nitroso-N-phenylhydroxyamino aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol ether diaminetetraacetic acid, 2,6-di-tertiary butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, and 1-nitroso-2-naphthol. 2-Nitrosamino-1-naphthol, 2-Nitrosamino-5-(N-ethyl-N-sulfopropylamino)phenol, N-Nitrosamino-N-(1-naphthyl)hydroxyaminoammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H, (3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, 2,2,6,6-tetramethylpiperidine 1-oxy radical, phenanthrene, phenanthrene, 1,1-diphenyl-2-picrylhydrazine, copper(II) dibutyl dithiocarbonate, nitrobenzene, aluminum salt of N-nitroso-N-phenylhydroxylamine, ammonium salt of N-nitroso-N-phenylhydroxylamine, etc. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International Patent Publication No. 2015 / 125469 can also be used, and this information is incorporated herein by reference.

[0327] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.

[0328] There may be only one polymerization inhibitor or two or more. When there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0329] <Other Additives> The resin composition of the present invention can be combined with various additives as needed within the scope of obtaining the effects of the present invention, such as photoacid generators, surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anticoagulants, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (e.g., defoamers, flame retardants, etc.). By appropriately containing such components, the physical properties of the membrane can be adjusted. Regarding such components, for example, reference can be made to paragraph 0183 onwards in Japanese Patent Application Publication No. 2012-003225 (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein by reference. When these additives are used, it is preferable that their total amount is set to less than 3% by mass of the solid component of the resin composition of the present invention.

[0330] 〔Surfactant〕 As a surfactant, various surfactants such as fluorinated surfactants, polysiloxane surfactants, and hydrocarbon surfactants can be used. The surfactant can be a nonionic surfactant, a cationic surfactant, or anionic surfactant.

[0331] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (especially flowability) when preparing the coating liquid can be further improved, and the uniformity of the coating thickness and the liquid-saving properties can be further improved. That is, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the coated surface and the coating liquid decreases, thereby improving the wettability of the coated surface and improving the coating properties of the coated surface. Therefore, it is possible to further and better form a film with a uniform thickness and less thickness unevenness.

[0332] Examples of fluorinated surfactants include, for example, MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (manufactured by 3M Japan Limited), and Surflon. S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (all manufactured by ASAHI GLASS CO.,LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. Fluorinated surfactants can also use compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Publication No. 2015-117327 and compounds described in paragraphs 0117 to 0132 of Japanese Patent Application Publication No. 2011-132503, the contents of which are included in this specification. Block polymers can also be used as fluorinated surfactants. For example, compounds described in Japanese Patent Application Publication No. 2011-89090, the contents of which are incorporated herein by reference, can be cited. Fluorinated surfactants can also preferably be fluorinated polymeric compounds (including repeating units derived from (meth)acrylate compounds having fluorine atoms and repeating units derived from (meth)acrylate compounds having two or more (preferably five or more) alkoxy groups (preferably ethoxy or propyleneoxy groups). The following compound can also be cited as a fluorinated surfactant used in this invention: [Chemical Formula 60]

[0333] The weight average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Regarding fluorinated surfactants, fluoropolymers with vinyl unsaturated groups on their side chains can also be used as fluorinated surfactants. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Furthermore, commercially available products include, for example, MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0334] The fluorine content in fluorinated surfactants is preferably 3-40% by mass, more preferably 5-30% by mass, and especially preferably 7-25% by mass. Fluorinated surfactants with fluorine content in this range are effective in terms of uniform coating thickness and liquid saving, and also have good solubility in the composition.

[0335] Examples of polysiloxane surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie GmbH).

[0336] As hydrocarbon-based surfactants, examples include PIONIN A-76, NEWKALGEN FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, PIONIN P-4050-T, etc. (all manufactured by TAKEMOTO OIL & FAT CO.,LTD).

[0337] Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, etc. Commercially available products include PLURONIC (registered trademark) 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 Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT CO.,LTD), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry CO.,Ltd.), etc.

[0338] Specifically, examples of cationic surfactants include organosiloxane polymers such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers such as POLYFLOW No.75, No.77, No.90, No.95 (manufactured by Kyoisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

[0339] Specifically, examples of anionic surfactants include WO04, WO05, WO17 (Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

[0340] Only one type of surfactant may be used, or two or more types may be used in combination. The surfactant content relative to the total solid content of the composition is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass.

[0341] [Higher fatty acid derivatives] In order to prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoic acid amide may be added to the resin composition of the present invention so that they are biased to the surface of the resin composition of the present invention during the drying process after coating.

[0342] Furthermore, higher fatty acid derivatives may also use compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0343] When the resin composition of the present invention contains higher fatty acid derivatives, the content of higher fatty acid derivatives relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 10% by mass. There may be only one type of higher fatty acid derivative, or there may be two or more types. When there are two or more types of higher fatty acid derivatives, it is preferable that their total content is within the above-mentioned range.

[0344] [Thermal Polymerization Initiator] The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy, initiating or promoting the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, thereby further improving solvent resistance. Furthermore, sometimes the aforementioned photopolymerization initiator also has the function of initiating polymerization by heat, and can sometimes be added as a thermal polymerization initiator.

[0345] As a thermal free radical polymerization initiator, specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 are included in this specification.

[0346] When a thermal polymerization initiator is included, its content relative to the total solids content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass. The thermal polymerization initiator may contain only one type, or it may contain two or more types. When two or more thermal polymerization initiators are included, the total amount within the above-mentioned range is preferred.

[0347] [Inorganic Particles] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

[0348] The average particle size of the aforementioned inorganic particles is preferably 0.01–2.0 μm, more preferably 0.02–1.5 μm, further preferably 0.03–1.0 μm, and particularly preferably 0.04–0.5 μm. The aforementioned average particle size is a primary particle size and a volume average particle size. The volume average particle size can be determined by dynamic light scattering based on a Nanotrac WAVE II EX-150 (manufactured by NIKKISO CO.,LTD.). If the above determination is difficult to perform, it can also be determined by centrifugal sedimentation transmission method, X-ray transmission method, or laser diffraction / scattering method.

[0349] [Ultraviolet Absorber] The composition of the present invention may include an ultraviolet absorber. As ultraviolet absorbers, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triterpenoid-based ultraviolet absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Furthermore, 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. Butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

[0350] Examples of acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triphenyl terpenoid ultraviolet absorbers include mono(hydroxyphenyl)triphenyl compounds such as 2-[4-[(2-hydroxy-3-dodecoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, 2-[4-[(2-hydroxy-3-tridecoxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl; and 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triphenyl, 2 ,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-tris(hydroxyphenyl) compounds, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-tris(hydroxyphenyl) compounds, etc.; 2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris(hydroxyphenyl) compounds, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-tris(hydroxyphenyl) compounds, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxyphenyl)phenyl]-1,3,5-tris(hydroxyphenyl) compounds, etc.

[0351] In this invention, the various ultraviolet absorbers described above can be used individually or in combination of two or more. The composition of this invention may or may not contain ultraviolet absorbers, but when ultraviolet absorbers are included, the content of ultraviolet absorbers relative to the total solid content of the composition of this invention is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.

[0352] [Organotitanium compound] The resin composition of this embodiment may contain an organotitanium compound. By containing an organotitanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0353] As usable organotitanium compounds, those in which the organic group is bonded to the titanium atom via a covalent bond or an ionic bond can be cited. Specific examples of organotitanium compounds are shown in I) to VII) below. I) Chelated titanium compounds: Among them, chelated titanium compounds having two or more alkoxy groups are preferred from the perspective of excellent preservation stability of the resin composition and obtaining a good curing pattern. Specific examples are bis(triethanolamine)diisopropoxy titanium, bis(n-butoxy)bis(2,4-glutarate) titanium, diisopropoxybis(2,4-glutarate) titanium, diisopropoxybis(tetramethylheptanediol) titanium, diisopropoxybis(ethyl acetoacetate) titanium, etc. II) Tetraalkoxy titanium compounds: Examples include tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearoxytitanium, tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc. III) Diocene titanium compounds: Examples include pentamethylcyclopentadienetrimethoxytitanium, bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: Examples include tris(dioctyl phosphate)isopropoxytitanium, tris(dodecyl benzenesulfonate)isopropoxytitanium, etc. V) Titanium oxide compounds: such as bis(glutarate) titanium oxide, bis(tetramethylheptane) titanium oxide, phthalocyanine titanium oxide, etc. VI) Tetraacetone titanium compounds: such as tetraacetone titanium, etc. VII) Titanium ester coupling agents: such as isopropyltris(2-dimethylbenzenesulfonyl)titanate, etc.

[0354] Among these, from the viewpoint of exhibiting better drug resistance, it is preferable that at least one compound is selected from the group consisting of I) chelated titanium compounds, II) tetraalkoxy titanium compounds and III) diacetic titanium compounds. In particular, diisopropoxybis(acetyl ethyl acetate)titanium, tetra(n-butoxy)titanium and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium are preferred.

[0355] When compounding with organotitanium compounds, the amount of the compounding relative to 100 parts by weight of a specific resin is preferably 0.05 to 10 parts by weight, and more preferably 0.1 to 2 parts by weight. When the amount of the compounding is 0.05 parts by weight or more, the resulting hardened pattern more effectively exhibits good heat resistance and chemical resistance; on the other hand, when the amount is 10 parts by weight or less, the storage stability of the composition is more excellent.

[0356] [Antioxidant] The composition of the present invention may include an antioxidant. By including an antioxidant as an additive, the tensile properties of the hardened film and its adhesion to metallic materials can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, hindered phenolic compounds can be mentioned. Compounds having a substituent at the site adjacent to the phenolic hydroxyl group (ortho position) are preferred. As the above-mentioned substituent, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, regarding antioxidants, compounds having a phenolic group and a phosphite group in the same molecule are also preferred. Furthermore, phosphorus-based antioxidants can also be preferred. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphonium-heptacyclic-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tertiary butyldibenzo[d,f][1,3,2]dioxaphosphonium-heptacyclic-2-yl)oxy]ethyl]amine, and bis(2,4-di-tertiary butyl-6-methylphenyl) ethyl phosphite. Commercially available antioxidants include, for example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, and ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, the antioxidants may also be compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, which are incorporated herein by reference. Additionally, the composition of the present invention may contain potential antioxidants as needed. As potential antioxidants, compounds in which the site of antioxidant activity is protected by a protecting group can be cited. In such compounds, the protecting group is removed by heating at 100–250°C or heating at 80–200°C in the presence of an acid / base catalyst, thereby enabling the antioxidant to function. Compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Application Publication No. 2017-008219 are examples of potential antioxidants, the contents of which are incorporated herein by reference. Commercially available potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION).Examples of better antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and compounds represented by formula (3).

[0357] [Chemical Formula 61]

[0358] In general formula (3), R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R6 represents an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). R7 represents a 1 to 4 valent organic group comprising at least one of an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer from 1 to 4.

[0359] The compound represented by formula (3) inhibits the oxidative degradation of the aliphatic groups and phenolic hydroxyl groups of the resin. Furthermore, it can inhibit metal oxidation by preventing rust on metal materials.

[0360] In order to act simultaneously on both the resin and the metal material, it is preferable that k is an integer from 2 to 4. Examples of R7 include alkyl, cycloalkyl, alkoxy, alkyl ether, alkyl silicone, alkoxy silicone, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, and may further have substituents. Among these, alkyl ethers and -NH- are preferred from the viewpoint of solubility in the developer and metal adhesion, while -NH- is more preferred from the viewpoint of interaction with the resin and metal adhesion based on the formation of metal complexes.

[0361] The following compounds are examples of compounds represented by general formula (3), but are not limited to the following structures.

[0362] [Chemical Formula 62]

[0363] [Chemical Formula 63]

[0364] [Chemical Formula 64]

[0365] [Chemical Formula 65]

[0366] The amount of antioxidant added relative to 100 parts by weight of a specific resin is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight. By setting the amount added to 0.1 parts by weight or more, it is easy to obtain the effects of tensile properties and improved adhesion to metal materials even under high temperature and high humidity environments. Furthermore, by setting it to 10 parts by weight or less, for example, the sensitivity of the resin composition is improved by utilizing the interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above-mentioned range.

[0367] [Anti-coagulant] The resin composition of this embodiment may contain an anti-coagulant as needed. Examples of anti-coagulants include sodium polyacrylate.

[0368] In this invention, one type of anti-coagulant may be used alone, or two or more may be used in combination. The composition of this invention may or may not contain an anti-coagulant, but when it does contain an anti-coagulant, the content of the anti-coagulant relative to the total solid content of the composition of this invention is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.02% by mass or more and 5% by mass or less.

[0369] [Phenolic Compounds] The resin composition of this embodiment may contain phenolic compounds as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (trade names, manufactured by ASAHI YUKIZAI CORPORATION), etc.

[0370] In this invention, a single phenolic compound may be used alone, or two or more may be used in combination. The composition of this invention may or may not contain phenolic compounds, but when phenolic compounds are included, the content of phenolic compounds relative to the total solid content of the composition of this invention is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

[0371] 〔Other polymeric compounds〕 Examples of other polymeric compounds include silicone resins, (meth)acrylic acid polymers copolymerized with (meth)acrylic acid, phenolic varnish resins, methyl phenolic resins, polyhydroxystyrene resins, and copolymers thereof. Other polymeric compounds may be modified forms incorporating crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[0372] In this invention, one or more other polymeric compounds may be used alone or in combination. The composition of this invention may or may not contain other polymeric compounds, but when they are included, the content of other polymeric compounds relative to the total solid content of the composition of this invention is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.

[0373] <Characteristics of the Resin Composition> The viscosity of the resin composition of the present invention can be adjusted according to the concentration of the solid components of the resin composition. From the viewpoint of coating film thickness, 1,000 mm² / s to 12,000 mm² / s is preferred, 2,000 mm² / s to 10,000 mm² / s is more preferred, and 2,500 mm² / s to 8,000 mm² / s is even more preferred. As long as it is within the above range, it is easy to obtain a coating film with high uniformity. For example, if it is 1,000 mm² / s or more, it is easy to coat with the film thickness required as an insulating film for rewiring, and if it is 12,000 mm² / s or less, a coating film with excellent coating surface can be obtained.

[0374] <Limitations on the Contents of the Resin Composition> It is preferable that the moisture content of the resin composition of the present invention is less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. As a method to maintain the moisture content, examples include humidity adjustment under storage conditions and reducing the porosity of the storage container during storage.

[0375] From the viewpoint of insulation, it is preferable that the metal content of the resin composition of the present invention is less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excluding metals contained as complexes of organic compounds and metals. When multiple metals are contained, it is preferable that the total amount of such metals is within the above-mentioned range.

[0376] Furthermore, as a method to reduce metal impurities accidentally included in the resin composition of the present invention, the following methods can be cited: selecting raw materials with low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention with a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

[0377] Regarding the resin composition of the present invention, considering its use as a semiconductor material, from the viewpoint of wiring corrosion resistance, it is preferable that the halogen atom content is less than 500 ppm by mass, more preferably less than 300 ppm by mass, and further preferably less than 200 ppm by mass. Among these, it is preferable that the content of halide ions is less than 5 ppm by mass, more preferably less than 1 ppm by mass, and further preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chloride ions and bromide ions, is within the above-mentioned ranges. As a method for adjusting the halogen atom content, ion exchange treatment is a preferred example.

[0378] Conventionally known containers can be used as the container for the resin composition of the present invention. Furthermore, for the purpose of preventing impurities from contaminating the raw materials or the resin composition of the present invention, it is preferable to use a multi-layer bottle with an inner wall composed of six types of six-layer resins, or a bottle with a seven-layer structure formed by six types of resins. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0379] <Curved Product of Resin Composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. Curing of the resin composition is preferably carried out by heating, preferably at a heating temperature in the range of 120°C to 400°C, further preferably in the range of 140°C to 380°C, and particularly preferably in the range of 170°C to 350°C. The form of the cured product of the resin composition is not particularly limited, and can be selected as film, rod, sphere, granule, etc., depending on the application. In the present invention, the cured product is preferably film-shaped. Furthermore, by patterning the resin composition, the shape of the cured product can be selected according to applications such as forming a protective film on a wall surface, forming conductive through-holes, adjusting impedance, electrostatic capacitance or internal stress, and imparting heat dissipation function. The film thickness of the cured product (the film composed of the cured product) is preferably 0.5 μm or more and 150 μm or less. It is preferable that the shrinkage rate of the resin composition during curing is 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated using the following formula: Shrinkage rate [%] = 100 - (Curved volume ÷ Uncured volume) × 100

[0380] <Characteristics of Cured Resin Compositions> It is preferable that the amide reaction rate of the cured resin composition of the present invention is 70% or more, more preferably 80% or more, and further preferably 90% or more. If it is 70% or more, it may sometimes result in a cured composition with excellent mechanical properties. It is preferable that the elongation at break of the cured resin composition of the present invention is 30% or more, more preferably 40% or more, and further preferably 50% or more. It is preferable that the glass transition temperature (Tg) of the cured resin composition of the present invention is 180°C or more, more preferably 210°C or more, and further preferably 230°C or more.

[0381] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be performed using conventionally known methods. Mixing can be performed using stirring blades, ball milling, or by rotating the container itself. A mixing temperature of 10–30°C is preferred, and 15–25°C is more preferred.

[0382] Furthermore, it is preferable to use a filter for filtration to remove foreign matter such as dust or particles from the resin composition of the present invention. Regarding the filter pore size, examples include 5 μm or less, 1 μm or less is preferred, 0.5 μm or less is more preferred, and 0.1 μm or less is even more preferred. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be pre-cleaned with an organic solvent. In the filtration step, multiple filters can be used in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be combined. For example, a connection method can be as follows: an HDPE filter with a 1 μm pore size is used as the first stage, and an HDPE filter with a 0.2 μm pore size is used as the second stage, and the two are connected in series. Furthermore, various materials can be filtered multiple times. Multiple filtrations can be performed as circulating filtration. Also, pressure filtration can be performed. When performing pressure filtration, for example, the applied pressure can be 0.01 MPa or higher and 1.0 MPa or lower, preferably 0.03 MPa or higher and 0.9 MPa or lower, more preferably 0.05 MPa or higher and 0.7 MPa or lower, and even more preferably 0.05 MPa or higher and 0.5 MPa or lower. In addition to filtration using a filter, impurity removal treatment using an adsorbent material can also be performed. Filtration using a filter and impurity removal treatment using an adsorbent material can also be combined. Known adsorbent materials can be used as the adsorbent material. For example, inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon can be used. After filtration using a filter, a further step can be performed where the resin composition filled in the bottle is placed under reduced pressure for degassing.

[0383] (Method for Manufacturing a Cured Material) The method for manufacturing a cured material of the present invention preferably includes a film forming step in which a resin composition is applied to a substrate to form a film. Furthermore, the method for manufacturing a cured material of the present invention is more preferably including the above-described film forming step, an exposure step in which the film formed by the film forming step is selectively exposed, and a developing step in which a developing solution is used to develop the film exposed by the exposure step to form a pattern. The method for manufacturing a cured material of the present invention is particularly preferably including at least one of the above-described film forming step, the above-described exposure step, the above-described developing step, a heating step in which the pattern obtained by the developing step is heated, and a post-developing exposure step in which the pattern obtained by the developing step is exposed. Furthermore, the method for manufacturing the present invention is also preferably including the above-described film forming step and the step of heating the above-described film. The details of each step will be described below.

[0384] <Film Forming Step> The resin composition of the present invention can be used in a film forming step for forming a film on a substrate. The method for manufacturing the cured material of the present invention preferably includes a film forming step in which the resin composition is applied to a substrate to form a film.

[0385] 〔Substrate〕 The type of substrate can be appropriately determined according to the application. Examples include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, the substrate and metal layer formed by metal can be any of the substrates formed by plating, deposition, etc.); paper; SOG (Spin On Glass); TFT (Thin Film Transistor) array substrates; molded substrates; and electrode plates for plasma display panels (PDPs). There are no particular limitations. In this invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are even more preferred. Furthermore, a close-bonding layer or an oxide layer formed of hexamethyldisilazane (HMDS) can be provided on the surface of such substrates. Furthermore, the shape of the substrate is not particularly limited; it can be circular or rectangular. Regarding the dimensions of the substrate, if it is circular, the diameter is, for example, 100–450 mm, preferably 200–450 mm. If it is rectangular, the length of the shorter side is, for example, 100–1000 mm, preferably 200–700 mm. Furthermore, the substrate can be plate-shaped, and a panel-shaped substrate (substrate) is preferred.

[0386] Furthermore, when a resin composition is applied to the surface of a resin layer (e.g., a layer composed of a hardened material) or a metal layer to form a film, the resin layer and the metal layer become substrates.

[0387] As a method for applying the resin composition of the present invention to a substrate, coating is preferred.

[0388] As applicable methods, examples include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slot coating, and inkjet coating. From the viewpoint of film thickness uniformity, spin coating, slot coating, spray coating, or inkjet coating is preferred. From the viewpoint of film thickness uniformity and productivity, spin coating and slot coating are preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred; for rectangular substrates, slot coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500 to 3,500 rpm can be applied for about 10 seconds to 3 minutes. Furthermore, the method of transferring a coating formed by pre-applying it to a dummy support using the aforementioned method onto a substrate is also applicable. Regarding the transfer method, in this invention, the manufacturing methods described in Japanese Patent Application Publication No. 2006-023696, paragraphs 0023, 0036-0051, or Japanese Patent Application Publication No. 2006-047592, paragraphs 0096-0108, are also preferred. Furthermore, a step of removing excess film at the ends of the substrate can also be performed. Examples of such steps include edge bead rinse (EBR) and back-side rinse. Furthermore, a pre-wetting step can also be employed whereby, before applying the resin composition to the substrate, various solvents are applied to the substrate to improve its wettability, and then the resin composition is applied.

[0389] <Drying Step> The above-mentioned film can be used in a drying step (drying step) after the film formation step (layer formation step) to remove solvent from the formed film (layer). That is, the method for manufacturing the cured product of the present invention may include a drying step for drying the film formed by the film formation step. Furthermore, it is preferable that the above-mentioned drying step is performed after the film formation step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and further preferably 90 to 110°C. Furthermore, drying can be performed by reduced pressure. As for the drying time, 30 seconds to 20 minutes, 1 minute to 10 minutes are preferred, and 2 minutes to 7 minutes are more preferred.

[0390] <Exposure Step> The above-described film can be used in an exposure step for selective exposure of the film. That is, the method for manufacturing the cured material of the present invention may include an exposure step for selectively exposing the film formed by the film forming step. Selective exposure refers to exposing a portion of the film. Furthermore, by selective exposure, exposed areas (exposed portions) and unexposed areas (non-exposed portions) are formed on the film. The exposure amount is not particularly limited as long as it is sufficient to cure the resin composition of the present invention. For example, based on the exposure energy at a wavelength of 365 nm, 50 to 10,000 mJ / cm² is preferred, and 200 to 8,000 mJ / cm² is more preferred.

[0391] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0392] Regarding the exposure wavelength, in terms of its relationship with the light source, examples include (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, gamma rays (wavelength 436nm), h rays (wavelength 405nm), i rays (wavelength 365nm), wide wavelengths (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, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc. Regarding the resin composition of the present invention, exposure based on high-pressure mercury lamps is particularly preferred, and exposure based on i rays is even more preferred. Therefore, high exposure sensitivity can be obtained. Furthermore, the exposure method is not particularly limited, as long as at least a portion of the film composed of the resin composition of the present invention is exposed, such as exposure using a photomask or exposure based on direct laser imaging.

[0393] <Post-exposure heating step> The above-mentioned film can be used in a post-exposure heating step. That is, the method for manufacturing the cured product of the present invention may include a post-exposure heating step of heating the film exposed by the exposure step. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. Regarding the heating rate in the post-exposure heating step, it is preferably 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature, more preferably 2 to 10°C / minute, and further preferably 3 to 10°C / minute. Furthermore, the heating rate can be appropriately changed during the heating process. There is no particular limitation on the heating method in the post-exposure heating step, and known heating plates, ovens, infrared heaters, etc., can be used. Furthermore, it is better to conduct the heating process in an environment with low oxygen concentration by circulating inert gases such as nitrogen, helium, or argon.

[0394] <Developing Step> The exposed film can be used in a developing step to form a pattern by developing it with a developing solution. That is, the method for manufacturing the cured material of the present invention may include a developing step in which a pattern is formed by developing the film exposed by the exposure step with a developing solution. By developing, one of the exposed and non-exposed portions of the film is removed, forming a pattern. Here, the development that removes the non-exposed portion of the film by the developing step is called negative development, and the development that removes the exposed portion of the film by the developing step is called positive development.

[0395] 〔Developer solution〕 Examples of developers used in the developing step include alkaline aqueous solutions or developers containing organic solvents.

[0396] When the developer is an alkaline aqueous solution, the alkaline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred alkaline compounds include TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylamine hydroxide, tetrabutylamine hydroxide, tetrapentylamine hydroxide, tetrahexylamine hydroxide, tetraoctylamine hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferably, TMAH is also mentioned. For example, when using TMAH, it is preferable that the content of alkaline compounds in the developer is 0.01 to 10% by mass of the total amount of developer, even better that it is 0.1 to 5% by mass, and further preferably 0.3 to 3% by mass.

[0397] When the developer contains an organic solvent, esters are preferably included, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetic acid esters (e.g., methyl alkoxyacetic acid, ethyl alkoxyacetic acid, butyl alkoxyacetic acid (e.g., methyl methoxyacetic acid, ethyl methoxyacetic acid, butyl methoxyacetic acid, methyl ethoxyacetic acid, ethyl ethoxyacetic acid, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g.: Methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., 2-methoxy-2-methylpropionate) Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably including diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celusone acetate, ethyl celusone acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as... Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; examples of sulfides include, for example, dimethyl sulfide; examples of alcohols include, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol; and examples of amides include, for example, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethyl methamide.

[0398] Furthermore, when the developer contains an organic solvent, one type of organic solvent or two or more types of organic solvent may be used. In this invention, it is particularly preferred that the developer contains at least one type selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone; it is even more preferred that the developer contains at least one type selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide; and it is most preferably a developer containing cyclopentanone.

[0399] When the developer contains organic solvent, it is preferable that the content of organic solvent relative to the total mass of the developer is 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and especially preferably 90% by mass or more. Furthermore, the above content can also be 100% by mass.

[0400] The developer may further contain other components. Examples of other components include, for instance, known surfactants and known defoamers.

[0401] [Developer Supply Method] As long as the desired pattern can be formed, the developer supply method is not particularly limited. Methods include: immersing the substrate with the film formed in the developer; swirling immersion development using a nozzle to supply the developer to the film formed on the substrate; or continuous development. The type of nozzle is not particularly limited; examples include direct-flow nozzles, spray nozzles, and atomizing nozzles. From the viewpoints of developer penetration, removal of non-image areas, and manufacturing efficiency, the method of supplying the developer using a direct-flow nozzle or the method of continuous supply using a spray nozzle is preferable. From the viewpoint of developer penetration into the image area, the method of supplying the developer using a spray nozzle is more preferable. Alternatively, the following steps can be used: after continuously supplying the developer using a direct-flow nozzle, rotating the substrate to remove the developer from the substrate; after rotation drying, continuously supplying the developer again using a direct-flow nozzle; and rotating the substrate to remove the developer from the substrate. This step can also be repeated several times. Furthermore, as a method for supplying the developer in the developing step, steps such as continuously supplying the developer to the substrate, maintaining the developer on the substrate in a substantially static state, vibrating the developer on the substrate using ultrasound or the like, and combining these methods are possible.

[0402] The preferred development time is 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. There is no particular limitation on the temperature of the developer during development, but it is preferred to be carried out at 10 to 45°C, and more preferably at 18°C ​​to 30°C.

[0403] In the developing step, the pattern can be further cleaned (rinsed) based on the rinsing solution after treatment with the developing solution. Alternatively, the rinsing solution can be supplied before the developing solution in contact with the pattern is completely dry.

[0404] 〔Rinse Solution〕 When the developer is an alkaline aqueous solution, water can be used as the rinsing solution, for example. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0405] When the rinsing solution contains an organic solvent, the organic solvent, preferably, is an ester, 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 alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionic acid esters (e.g.: Methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., 2-methoxy-2-methylpropionate) Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably including diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celusone acetate, ethyl celusone acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as... Examples of ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene; examples of sulfides include, for example, dimethyl sulfide; examples of alcohols include, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, and triethylene glycol; and examples of amides include, for example, N-methylpyrrolidone, N-ethylpyrrolidone, and dimethyl methamide.

[0406] When the rinsing solution contains an organic solvent, one type of organic solvent or two or more types of organic solvent may be used. In this invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are even more preferred, and cyclohexanone and PGMEA are further preferred.

[0407] When the rinsing solution contains an organic solvent, it is preferable that the rinsing solution contains 50% or more by mass of an organic solvent, more preferably 70% or more by mass of an organic solvent, and even more preferably 90% or more by mass of an organic solvent. Alternatively, the rinsing solution may contain 100% by mass of an organic solvent.

[0408] The rinsing solution may further contain other ingredients. Examples of other ingredients include, for instance, known surfactants and known defoamers.

[0409] [Method for supplying rinsing solution] As long as the desired pattern can be formed, the method of supplying the rinsing solution is not particularly limited, and the following methods are available: immersing the substrate in the rinsing solution; supplying the rinsing solution by swirling and immersing it on the substrate; supplying the rinsing solution to the substrate using a spray nozzle; or continuously supplying the rinsing solution to the substrate using a direct current nozzle, etc. From the viewpoints of the rinsing solution's permeability, the removal of non-image areas, and manufacturing efficiency, methods such as using spray nozzles, direct current nozzles, and aerosol nozzles to supply the rinsing solution are preferred. The method of continuous supply using a aerosol nozzle is preferable, and from the viewpoint of the rinsing solution's permeability to the image area, the method of supplying using a aerosol nozzle is even better. There is no particular limitation on the type of nozzle; direct current nozzles, spray nozzles, and aerosol nozzles are examples. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing solution to the exposed film using a direct current nozzle, and a step of supplying the rinsing solution using a aerosol nozzle is even better. Furthermore, as a method for supplying the rinsing fluid in the rinsing step, one can employ a step of continuously supplying the rinsing fluid to the substrate, a step of keeping the rinsing fluid on the substrate in a substantially static state, a step of vibrating the rinsing fluid on the substrate using ultrasound or the like, and a combination of these methods.

[0410] The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. There is no particular limitation on the temperature of the rinsing solution, but it is preferably carried out at 10 to 45°C, and more preferably at 18 to 30°C.

[0411] <Heating Step> The pattern obtained by the developing step (or the washed pattern if a rinsing step is performed) can be used in a heating step to heat the pattern obtained by the developing step. That is, the method for manufacturing the cured product of the present invention may include a heating step to heat the pattern obtained by the developing step. Furthermore, the method for manufacturing the cured product of the present invention may also include a heating step to heat a pattern obtained by other methods without a developing step, or a film obtained by a film forming step. In the heating step, a resin such as a polyimide precursor is cyclized into a resin such as polyimide. Furthermore, crosslinking of unreacted crosslinking groups in a specific resin or a crosslinking agent other than a specific resin is also performed. As the heating temperature (maximum heating temperature) in the heating step, 50–450°C is preferred, 150–350°C is more preferred, 150–250°C is further preferred, 160–250°C is even more preferred, and 160–230°C is particularly preferred.

[0412] The heating step is preferably as follows: by utilizing the effect of the alkali generated from the above-mentioned alkali generating agent through heating, the cyclization reaction of the above-mentioned polyimide precursor is promoted within the above-mentioned pattern.

[0413] Regarding the heating step, it is preferable to increase the temperature at a rate of 1 to 12°C / minute from the initial temperature to the maximum heating temperature. A rate of 2 to 10°C / minute is more preferable, and 3 to 10°C / minute is even more preferable. By setting the heating rate to 1°C / minute or higher, productivity can be ensured while preventing excessive evaporation of acid or solvent. By setting the heating rate to 12°C / minute or lower, residual stress in the hardened material can be mitigated. Furthermore, in the case of an oven capable of rapid heating, it is preferable to increase the temperature at a rate of 1 to 8°C / second from the initial temperature to the maximum heating temperature, 2 to 7°C / second is more preferable, and 3 to 6°C / second is even more preferable.

[0414] The initial heating temperature is preferably 20–150°C, more preferably 20–130°C, and further preferably 25–120°C. The initial heating temperature refers to the temperature at which the step of heating to the maximum heating temperature begins. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature of the dried film (layer) is preferred; for example, it is preferable to start heating from a temperature 30–200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

[0415] The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0416] In particular, when forming a multilayered body, from the viewpoint of interlayer adhesion, a heating temperature of 30°C or higher is preferred, 80°C or higher is more preferred, 100°C or higher is even more preferred, and 120°C or higher is especially preferred. The upper limit of the above temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

[0417] Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at a rate of 3°C / minute and holding at 120°C for 60 minutes, then heating from 120°C to 180°C at a rate of 2°C / minute and holding at 180°C for 120 minutes. Furthermore, as described in U.S. Patent No. 9,159,547, it is also preferable to perform the treatment simultaneously with ultraviolet irradiation. Such pretreatment steps can improve the properties of the membrane. The pretreatment step can be performed in a short time of approximately 10 seconds to 2 hours, with 15 seconds to 30 minutes being more preferred. The pretreatment can be performed in two or more stages; for example, the first stage of the pretreatment step can be performed in the range of 100 to 150°C, and then the second stage of the pretreatment step can be performed in the range of 150 to 200°C. Furthermore, cooling can be performed after heating, with a cooling rate of 1 to 5°C / minute being preferable.

[0418] Regarding the heating step, from the perspective of preventing the decomposition of specific resins, it is preferable to carry out the process under reduced pressure using inert gases such as nitrogen, helium, or argon, in an environment with a low oxygen concentration. An oxygen concentration of 50 ppm (volume ratio) or less is preferred, and 20 ppm (volume ratio) or less is even better. There are no particular limitations on the heating method used in the heating step; examples include heating plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0419] <Post-development exposure step> The pattern obtained by the development step (or the washed pattern in the case of a washing step) can be used instead of the heating step described above, or in addition to the heating step described above, for exposing the pattern after the development step in a post-development exposure step. That is, the method for manufacturing the cured product of the present invention may include a post-development exposure step for exposing the pattern obtained by the development step. The method for manufacturing the cured product of the present invention may include a heating step and a post-development exposure step, or may include either a heating step or a post-development exposure step. In the post-development exposure step, for example, a cyclization reaction of polyimide precursors, etc., can be promoted by photosensitive alkali generating agent, or a reaction of decomposing acidic groups by photosensitive acid generating agent. In the post-development exposure step, it is sufficient for at least a portion of the pattern obtained in the development step to be exposed, but it is preferable for all of the above-mentioned pattern to be exposed. Based on the exposure energy conversion at the wavelength where the photosensitive compound has sensitivity, the exposure amount in the post-development exposure step is preferably 50–20,000 mJ / cm², and more preferably 100–15,000 mJ / cm². Regarding the post-development exposure step, the light source used in the above-mentioned exposure step can be used, and broadband light is preferred.

[0420] <Metal Layer Forming Step> A metal layer forming step in which the pattern obtained by the developing step (preferably the user in at least one of the heating step and the post-development exposure step) can be used to form a metal layer on the pattern. That is, the method for manufacturing the cured material of the present invention preferably includes a metal layer forming step in which a metal layer is formed on the pattern obtained by the developing step (preferably the user in at least one of the heating step and the post-development exposure step).

[0421] As a metal layer, there are no particular limitations, and existing metal types can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver and alloys containing such metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0422] There is no particular limitation on the method for forming the metal layer, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and methods combining the above can be considered. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electrolytic plating can be cited. As a preferred example of electroplating, electrolytic plating using copper sulfate plating solution and copper cyanide plating solution can be cited.

[0423] As for the thickness of the metal layer, 0.01 to 50 μm is preferred, and 1 to 10 μm is even more preferred, based on the thickest part.

[0424] <Applications> Examples of applications applicable to the manufacturing method of the cured material of the present invention or the cured material of the present invention include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress-relief films, etc. Other examples include sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or patterns formed on insulating films used for practical mounting purposes, such as those described above. For these applications, for example, reference c...

Claims

1. A resin composition comprising: a cyclized resin or a precursor thereof; and compound A, represented by the following formula (1-1), wherein the aforementioned cyclized resin or precursor thereof is at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor, wherein in formula (1-1), R1 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms that can be substituted, R2 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms that can be substituted, L is any of the m+n valence linkages represented below, x represents an integer of 1 to 3, m is 1, n is 1, * represents a bonding site with the Si atom in formula (1-1), and # represents a bonding site with the hydroxyl group in formula (1-1).

2. The resin composition as claimed in claim 1, wherein the content of carboxylic anhydride relative to the total mass of the resin composition is 0.5% by mass or less.

3. The resin composition as claimed in claim 1, wherein the molecular weight of the aforementioned compound A is 300 to 1,000.

4. A resin composition comprising: a cyclized resin or a precursor thereof; and compound A, a compound represented by formula (2-1), wherein the aforementioned cyclized resin or precursor thereof is at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor, wherein in formula (2-1), R1 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms that can be substituted, R2 independently represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms that can be substituted, L1 represents a single bond or a divalent linkage, Z represents an amino group, the orientation of the amino group in Z is not particularly limited, L2 represents a single bond or a divalent linkage, Ar represents an aromatic group, X represents an alkyl group, and x represents an integer of 1 or more and 3 or less.

5. The resin composition as claimed in claim 4, wherein the molecular weight of the aforementioned compound A is 300 to 1,000.

6. The resin composition as described in any one of claims 1 to 5, comprising a photopolymerization initiator.

7. The resin composition as described in any one of claims 1 to 5, comprising a polymeric compound.

8. The resin composition as described in any one of claims 1 to 5, comprising an alkali generating agent.

9. A resin composition as described in any one of claims 1 to 5, used to form an interlayer insulating film for a rewiring layer.

10. A cured material formed by curing any one of the resin compositions described in claims 1 to 9.

11. A laminate comprising two or more layers made of the curing material described in claim 10, wherein any layer made of the aforementioned curing material contains a metal layer between each other.

12. A method for manufacturing a hardened material, comprising a film forming step of applying a resin composition described in any one of claims 1 to 9 to form a film on a substrate.

13. The method for manufacturing a hardened material as claimed in claim 12, comprising an exposure step of selectively exposing the aforementioned film and a development step of developing the aforementioned film using a developer to form a pattern.

14. A method for manufacturing a hardened material as described in claim 12, comprising a heating step of heating the aforementioned film at 50 to 450°C.

15. A semiconductor device comprising the hardened material described in claim 10.