Resin composition, cured product, laminate, method for manufacturing a cured product, method for manufacturing a laminate, method for manufacturing a semiconductor device, and semiconductor device

Abstract

Provided are: a resin composition having excellent storage stability and excellent chemical resistance of the resulting cured article; a cured article obtained by curing the resin composition; a laminate including the cured article; a method for producing a cured article; a method for producing a laminate; a method for producing a semiconductor device, which includes a method for producing a laminate; and a semiconductor device that includes a cured article or a laminate.　The resin composition contains a resin and a metal complex having at least one π-conjugated site containing a nitrogen atom.

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a cured product, a laminate, a method for manufacturing a cured product, a method for manufacturing a laminate, a method for manufacturing a semiconductor device, and a semiconductor device. [Background technology]

[0002] In modern times, resin materials are being utilized in various fields using resin compositions that contain resin. For example, cyclopolymer resins such as polyimide are used in a variety of applications due to their excellent heat resistance and insulation properties. While not limited to these applications, examples of such applications include their use as insulating films, encapsulants, or protective films in semiconductor devices for packaging. They are also used as base films and coverlays for flexible substrates.

[0003] For example, in the applications described above, cyclized resins such as polyimide are used in the form of a resin composition containing a precursor of the cyclized resin, such as a polyimide precursor. Such a resin composition can be applied to a substrate, for example by coating, to form a photosensitive film, and then, if necessary, exposure, development, heating, etc., can be performed to form a cured product on the substrate. The precursors of the cyclized resin, such as polyimide precursors, are cyclized, for example, by heating, and become cyclized resins such as polyimide in the cured product. Since the resin composition can be applied by known coating methods, it can be said to have excellent manufacturing adaptability, such as a high degree of freedom in designing the shape, size, and application location of the resin composition when applied. In addition to the high performance of cyclized resins such as polyimides, the industrial application development of the above-mentioned resin composition is increasingly expected from the standpoint of such excellent manufacturing adaptability.

[0004] For example, Patent Document 1 describes a resin composition comprising a polyimide precursor having a specific structural unit and a metal complex compound having a specific structure. Furthermore, Patent Document 2 describes a negative-type photosensitive resin composition containing a polyimide precursor, which is a blend of resins having a specific structure, and a photosensitive agent. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2014-122279 [Patent Document 2] International Publication No. 2017 / 170600 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] In resin compositions for obtaining cured products, there is a need for the resin composition itself to have good storage stability, and for the resulting cured product to have excellent chemical resistance.

[0007] The present invention aims to provide a resin composition having excellent storage stability and excellent chemical resistance of the resulting cured product; a cured product obtained by curing the resin composition; a laminate containing the cured product; a method for manufacturing the cured product; a method for manufacturing the laminate; a method for manufacturing a semiconductor device including the method for manufacturing the laminate; and a semiconductor device containing the cured product or the laminate. [Means for solving the problem]

[0008] Examples of typical embodiments of the present invention are shown below. <1> resin and A metal complex having one or more π-conjugated sites containing a nitrogen atom, and Resin composition. <2> The above metal complex includes a substructure represented by the following formula (1-1) as a structure containing a π-conjugated moiety that includes the above nitrogen atom, <1> The resin composition described above. [ka] In formula (1-1), X 1 ~X3 Each independently represents -C(-*)= or -N=, * represents a bonding site with another structure, and # represents a bonding site with a metal atom. <3> The resin composition according to <1> or <2>, wherein the metal complex has, on the same ligand, a π-conjugated site containing the nitrogen atom and at least one group selected from the group consisting of a hydroxy group, a mercapto group, and a carboxy group. <4> The resin composition according to any one of <1> to <3>, wherein the metal complex contains a partial structure represented by the following formula (3-1) as a structure containing a π-conjugated site containing the nitrogen atom. <0​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​14 ~R 17 Each of these independently consists of a hydrogen atom, alkyl group, alkoxy group, allyloxy group, acyl group, phenyl group, acyloxy group, ester group, halogen atom, nitro group, cyano group, and -NR. 101 R 102 , -SR 103 -SO2NR 104 R 105 ,-CONR 106 R 107 or -NR 108 COR 109 Represents R 101 and R 102 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R 101 and R 102 They may be bonded together to form a ring, R 103 ~R 109 Each of these independently represents an alkyl group or an aryl group, and * represents X in formula (3-1). 1 The # represents the bonding site with the nitrogen atom in equation (3-1). <5> The above L 1 The group is represented by formula (L-2), and the above R 18 is a hydrogen atom, and the above R 1 , R 2 , R 3 , R 4 , R 14 , R 15 , R 16 , R 17 At least one of these is a methyl group, alkoxy group, allyloxy group, phenyl group, acyloxy group, acyl group, ester group, halogen atom, nitro group, cyano group, -NR 101 R 102 , -SR 103 -SO2NR 104 R 105 ,-CONR 106 R 107 or -NR 108 COR 109 Represents R 101 and R 102 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R 101 and R 102may combine to form a ring, and R 103 ~R 109 each independently represents an alkyl group or an aryl group, and the resin composition according to <4>. <6> The resin composition according to any one of <1> to <5>, wherein the metal complex has a partial structure represented by the following formula (4-1) as a structure containing a π-conjugated site containing the nitrogen atom. [Chemical formula] In formula (4-1), R 1 ~R 7 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acyl group, a phenyl group, an acyloxy group, an ester group, a halogen atom, a nitro group, a cyano group, -NR 101 R 102 , -SR 103 , -SO2NR 104 R​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​In formula (2-1), M is titanium, zirconium or hafnium, l1 is an integer from 0 to 2, l2 is 0 or 1, l1 + l2×2 is an integer from 0 to 2, m is an integer from 0 to 4, n is an integer from 0 to 2, and l1 + l2 + m + n×2 = 4, R 11 is each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group, R 12 is a substituted or unsubstituted hydrocarbon group, R 2 is each independently a group containing the structure represented by the following formula (2-2), R 3 is each independently a group containing the structure represented by the following formula (2-2), X A is each independently an oxygen atom or a sulfur atom.

Chemical formula

[0009] The present invention provides a resin composition having excellent storage stability and excellent chemical resistance of the resulting cured product, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the laminate, and a semiconductor device containing the cured product or the laminate. [Modes for carrying out the invention]

[0010] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments specified. In this specification, a numerical range represented by the symbol "~" means a range that includes the numbers written before and after "~" as the lower limit and upper limit, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes insofar as they achieve their intended function. In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both groups (atomic groups) with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids refers to the total mass of all components of the composition excluding the solvent. In this specification, solids concentration refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are defined as polystyrene equivalent values, unless otherwise specified, and are measured using gel permeation chromatography (GPC). In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, if THF is unsuitable as an eluent, such as in cases of low solubility, NMP (N-methyl-2-pyrrolidone) may be used. Furthermore, unless otherwise specified, detection in GPC measurements will be performed using a UV (ultraviolet) wavelength 254nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that the other layer is above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component. Furthermore, unless otherwise specified, the content of each component in a composition means the total content of all compounds corresponding 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, a combination of preferred embodiments is a more preferred embodiment.

[0011] (Resin Composition) The resin composition according to the first aspect of the present invention includes a resin and a metal complex having one or more π-conjugated sites containing a nitrogen atom. The resin composition according to the second aspect of the present invention includes a resin and a compound represented by the following formula (2-1). [Chemical Formula] In formula (2-1), M is titanium, zirconium, or hafnium; l1 is an integer from 0 to 2; l2 is 0 or 1; l1 + l2×2 is an integer from 0 to 2; m is an integer from 0 to 4; n is an integer from 0 to 2; and l1 + l2 + m + n×2 = 4. R 11 are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group. R 12 is a substituted or unsubstituted hydrocarbon group. R 2 are each independently a group containing a structure represented by the following formula (2-2). R 3 are each independently a group containing a structure represented by the following formula (2-2). X A are each independently an oxygen atom or a sulfur atom. [Chemical Formula] In formula (2-2), X 1 ~X 3 each independently represents -C(-*)= or -N=, where * represents the bonding site with another structure, and # represents the bonding site with the metal atom.

[0012] Hereinafter, the resin composition according to the first aspect of the present invention or the resin composition according to the second aspect of the present invention is also collectively referred to as "the resin composition of the present invention" or simply "the composition of the present invention". The above metal complex contained in the resin composition according to the first aspect of the present invention is also referred to as "the first specific metal complex". The above compound contained in the resin composition according to the second aspect of the present invention is also referred to as the "second specific metal complex". In addition, a metal complex corresponding to at least one of the first specific metal complex and the second specific metal complex is also simply referred to as the "specific metal complex".

[0013] The resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to exposure and development, and is preferably used for forming a film to be subjected to exposure and development using a developer containing an organic solvent. The resin composition of the present invention can be used, for example, for forming an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used for forming an interlayer insulating film for a rewiring layer. In particular, it is also one of the preferred embodiments of the present invention that the resin composition of the present invention contains a cyclized resin or a precursor thereof as a resin and is used for forming an interlayer insulating film for a rewiring layer. In addition, the resin composition of the present invention may be used for forming a photosensitive film to be subjected to positive development or may be used for forming a photosensitive film to be subjected to negative development. In the present invention, negative development refers to development in which unexposed portions are removed by development in exposure and development, and positive development refers to development in which exposed portions are removed by development. As the above exposure method, the above developer, and the above development method, for example, the exposure method described in the exposure step in the description of the method for producing a cured product described later, the developer and the development method described in the development step are used.

[0014] The resin composition of the present invention is excellent in storage stability and chemical resistance of the obtained cured product. The mechanism by which the above effects are obtained is unclear, but it is presumed as follows.

[0015] Conventionally, in various fields, an operation of curing a resin composition to obtain a cured product has been performed. For example, an operation of forming a composition film from a resin composition, exposing and heating this to obtain a cured product can be mentioned. Prior art uses metal complexes containing acetylacetonate ligands or triethanolamine ligands, but our research has revealed that improvements are needed in the following respects. When using metal complexes containing acetylacetonate ligands, the instability of the compound can lead to complex formation between resins, increasing the viscosity of the composition. Furthermore, when using metal complexes containing amino groups such as triethanolamine, the main chain of the resin can be cleaved, leading to a decrease in the viscosity of the composition. Thus, compositions using metal complexes described in prior art documents have been found to have poor storage stability, such as changes in viscosity during storage. Therefore, all metal complexes have room for improvement in terms of storage stability. Furthermore, it was found that when a composition without metal complexes was used to improve storage stability, the chemical resistance of the cured product obtained from the composition decreased. In the resin composition according to the first aspect of the present invention, the first specific metal complex has one or more π-conjugated moieties containing nitrogen atoms, thereby achieving both the stability of the metal complex and low reactivity with the resin. Furthermore, in the resin composition according to the second aspect of the present invention, the compound having a specific structure represented by formula (2-1) (the second specific metal complex) is used, thereby achieving both the stability of the compound and low reactivity with the resin. As a result, the resin composition of the present invention exhibits excellent storage stability, and the resulting cured product exhibits excellent chemical resistance. Furthermore, the π-conjugated moiety containing the nitrogen atom in the first specific metal complex can also act as a neutral base generator because it decomposes during heat treatment to generate a base. Similarly, the moiety containing the structure represented by formula (2-2) in the second specific metal complex can also act as a neutral base generator because it decomposes during heat treatment to generate a base. This is presumed to be because, for example, the basicity of the π-conjugated moiety containing the nitrogen atom or the moiety containing the structure represented by formula (2-2) is reduced by coordination with the metal atom, and when the metal complex decomposes due to heat, it acts as a base or undergoes further hydrolysis, like an imine compound, to generate a stronger base. Here, for example, if the resin composition contains a precursor of a cyclized resin such as a polyimide precursor as the resin, it is thought that the elongation at break will also increase due to the base generated from the metal complex. Thus, by including a metal complex having a coordination bond via a conjugated amino group, there is an unexpected effect in that it also acts as a base generator when heated, etc., and interacts with the resin.

[0016] However, neither Patent Document 1 nor 2 describes a resin composition containing a specific metal complex.

[0017] The components included in the resin composition of the present invention will be described in detail below.

[0018] <Resin> The resin composition of the present invention contains a resin. The resin is not particularly limited, and examples include resins used in conventional pattern-forming compositions. However, it is preferable to include at least one resin (specific resin) selected from the group consisting of cyclized resins and their precursors, and it is more preferable to include a precursor of a cyclized resin. Furthermore, the acid value of the resin (especially the acid value of the cyclized resin and its precursor) is preferably 0 to 0.8 mmol / g, more preferably 0.05 to 0.5 mmol / g, and even more preferably 0.1 to 0.3 mmol / g. Because the specific metal complex in this invention has high stability, it is presumed that a composition with excellent storage stability can be obtained even when used simultaneously with a resin having such an acid value. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, from the viewpoint of achieving both storage stability and developability, acid groups with a pKa of 0 to 10 are preferred for the acid groups contained in the resin, and acid groups with a pKa of 3 to 8 are more preferred. pKa is the negative common logarithm of the equilibrium constant Ka, expressed as pKa, when considering a dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa values ​​shall be those calculated using ACD / ChemSketch®. Alternatively, values ​​published in the "Revised 5th Edition Chemical Handbook, Basic Edition" edited by the Chemical Society of Japan may be referred to. Furthermore, if the acidic group is a polyvalent acid such as phosphoric acid, the above pKa is the first dissociation constant. The resin preferably contains at least one of the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains either a carboxyl group or a phenolic hydroxyl group.

[0019] The cyclized resin is preferably a resin that contains an imide ring structure or an oxazole ring structure in its main chain structure. In this invention, the main chain refers to the relatively longest bonding chain within the resin molecule. Examples of cyclized resins include polyimide, polybenzoxazole, and polyamideimide. A precursor of a cyclized resin is a resin that undergoes a change in chemical structure due to external stimuli to become a cyclized resin. Resins that undergo a change in chemical structure due to heat to become a cyclized resin are preferred, and resins that undergo a ring-closing reaction due to heat to form a ring structure to become a cyclized resin are more preferred. Examples of precursors for cyclized resins include polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors. In other words, the resin composition of the present invention preferably contains, as a specific resin, at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. The resin composition of the present invention preferably contains polyimide or a polyimide precursor as a specific resin. Furthermore, the specific resin preferably has polymerizable groups, and more preferably contains radical polymerizable groups. When a specific resin has radical polymerizable groups, the resin composition of the present invention preferably contains a radical polymerization initiator as described below, and more preferably contains a radical polymerization initiator as described below and a radical crosslinking agent as described below. Furthermore, it may optionally contain a sensitizer as described below. A negative-type photosensitive film can be formed from such a resin composition of the present invention. Furthermore, the specific resin may have polarity-converting groups such as acid-degradable groups. When a specific resin has an acid-degradable group, the resin composition of the present invention preferably contains a photoacid generator as described below. From such a resin composition of the present invention, for example, a chemically amplified positive-type or negative-type photosensitive film can be formed.

[0020] [Polyimide precursor] The polyimide precursor used in this invention is not particularly limited in type, but it is preferable that it contains repeating units represented by the following formula (2). [ka] In formula (2), A 1 and A 2 Each of these independently represents an oxygen atom or -NH-, and R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 Each of these independently represents either a hydrogen atom or a monovalent organic group.

[0021] A in equation (2) 1 and A 2 Each of these independently represents either an oxygen atom or -NH-, with the oxygen atom being preferred. R in equation (2) 111-Ar- and -Ar-L-Ar- are examples of divalent organic groups. Examples of divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. Preferably, the group consists of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably, a group containing an aromatic group having 6 to 20 carbon atoms. In the linear or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and aromatic group, the hydrocarbon group of the ring member may be substituted with a group containing a heteroatom. As a preferred embodiment of the present invention, the group is exemplified by groups represented by -Ar- and -Ar-L-Ar-, and particularly preferably by groups represented by -Ar-L-Ar-. However, Ar is an aromatic group independently, and L is a single bond, or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the above. The preferred ranges for these are as described above.

[0022] R 111 It is preferable that the polyimide precursor is derived from a diamine. Examples of diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. One type of diamine may be used, or two or more types may be used. Specifically, the diamine is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. The linear or branched aliphatic group may have hydrocarbon groups in the chain substituted with groups containing heteroatoms, and the cyclic aliphatic group and aromatic group may have hydrocarbon groups in the ring members substituted with groups containing heteroatoms. Examples of groups containing aromatic groups are listed below.

[0023] [ka] In the formula, A represents a single bond or a divalent linking group, and is preferably a single bond or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a group selected from a combination thereof; more preferably a single bond or a C1-C3 alkylene group which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO2-; and even more preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-. In the formula, * represents a bonding site with another structure.

[0024] Diamines include, specifically, 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 isophoronediamines; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'- or 3,3'-diaminodiphenylmethane, 4,4'- or 3,3'-diaminodiphenyl sulfone, 4,4'- or 3,3'-diaminodiphenyl sulfide, 4,4'- or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'- Diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 4 ,4'-diaminoparaterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-Bis(4-aminophenyl)benzene, 3,3'-Diethyl-4,4'-Diaminodiphenylmethane, 3,3'-Dimethyl-4,4'-Diaminodiphenylmethane, 4,4'-Diaminooctafluorobiphenyl, 2,2-Bis[4-(4-aminophenoxy)phenyl]propane, 2,2-Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-Bis(4-aminophenyl)-10-Hydroanthracene, 3,3',4,4'-Tetraaminobiphenyl, 3,3',4,4'-Tetraaminodiphenyl ether 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine , bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-Bis(4-aminophenyl)tetradecafluoroheptane, 2,2-Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-Bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,Examples include at least one diamine selected from 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotidine, and 4,4'-diaminoquaterphenyl.

[0025] Furthermore, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0026] Furthermore, diamines having two or more alkylene glycol units as the main chain, as described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598, are also preferably used.

[0027] R 111 From the viewpoint of the flexibility of the resulting organic film, it is preferable that it be represented as -Ar-L-Ar-. However, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the above. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. Here, the aliphatic hydrocarbon group is preferably an alkylene group.

[0028] Also, R 111From the viewpoint of i-ray transmittance, it is preferable that the group is a divalent organic group represented by formula (51) or formula (61) below. In particular, from the viewpoint of i-ray transmittance and availability, it is more preferable that the group is a divalent organic group represented by formula (61). Formula (51) [ka] In formula (51), R 50 ~R 57 Each of these is independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and R 50 ~R 57 At least one of them is a fluorine atom, a methyl group, or a trifluoromethyl group, and * independently represents a bonding site with the nitrogen atom in formula (2). R 50 ~R 57 Examples of monovalent organic groups 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). [ka] In formula (61), R 58 and R 59 Each of these is independently a fluorine atom, a methyl group, or a trifluoromethyl group, and each of these independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These may be used individually or in combination of two or more.

[0029] R in equation (2) 115 represents a tetravalent organic group. Preferably, the tetravalent organic group is one containing an aromatic ring, and more preferably, a group represented by formula (5) or formula (6) below. In formula (5) or formula (6), * independently represents a bonding site with another structure. [ka] In formula (5), R 112 The linking group is a single bond or a divalent linking group, preferably a single bond or a C1-C10 aliphatic hydrocarbon group which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, and -NHCO-, and a group selected from combinations thereof; more preferably a single bond or a C1-C3 alkylene group which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO2-; and even more preferably a divalent group selected from the group consisting of -CH2-, -C(CF3)2-, -C(CH3)2-, -O-, -CO-, -S-, and -SO2-.

[0030] R 115 Specifically, examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. Polyimide precursors are R 115 The structure may contain only one tetracarboxylic dianhydride residue, or it may contain two or more. Tetracarboxylic acid dianhydrides are preferably represented by the following formula (O). [ka] In formula (O), R 115 R represents a tetravalent organic group. 115 The preferred range of R in equation (2) is 115 This is synonymous with the same thing, and the preferred range is also similar.

[0031] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, and 2,2 ',3,3'-diphenylmethanetetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,7-naphthalenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, Examples include 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 of these having 1 to 6 carbon atoms.

[0032] Furthermore, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 are also preferred examples.

[0033] In equation (2), R 111 and R 115It is also possible that at least one of them has an OH group. More specifically, R 111 Examples include residues of bisaminophenol derivatives.

[0034] R in equation (2) 113 and R 114 Each of these independently represents a hydrogen atom or a monovalent organic group. Preferably, the monovalent organic group includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group. Also, R 113 and R 114 It is preferable that at least one of them contains a polymerizable group, and more preferably that both contain a polymerizable group. 113 and R 114 It is also preferable that at least one of the components contains two or more polymerizable groups. The polymerizable groups are groups that can undergo crosslinking reactions by the action of heat, radicals, etc., and radical polymerizable groups are preferred. Specific examples of polymerizable groups include groups having ethylenically unsaturated bonds, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups in the polyimide precursor, groups having ethylenically unsaturated bonds are preferred. Groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl groups), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

[0035] [ka]

[0036] In equation (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In equation (III), * represents a bonding site with another structure. In equation (III), R 201 This represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkylene oxy group. Suitable R 201 Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, -CH2CH(OH)CH2-, and polyalkylene oxy groups. More preferably, alkylene groups such as ethylene and propylene, -CH2CH(OH)CH2-, cyclohexyl, and polyalkylene oxy groups are preferred, and even more preferably, alkylene groups such as ethylene and propylene, or polyalkylene oxy groups. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When a polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of alkylene oxy groups in the polyalkylene oxy group may be random, block-like, or have alternating patterns. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, still more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the alkylene group may have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like. Furthermore, the number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the above-mentioned group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating or other patterned arrangements. The preferred configuration of the number of repeating ethylene oxy groups in these groups is as described above.

[0037] In equation (2), R 113 If R is a hydrogen atom, 114 If the atom is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0038] In equation (2), R 113 and R 114 At least one of the groups may be a polarity-converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it decomposes under the action of an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but acetal groups, ketal groups, silyl groups, silyl ether groups, tertiary alkyl ester groups, etc. are preferred, and from the viewpoint of exposure sensitivity, acetal groups or ketal groups are more preferred. Specific examples of acid-degradable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, and trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl group or tetrahydrofuranyl group are preferred.

[0039] Furthermore, the polyimide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0040] Furthermore, to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane as the diamine.

[0041] The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having the repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to broaden the exposure latitude. Formula (2-A) [ka] In formula (2-A), A 1 and A 2 represents an oxygen atom, R 111 and R 112 Each of these independently represents a divalent organic group, R 113 and R 114 Each of these independently represents a hydrogen atom or a monovalent organic group, R 113 and R 114 Preferably, at least one of the groups is a polymerizable group, and both are polymerizable groups.

[0042] A 1 , A 2 , R 111 , R 113 and R 114 These are, independently of A in equation (2), 1 , A 2 , R 111 , R 113 and R114 This is synonymous with the same thing, and the preferred range is also similar. R 112 R in equation (5) is 112 This is synonymous with the same thing, and the preferred range is also similar.

[0043] The polyimide precursor may contain one type of repeating unit represented by formula (2), or it may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of formula (2), the polyimide precursor may also contain other types of repeating units.

[0044] One embodiment of the polyimide precursor in the present invention is one in which the content of repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).

[0045] The weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 10,000 to 50,000, and particularly 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 degree of molecular weight dispersion of the 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 upper limit to the degree of molecular weight dispersion of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, the degree of molecular weight dispersion is the value calculated by dividing the weight-average molecular weight by the number-average molecular weight. Furthermore, if the resin composition contains multiple types of polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyimide precursors as a single resin are, respectively, within the above ranges.

[0046] [Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide, or a polyimide soluble in a developer mainly composed of an organic solvent. In this specification, alkali-soluble polyimide refers to a polyimide that dissolves at a rate of 0.1 g or more in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium at 23°C. From the viewpoint of pattern formation, it is preferable that the polyimide dissolves at a rate of 0.5 g or more, and more preferably at a rate of 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less. Furthermore, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyimide is preferably a polyimide having multiple imide structures in its main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the polymer compound molecule constituting the resin, and "side chain" refers to the other bonding chains.

[0047] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains fluorine atoms. Fluorine atoms are, for example, R in the repeating unit represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 Preferably, it is included in the repeating unit R represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0048] -Silicon atom- From the viewpoint of the film strength of the resulting organic film, it is also preferable that the polyimide contains silicon atoms. For example, silicon atoms are R in the repeating unit represented by formula (4) described later. 131 Preferably, it is included in the repeating unit R represented by formula (4) described later. 131 It is more preferable that it be included as an organically modified (poly)siloxane structure, as described later. Furthermore, the silicon atoms or the organically modified (poly)siloxane structure may be included in the side chains of the polyimide, but it is preferable that they be included in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.

[0049] -Ethylene unsaturated bond- From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyimide has ethylenically unsaturated bonds. Polyimides may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but it is preferable that they be in the side chains. The above ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 Preferably, it is included in the repeating unit R represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 It is more preferable that it be included as a group having an ethylenically unsaturated bond. Among these, the ethylenically unsaturated bond is R in the repeating unit represented by formula (4) described later. 131 Preferably, it is included in the repeating unit R represented by formula (4) described later.131 It is more preferable that it be included as a group having an ethylenically unsaturated bond. Groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, vinylphenyl groups, and other groups having a vinyl group that is directly bonded to an aromatic ring and may be substituted, (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (IV).

[0050] [ka]

[0051] In formula (IV), R 20 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred.

[0052] In formula (IV), R 21 This represents an alkylene group having 2 to 12 carbon atoms, -O-CH2CH(OH)CH2-, -C(=O)O-, -O(C=O)NH-, a (poly)alkylene oxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group formed by combining two or more of these. Furthermore, the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination thereof. Of the above alkylene groups having 2 to 12 carbon atoms, alkylene groups having 2 to 8 carbon atoms are preferred, and alkylene groups having 2 to 4 carbon atoms are more preferred.

[0053] Among these, R 21 It is preferable that the group is represented by any of the following formulas (R1) to (R3), and more preferably by the group represented by formula (R1). [ka] In formulas (R1) to (R3), L represents a single bond, or an alkylene group having 2 to 12 carbon atoms, a (poly)alkylene oxy 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 another structure; and ● represents R in formula (IV). 21 This represents the bonding site with the oxygen atom to which it is bonded. In formulas (R1) to (R3), preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkylene oxy group having 2 to 30 carbon atoms in L are as described above for R 21 This is similar to the preferred embodiment of the alkylene group having 2 to 12 carbon atoms, or the (poly)alkylene oxy group having 2 to 30 carbon atoms. In formula (R1), X is preferably an oxygen atom. In equations (R1) to (R3), * is equivalent to * in equation (IV), and the same applies to the preferred embodiment. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group, such as a phenolic hydroxyl group, with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate).

[0054] In formula (IV), * represents a binding site with another structure, and is preferably a binding site with the polyimide main chain.

[0055] The amount of ethylenically 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.

[0056] -Polymerizable groups other than those having ethylenically unsaturated bonds- Polyimides may have polymerizable groups other than those having ethylenically unsaturated bonds. Polymerizable groups other than those having ethylenically unsaturated bonds include epoxy groups, cyclic ether groups such as oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups. Polymerizable groups other than those having an ethylenically unsaturated bond include, for example, R in the repeating unit represented by formula (4) described later. 131 It is preferable that it be included in The amount of polymerizable groups other than those having ethylenically unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0057] -Polar Conversion Group- Polyimides may have polarity-changing groups such as acid-degradable groups. The acid-degradable group in polyimides is R in formula (2) above. 113 and R 114 The acid-degradable group is the same as described above, and the preferred embodiment is also the same. The polarity conversion group is, for example, R in the repeating unit represented by formula (4) described later. 131 , R 132 It is found at the ends of polyimides, etc.

[0058] - Acid Value - When polyimide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyimide is preferably 30 mg KOH / g or higher, more preferably 50 mg KOH / g or higher, and even more preferably 70 mg KOH / g or higher. Furthermore, the above acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. Furthermore, when polyimide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyimide is preferably 1 to 35 mg KOH / g, more preferably 2 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, regarding the acid groups contained in polyimide, from the viewpoint of achieving both storage stability and developability, acid groups with a pKa of 0 to 10 are preferred, and acid groups with a pKa of 3 to 8 are more preferred. The polyimide preferably contains at least one of the group consisting of a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

[0059] -Phenolenic hydroxyl group- From the viewpoint of ensuring an appropriate development speed with an alkaline developer, it is preferable that the polyimide has a phenolic hydroxyl group. Polyimides may have phenolic hydroxyl groups at the ends of their main chains or in their side chains. The phenolic hydroxyl group is, for example, R in the repeating unit represented by formula (4) described later. 132 , or R in the repeating unit represented by formula (4) described later. 131 It is preferable that it be included in The amount of phenolic hydroxyl groups relative to the total mass of polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0060] The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it is preferable that it contains repeating units represented by the following formula (4). [ka] In formula (4), R 131 represents a divalent organic group, R 132This represents a tetravalent organic group. If it has polymerizable groups, the polymerizable groups are R 131 and R 132 It may be located at least one of the two, 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) [ka] In formula (4-1), R 133 is a polymerizable group, and the other groups are equivalent to formula (4). Formula (4-2) [ka] R 134 and R 135 At least one of the groups is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is equivalent to formula (4).

[0061] Examples of polymerizable groups include groups containing the ethylenically unsaturated bond described above, or crosslinkable groups other than those having the ethylenically unsaturated bond described above. R 131 R represents a divalent organic group. As an example of a divalent organic group, R in formula (2) is 111 Similar examples are given, and the preferred range is also similar. Also, R 131 Examples include diamine residues remaining after the removal of the amino group of a diamine. Examples of diamines include aliphatic, cyclic aliphatic, or aromatic diamines. A specific example is R in formula (2) of the polyimide precursor. 111 Examples include:

[0062] R 131It is preferable that the diamine residue has at least two alkylene glycol units in its main chain, as this more effectively suppresses warping during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule, and even more preferably, it is the above-mentioned diamine that does not contain an aromatic ring.

[0063] Examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in a single molecule include, but are not limited to, Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.

[0064] R 132 R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) is 115 Similar examples are given, and the preferred range is also similar. For example, R 115 The four bonds of the tetravalent organic group, as exemplified above, bond with the four -C(=O)- parts in formula (4) above to form a fused ring.

[0065] Also, R 132 Examples include tetracarboxylic acid residues remaining after the removal of the anhydride group from tetracarboxylic dianhydride. A specific example is R in formula (2) of the polyimide precursor. 115 Examples include: From the standpoint of the strength of the organic film, R 132 It is preferable that it is an aromatic diamine residue having 1 to 4 aromatic rings.

[0066] R 131 and R 132It is also preferable that at least one of them has an OH group. More specifically, R 131 As examples, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are listed as preferred examples, R 132 As such, (DAA-1) to (DAA-5) above can be cited as more preferable examples.

[0067] Furthermore, it is preferable that the polyimide contains fluorine atoms in its structure. The fluorine atom content in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.

[0068] Furthermore, to improve adhesion to the substrate, the polyimide may be copolymerized with aliphatic groups having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0069] Furthermore, in order to improve the storage stability of the resin composition, it is preferable that the main chain ends of the polyimide are encapsulated with end-captives such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. Of these, the use of monoamines is more preferable, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, and 1-carboxy Examples include -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants.

[0070] -Imidization rate (ring closure rate)- The imidization rate (also called the "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film. There is no particular upper limit to the imidization rate mentioned above; it is acceptable as long as it is 100% or less. The above imidization rate can be measured, for example, by the following method. The infrared absorption spectrum of polyimide was measured, and the absorption peak originating from the imide structure was found at 1377 cm⁻¹. -1 The peak intensity P1 in the vicinity is determined. Next, the polyimide is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again, at 1377 cm⁻¹. -1 Determine the nearby peak intensity P2. Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula. Imidization rate (%) = (Peak intensity P1 / Peak intensity P2) × 100

[0071] Polyimides are all of the same type R 131 or R 132 It may include the repeating unit represented by the above formula (4), and may include two or more different types of R 131 or R 132 The polyimide may also contain repeating units represented by the above formula (4). In addition to the repeating units represented by the above formula (4), the polyimide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (2).

[0072] Polyimides can be synthesized by obtaining polyimide precursors using methods such as: reacting tetracarboxylic dianhydride with a diamine (partially substituted with a monoamine end-captive) at low temperatures; reacting tetracarboxylic dianhydride (partially substituted with an acid anhydride, monoacid chloride compound, or monoactive ester compound end-captive) with a diamine at low temperatures; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then reacting it with a diamine (partially substituted with a monoamine end-captive) in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol, and then acid-chloridizing the remaining dicarboxylic acid and reacting it with a diamine (partially substituted with a monoamine end-captive); completely imidizing the precursor using a known imidation reaction method; stopping the imidation reaction midway to introduce a partial imide structure; or introducing a partial imide structure by blending a fully imidized polymer with its polyimide precursor. Other known methods for synthesizing polyimides can also be applied.

[0073] The weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 10,000 to 50,000, and particularly preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the flexural resistance of the cured film can be improved. To obtain 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 degree of molecular weight dispersion of the polyimide is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit set for the degree of molecular weight dispersion of the polyimide, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyimides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimides are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyimides are treated as a single resin are, respectively, within the above ranges.

[0074] [Polybenzoxazole precursor] The polybenzoxazole precursor used in this invention does not have any particular structure, but preferably contains repeating units represented by the following formula (3). [ka] In formula (3), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, R 123 and R 124 Each of these independently represents either a hydrogen atom or a monovalent organic group.

[0075] In equation (3), R 123 and R 124 These are R in equation (2), respectively. 113 This is synonymous with the same as the preferred range. That is, it is preferable that at least one of them is a polymerizable group. In equation (3), R 121 R represents a divalent organic group. A divalent organic group is preferably one containing at least one of an aliphatic group and an aromatic group. A linear aliphatic group is preferred. 121 A dicarboxylic acid residue is preferred. One or more dicarboxylic acid residues may be used.

[0076] As the dicarboxylic acid residue, dicarboxylic acid residues containing an aliphatic group and dicarboxylic acid residues containing an aromatic group are preferred, and dicarboxylic acid residues containing an aromatic group are more preferred. As for dicarboxylic acids containing an aliphatic group, dicarboxylic acids containing a linear or branched (preferably linear) aliphatic group are preferred, and dicarboxylic acids consisting of a linear or branched (preferably linear) aliphatic group and two -COOH groups are more preferred. The number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succicic 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-tetramethylpimelic acid. Examples include suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and dicarboxylic acids represented by the following formula.

[0077] [ka] (In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

[0078] As for dicarboxylic acids containing aromatic groups, dicarboxylic acids having the following aromatic groups are preferred, and dicarboxylic acids consisting only of the following aromatic groups and two -COOH groups are more preferred.

[0079] [ka] In the formula, A represents a divalent group selected from the group consisting of -CH2-, -O-, -S-, -SO2-, -CO-, -NHCO-, -C(CF3)2-, and -C(CH3)2-, and * represents a binding site with another structure, independently.

[0080] Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

[0081] In equation (3), R 122 R represents a tetravalent organic group. As an example of a tetravalent organic group, R in formula (2) above is 115 This is synonymous with the same thing, and the preferred range is also similar. R 122It is also preferable that the group is derived from a bisaminophenol derivative, and examples of groups derived from bisaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis-(4-amino Examples include 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, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used individually or in combination.

[0082] Among bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferred.

[0083] [ka] In the formula, X1 represents -O-, -S-, -C(CF3)2-, -CH2-, -SO2-, and -NHCO-, and * and # represent bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Also, R 122 It is also preferable that the structure be represented by the above formula. 122However, if the structure is represented by the above formula, then of the four * and # characters, any two of them are R in formula (3). 122 The bond site with the nitrogen atom to which it is bonded, and the other two are R in formula (3). 122 It is preferable that the bond site is with the oxygen atom to which it is bonded, and the two *s are R in formula (3). 122 The bond site with the oxygen atom to which it is bonded, and the two #s are R in formula (3). 122 Either the bond site with the nitrogen atom to which it is bonded, or the two *s are R in formula (3). 122 The bond site with the nitrogen atom to which it is bonded, and the two #s are R in formula (3). 122 It is more preferable that the bond site is with the oxygen atom to which it is bonded, and the two *s are R in formula (3). 122 The bond site with the oxygen atom to which it is bonded, and the two #s are R in formula (3). 122 It is even more preferable that the site is a bonding site with the nitrogen atom to which it is bonded.

[0084] The bisaminophenol derivative is also preferably a compound represented by formula (As). [ka]

[0085] In formula (As), R1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO2-, -CO-, -NHCO-, a single bond, or an organic group selected from the group of formulas (A-sc) below. R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different. R3 is a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.

[0086] [ka] (In formula (A-sc), * indicates bonding to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by formula (As) above.)

[0087] In the above formula (As), having a substituent at the ortho position of the phenolic hydroxyl group, i.e., R3, is considered to bring the carbonyl carbon of the amide bond and the hydroxyl group closer together, and is particularly preferable because it further enhances the effect of high cyclization rate when cured at low temperatures.

[0088] Furthermore, in the above formula (As), it is preferable that R2 is an alkyl group and R3 is an alkyl group, as this maintains the effects of high transparency to i-lines and a high cyclization rate when cured at low temperatures.

[0089] Furthermore, it is even more preferable that R1 in the above formula (As) is an alkylene or a substituted alkylene. Specific examples of alkylenes and substituted alkylenes for R1 include linear or branched alkyl groups having 1 to 8 carbon atoms. Among these, -CH2-, -CH(CH3)-, and -C(CH3)2- are more preferable because they allow for the production of a well-balanced polybenzoxazole precursor that maintains high transparency to i-lines and a high cyclization rate when cured at low temperatures, while also having sufficient solubility in solvents.

[0090] For a method of producing the bisaminophenol derivative represented by the above formula (As), refer to, for example, 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.

[0091] Specific examples of the structure of the bisaminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506, and these contents are incorporated herein by reference. Of course, we are not limited to these.

[0092] The polybenzoxazole precursor may include other types of repeating structural units in addition to the repeating unit of formula (3) above. The polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit, in that it can suppress the occurrence of warping associated with ring closure.

[0093] [ka] In equation (SL), Z has an a structure and a b structure, and R 1s R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. 2s R is a hydrocarbon group having 1 to 10 carbon atoms. 3s , R 4s , R 5s , R 6s At least one of the groups is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. Polymerization of structures a and b may be block polymerization or random polymerization. The molar percentage of the Z portion is 5 to 95 mol% for structure a, 95 to 5 mol% for structure b, and 100 mol% for a + b.

[0094] In formula (SL), preferred Z is R in the b structure. 5s and R 6s Examples include those in which the group is a phenyl group. 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, it is possible to more effectively reduce the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor, thereby achieving both the effect of suppressing warping and the effect of improving solvent solubility.

[0095] When other types of repeating units include diamine residues represented by formula (SL), it is also preferable to include tetracarboxylic acid residues remaining after the removal of the anhydride group from the tetracarboxylic dianhydride as repeating units. An example of such tetracarboxylic acid residues is R in formula (2). 115 Examples include:

[0096] 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. 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 degree of molecular weight dispersion of the polybenzoxazole precursor is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no upper limit to the degree of molecular weight dispersion of the polybenzoxazole precursor, but for example, it is preferably 2.6 or lower, more preferably 2.5 or lower, even more preferably 2.4 or lower, even more preferably 2.3 or lower, and even more preferably 2.2 or lower. Furthermore, if the resin composition contains multiple types of polybenzoxazole precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polybenzoxazole precursors are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polybenzoxazole precursors as a single resin are, respectively, within the above range.

[0097] [Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and more preferably a compound represented by the following formula (X) that has a polymerizable group. A radical polymerizable group is preferred as the polymerizable group. Alternatively, it may be a compound represented by the following formula (X) that has a polarity conversion group such as an acid-degradable group. [ka] In formula (X), R 133 represents a divalent organic group, R 134 This represents a tetravalent organic group. If it has a polarity-converting group such as a polymerizable group or an acid-degradable group, the polarity-converting group such as a polymerizable group or an acid-degradable group is R 133 and R 134 It may be located at least one of the two, or it may be located at the terminal end of the polybenzoxazole as shown in formula (X-1) or formula (X-2) below. Formula (X-1) [ka] In formula (X-1), R 135 and R 136 At least one of the groups is a polarity-converting group such as a polymerizable group or an acid-degradable group; if it is not a polarity-converting group such as a polymerizable group or an acid-degradable group, it is an organic group; and the other group is equivalent to formula (X). Formula (X-2) [ka] In formula (X-2), R 137 is a polarity-converting group such as a polymerizable group or an acid-degradable group, the others are substituents, and the other groups are synonymous with formula (X).

[0098] Polarity-converting groups such as polymerizable groups or acid-degradable groups are synonymous with the polymerizable groups described above in relation to the polymerizable groups of the polyimide precursor.

[0099] R 133 R represents a divalent organic group. Examples of divalent organic groups include aliphatic groups and aromatic groups. A specific example is R in formula (3) of the polybenzoxazole precursor. 121 Examples include R. 121 It is similar to that.

[0100] R 134 R represents a tetravalent organic group. An example of a tetravalent organic group is R in formula (3) of the polybenzoxazole precursor. 122 Examples include R. 122 It is similar to that. For example, R 122The four bonders of the tetravalent organic group, as exemplified above, bond with the nitrogen and oxygen atoms in formula (X) to form a fused ring. For example, R 134 However, if it is the following organic group, it forms the following structure. In the following structure, * represents the bonding site with the nitrogen atom or oxygen atom in formula (X), respectively. [ka]

[0101] The polybenzoxazole preferably has an oxazole conversion rate of 85% or more, and more preferably 90% or more. There is no particular upper limit, and it may be 100%. By having an oxazole conversion rate of 85% or more, the membrane shrinkage due to ring closure that occurs when oxazole is converted by heating is reduced, and the occurrence of warping can be suppressed more effectively. The above oxazole conversion rate can be measured, for example, by the following method. The infrared absorption spectrum of polybenzoxazole was measured, and the absorption peak at 1650 cm², which originates from the amide structure of the precursor, was observed. -1 Determine the peak intensity Q1 in the vicinity. Next, 1490 cm -1 The absorption intensity of aromatic rings found nearby is used for normalization. After heat treatment of the polybenzoxazole at 350°C for 1 hour, the infrared absorption spectrum is measured again, and the spectroscopy is performed at 1650 cm⁻¹. -1 The peak intensity Q2 in the vicinity was calculated to be 1490 cm. -1 The absorption intensity of the aromatic rings observed nearby is used for normalization. Using the normalized peak intensities Q1 and Q2 obtained, the oxazole rate of polybenzoxazole can be determined based on the following formula. Oxazole conversion rate (%) = (Specific value of peak intensity Q1 / Specific value of peak intensity Q2) × 100

[0102] Polybenzoxazoles are all of the same type as R 131 or R 132 The repeating unit of the above formula (X) may include two or more different types of R 131 or R 132The polybenzoxazole may contain repeating units of the above formula (X), including the above formula (X). In addition, the polybenzoxazole may contain other types of repeating units besides the repeating units of the above formula (X).

[0103] Polybenzoxazoles are, for example, bisaminophenol derivatives and R 133 It is obtained by reacting a dicarboxylic acid containing or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor, and then oxazoleizing this using a known oxazole reaction method. In the case of dicarboxylic acids, to increase the reaction yield, etc., an activated ester-type dicarboxylic acid derivative that has been pre-reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used.

[0104] The weight-average molecular weight (Mw) of the 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 types of polybenzoxazole are contained, it is preferable that the weight-average molecular weight of at least one of the polybenzoxazoles 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. The degree of molecular weight dispersion of the polybenzoxazole is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no upper limit to the degree of molecular weight dispersion of the polybenzoxazole, but for example, it is preferably 2.6 or lower, more preferably 2.5 or lower, even more preferably 2.4 or lower, even more preferably 2.3 or lower, and even more preferably 2.2 or lower. Furthermore, if the resin composition contains multiple types of polybenzoxazole as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polybenzoxazoles are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polybenzoxazole are treated as a single resin are, respectively, within the above range.

[0105] [Polyamide-imide precursors] The polyamide-imide precursor preferably contains repeating units represented by the following formula (PAI-2). [ka] In formula (PAI-2), R 117 represents a trivalent organic group, R 111 represents a divalent organic group, A 2 represents an oxygen atom or -NH-, R 113 represents a hydrogen atom or a monovalent organic group.

[0106] In formula (PAI-2), R 117 Examples include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, these are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these by single bonds or linking groups. More preferably, these are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. The above-mentioned linking groups are preferably -O-, -S-, -C(=O)-, -S(=O)2-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked, and more preferably -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked. The alkylene group described above is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group described above is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atoms in the halogenated alkylene group may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. An example of a preferred halogenated alkylene group is the (ditrifluoromethyl)methylene group. The above-mentioned arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0107] Also, R 117 It is preferable that it be derived from a tricarboxylic acid compound in which at least one carboxyl group may be halogenated. Chlorination is preferred as the halogenation. 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 above tricarboxylic acid compound may be converted to acid anhydrides. Examples of tricarboxylic acid compounds that may be halogenated and used in the production of polyamide-imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used individually or in combination of two or more.

[0108] Specifically, preferred tricarboxylic acid compounds include a linear 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 single bonds or linking groups. More preferred tricarboxylic acid compounds include 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 single bonds or linking groups.

[0109] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalentricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked by a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or phenylene group. These compounds may be compounds in which two carboxyl groups have been converted to anhydrides (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group has been converted to a halogen (e.g., trimellitic anhydride chloride).

[0110] In formula (PAI-2), R 111 , A 2 , R 113 These are the R values ​​in equation (2) above. 111 , A 2 , R 113 This is synonymous with the same as the preferred configuration.

[0111] The polyamide-imide precursor may further contain other repeating units. Other repeating units include the repeating unit represented by equation (2) above, and the repeating unit represented by equation (PAI-1) below. [ka]

[0112] In formula (PAI-1), R 116 represents a divalent organic group, R111 This represents a divalent organic group. In formula (PAI-1), R 116 Examples include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, or groups formed by linking two or more of these by single bonds or linking groups. Preferably, these are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more of these by single bonds or linking groups. More preferably, these are aromatic groups having 6 to 20 carbon atoms, or groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms by single bonds or linking groups. The above-mentioned linking groups are preferably -O-, -S-, -C(=O)-, -S(=O)2-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked, and more preferably -O-, -S-, alkylene groups, halogenated alkylene groups, arylene groups, or linking groups in which two or more of these are linked. The alkylene group described above is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group described above is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. The halogen atoms in the halogenated alkylene group may include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being preferred. The halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferable that all of the hydrogen atoms are substituted with halogen atoms. An example of a preferred halogenated alkylene group is the (ditrifluoromethyl)methylene group. The above-mentioned arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0113] Also, R 116It is preferable that it be derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present 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 group in a dicarboxylic acid dihalide compound may be halogenated, but it is preferable that it is chlorinated, for example. In other words, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. Examples of halogenated dicarboxylic acid compounds or dicarboxylic acid dihalide compounds used in the production of polyamide-imide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds. These dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used individually or in combination of two or more.

[0114] Specifically, preferred dicarboxylic acid compounds or dicarboxylic acid dihalide compounds include a linear 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 single bonds or linking groups. More preferred dicarboxylic acid compounds or dicarboxylic acid dihalide compounds include 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 single bonds or linking groups.

[0115] Furthermore, specific examples of dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succicic 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, suberic acid, dodecafluorosuberic acid, azelaic acid, and sebaci. Examples include nic acid, hexadecafluorosebacic acid, 1,9-nonanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, pentadecanediic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanediic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, etc. Specific examples of dicarboxylic acid dihalide compounds include compounds in which the two carboxyl groups in the above-mentioned specific examples of dicarboxylic acid compounds are halogenated.

[0116] In formula (PAI-1), R 111 R in equation (2) above is 111 This is synonymous with the same as the preferred configuration.

[0117] Furthermore, the polyamide-imide precursor preferably contains fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

[0118] Furthermore, to improve adhesion to the substrate, the polyamide-imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples include using bis(3-aminopropyl)tetramethyldisiloxane or bis(p-aminophenyl)octamethylpentasiloxane as the diamine component.

[0119] One embodiment of the polyamideimide precursor in the present invention is one in which the total content of repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1), and repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor, excluding the terminals, may be any of the repeating units represented by formula (PAI-2), repeating units represented by formula (PAI-1), and repeating units represented by formula (2). Another embodiment of the polyamideimide precursor in the present invention is one in which the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is 50 mol% or more of the total repeating units. The above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the above total content is not particularly limited, and all repeating units in the polyamideimide precursor, excluding the terminals, may be either repeating units represented by formula (PAI-2) or repeating units represented by formula (PAI-1).

[0120] 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 degree of 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 upper limit to the degree of molecular weight dispersion of the polyamide-imide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyamide-imide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyamide-imide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyamide-imide precursors as a single resin are, respectively, within the above ranges.

[0121] [Polyamide-imide] The polyamide-imide used in the present invention may be an alkali-soluble polyamide-imide, or a polyamide-imide that is soluble in a developer mainly composed of an organic solvent. In this specification, alkali-soluble polyamide-imide refers to a polyamide-imide that dissolves at a rate of 0.1 g or more in 100 g of a 2.38% by mass aqueous solution of tetramethylammonium at 23°C. From the viewpoint of pattern formation, it is preferable that the polyamide-imide dissolves at a rate of 0.5 g or more, and more preferably at a rate of 1.0 g or more. The upper limit of the above dissolution amount is not particularly limited, but it is preferably 100 g or less. Furthermore, from the viewpoint of the film strength and insulating properties of the resulting organic film, the polyamide-imide is preferably a polyamide-imide having multiple amide bonds and multiple imide structures in its main chain.

[0122] -Fluorine atom- From the viewpoint of the film strength of the resulting organic film, it is preferable that the polyamide-imide contains fluorine atoms. Fluorine atoms, for example, are R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111Preferably, it is included in the repeating unit R represented by formula (PAI-3) described later. 117 , or R 111 It is more preferable that it be included as an alkyl fluoride. The amount of fluorine atoms relative to the total mass of the polyamide-imide is preferably 5% by mass or more, and preferably 20% by mass or less.

[0123] -Ethylene unsaturated bond- From the viewpoint of the film strength of the resulting organic film, the polyamide-imide may have ethylenically unsaturated bonds. Polyamide-imides may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, but it is preferable that they be in the side chains. The above ethylenically unsaturated bond preferably has radical polymerizability. The ethylenically unsaturated bond is R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 Preferably, it is included in the repeating unit R represented by formula (PAI-3) described later. 117 , or R 111 It is more preferable that it be included as a group having an ethylenically unsaturated bond. A preferred embodiment of the group having an ethylenically unsaturated bond is the same as the preferred embodiment of the group having an ethylenically unsaturated bond in the polyimide described above.

[0124] The amount of ethylenically unsaturated bonds relative to the total mass of polyamide-imide is preferably 0.0001 to 0.1 mol / g, and more preferably 0.001 to 0.05 mol / g.

[0125] -Polymerizable groups other than ethylenically unsaturated bonds- Polyamide-imides may have polymerizable groups other than ethylenically unsaturated bonds. Polymerizable groups other than ethylenically unsaturated bonds in polyamide-imides include the same groups as those described above for polymerizable groups other than ethylenically unsaturated bonds in polyimides. Polymerizable groups other than ethylenically unsaturated bonds include, for example, R in the repeating unit represented by formula (PAI-3) described later. 111 It is preferable that it be included in The amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamide-imide is preferably 0.05 to 10 mol / g, and more preferably 0.1 to 5 mol / g.

[0126] -Polar Conversion Group- Polyamide-imides may have polarity-changing groups such as acid-degradable groups. The acid-degradable group in polyamide-imides is R in formula (2) above. 113 and R 114 The acid-degradable group is the same as described above, and the preferred embodiment is also the same.

[0127] - Acid Value - When polyamide-imide is subjected to alkaline development, from the viewpoint of improving developability, the acid value of the polyamide-imide is preferably 30 mg KOH / g or higher, more preferably 50 mg KOH / g or higher, and even more preferably 70 mg KOH / g or higher. Furthermore, the above acid value is preferably 500 mg KOH / g or less, more preferably 400 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. Furthermore, when polyamide-imide is subjected to development using a developer mainly composed of an organic solvent (for example, "solvent development" described later), the acid value of the polyamide-imide is preferably 2 to 35 mg KOH / g, more preferably 3 to 30 mg KOH / g, and even more preferably 5 to 20 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992. Furthermore, examples of acid groups contained in polyamideimides include the same groups as those in the polyimides described above, and the preferred embodiments are also the same.

[0128] -Phenolenic hydroxyl group- From the viewpoint of ensuring an appropriate development speed with an alkaline developer, it is preferable that the polyamide-imide has a phenolic hydroxyl group. Polyamide-imides may have phenolic hydroxyl groups at the ends of their main chains or in their side chains. Phenolic hydroxyl groups are, for example, R in the repeating unit represented by formula (PAI-3) described later. 117 , or R 111 It is preferable that it be included in The amount of phenolic hydroxyl groups relative to the total mass of polyamideimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

[0129] The polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it is preferable that it contains a repeating unit represented by the following formula (PAI-3). [ka] In formula (PAI-3), R 111 and R 117 These are the R values ​​in equation (PAI-2), respectively. 111 and R 117 This is synonymous with the same as the preferred configuration. If it has polymerizable groups, the polymerizable groups are R 111 and R 117 It may be located at least one of the two or at the end of the polyamide-imide.

[0130] Furthermore, in order to improve the storage stability of the resin composition, it is preferable to encapsulate the main chain ends of the polyamide-imide with an end-capturing agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. The preferred embodiment of the end-capturing agent is the same as the preferred embodiment of the end-capturing agent in polyimide described above.

[0131] -Imidization rate (ring closure rate)- The imidization rate (also called the "ring closure rate") of polyamide-imide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength and insulating properties of the resulting organic film. There is no particular upper limit to the imidization rate mentioned above; it is acceptable as long as it is 100% or less. The above imidization rate is measured by the same method as the ring closure rate of the polyimide described above.

[0132] Polyamide-imides are all of the same type R 111 or R 117 It may include the repeating unit represented by the above formula (PAI-3), and may contain two or more different types of R 131 or R 132 The polyamide-imide may also contain repeating units represented by the above formula (PAI-3). In addition to the repeating units represented by the above formula (PAI-3), the polyamide-imide may also contain other types of repeating units. Examples of other types of repeating units include the repeating units represented by the above formula (PAI-1) or formula (PAI-2).

[0133] Polyamide-imides can be synthesized, for example, by obtaining a polyamide-imide precursor by a known method and then completely imidizing it using a known imidation reaction method, or by stopping the imidation reaction midway and introducing a partial imide structure, or by blending a fully imidized polymer with its polyamide-imide precursor to introduce a partial imide structure.

[0134] 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 degree of molecular weight dispersion of the polyamide-imide is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no upper limit for the degree of molecular weight dispersion of the polyamide-imide, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. Furthermore, if the resin composition contains multiple types of polyamide-imides as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyamide-imides are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyamide-imides are treated as a single resin are, respectively, within the above ranges.

[0135] [Method for producing polyimide precursors, etc.] Polyimide precursors can be obtained by methods such as reacting tetracarboxylic dianhydride with a diamine at low temperature, reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and esterifying it with a condensing agent or alkylating agent, obtaining a diester from tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine in the presence of a condensing agent, or obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine. Of the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferred. Examples of the condensing agents mentioned above include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agents mentioned above include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dialkylformamide dialkylacetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agents mentioned above include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing polyimide precursors, it is preferable to use an organic solvent during the reaction. One organic solvent may be used, or two or more may be used. The organic solvent can be appropriately determined depending on the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diglym), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing polyimide precursors, it is preferable to add a basic compound during the reaction. The basic compound may be one type or two or more types. The basic compound can be appropriately determined depending on the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, and N,N-dimethyl-4-aminopyridine.

[0136] -End-capturing agent- In the production method of polyimide precursors, etc., it is preferable to encapsulate the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin ends of the polyimide precursor, etc., in order to further improve storage stability. When encapsulating the carboxylic acid anhydride and acid anhydride derivative remaining at the resin ends, examples of end encapsulants include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and from the standpoint of reactivity and film stability, monoalcohols, phenols, and monoamines are more preferable. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, and other phenolic compounds.Furthermore, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants. Furthermore, when sealing the amino groups at the ends of the resin, it is possible to seal them with compounds having functional groups that can react with the amino groups. Preferred sealing agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. Preferred carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic acid anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride. Furthermore, preferred carboxylic acid chloride compounds include acetyl chloride, acrylate chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantane carbonyl chloride, heptafluorobutyryl chloride, stearate chloride, and benzoyl chloride.

[0137] Furthermore, by using a compound having a structure that generates bases as a terminal encapsulant, it is possible to introduce a structure that generates bases at the terminals of a specific resin. As such end-capturing agents, for example, compounds can be used that have a structure exhibiting the property of generating a base and a reactive group such as a hydroxyl group, thiol group, amino group, carboxyl group, carboxylic acid anhydride group, carboxylic acid halide group, sulfonic acid anhydride group, sulfonic acid halide group, or sulfonic acid carboxylic acid anhydride group. As an end-capturing agent, for example, a compound having a structure that exhibits the property of generating one or more bases and one of the above-mentioned reactive groups can be used. The preferred embodiment of the structure exhibiting the property of generating bases is as described above.

[0138] Furthermore, a compound represented by formula (T-1) may be used as an end-capping agent. By encapsulating the ends with such a compound, a structure that readily generates bases at the ends can be introduced, which is thought to improve the elongation at break even when cured at low temperatures. [ka] In formula (T-1), L T Z is a divalent organic group. 1 and Z 2 Each of these independently represents an organic group, Z 1 and Z 2 They may be bonded together to form a ring structure.

[0139] In formula (T-1), L T It is preferably a hydrocarbon group, and may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group, but is preferably an aromatic hydrocarbon group, an unsaturated aliphatic hydrocarbon group, or a cyclic aliphatic hydrocarbon group. L T Linked chain length in (i.e., L T The minimum number of atoms connecting the two carbonyl groups bonded to each other is preferably 2 to 4, and more preferably 2. In formula (T-1), Z 1 and Z 2 This is Z in equation (3-1). 1 and Z 2 This is synonymous with the same as the preferred configuration. In particular, Z 1 , Z 2 and L T An embodiment in which at least one of the members has a polymerizable group is also one of the preferred embodiments of the present invention. Examples of polymerizable groups include radical polymerizable groups, epoxy groups, oxetanyl groups, methylol groups, and alkoxymethyl groups, with radical polymerizable groups being preferred. Preferred radical polymerizable groups are those having an ethylenically unsaturated group, such as (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, maleimide group, styryl group, vinyl group, and (meth)allyl group. Among these, the (meth)acryloxy group is preferred from the viewpoint of reactivity. These polymerizable groups may be directly bonded to the nitrogen atom in formula (T-1), or they may be bonded via linking groups such as hydrocarbon groups (e.g., alkylene groups).

[0140] -Solid precipitation- The method for producing polyimide precursors may include a step for precipitating a solid. Specifically, after filtering out the water-absorbing by-products of the dehydrating condensation agent present in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid, which is then dried to obtain the polyimide precursor. To improve the degree of purity, the polyimide precursor may be repeatedly redissolved, reprecipitation, and dried. Furthermore, the method may include a step for removing ionic impurities using an ion exchange resin.

[0141] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one specific resin or may contain two or more specific resins. When it contains two or more specific resins, it is preferable that the total amount is within the above range.

[0142] Furthermore, the resin composition of the present invention preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described later, or it may contain two or more specific resins, but it is preferable to contain two or more specific resins. When the resin composition of the present invention contains two or more specific resins, for example, a polyimide precursor with a structure derived from a dianhydride (R in formula (2) above). 115 Preferably, the polyimide precursor contains two or more different types of polyimide precursors.

[0143] <Other resins> The resin composition of the present invention may contain, in addition to or in place of the specified resin described above, another resin different from the specified resin (hereinafter also simply referred to as "other resin"). Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding (meth)acrylic resin, a resin composition with excellent coatability can be obtained, as well as a pattern (cured product) with excellent solvent resistance. For example, instead of the polymerizable compounds described later, or in addition to the polymerizable compounds described later, a polymerizable compound with a high polymerizable value of 20,000 or less weight-average molecular weight (for example, the molar amount of polymerizable groups in 1g of resin is 1 × 10⁻⁶) -3 By adding (meth)acrylic resin (in a quantity of mol / g or more) to the resin composition, the coatability of the resin composition, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0144] If the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. Furthermore, in a preferred embodiment of the resin composition of the present invention, the content of other resins may be low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the above content is not particularly limited and may be 0% by mass or more. The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0145] <Specific Metal Complexes> The resin composition of the present invention contains a specific metal complex.

[0146] The specific metal complex (first specific metal complex) contained in the resin composition according to the first aspect of the present invention has one or more π-conjugated moieties containing a nitrogen atom.

[0147] [Metal atom] The type of metal atom included in the specific metal complex is not particularly limited, but Group 4 metal atoms are preferred, titanium atoms, zirconium atoms, or hafnium atoms are more preferred, and titanium atoms are even more preferred from the viewpoint of storage stability. This is presumably because titanium atoms have a small atomic radius, which improves the stability of the compound. The number of metal atoms contained in the specific metal complex is not particularly limited, but it should be 1 or more, more preferably 1 to 4, even more preferably 1 or 2, and particularly preferably 1. Furthermore, if the specific metal complex contains two or more of the above-mentioned metal atoms, the types of the metal atoms may be the same or different. For example, if the specific metal complex contains two of the above-mentioned metal atoms, it may contain two titanium atoms, or it may contain a titanium atom and a zirconium atom.

[0148] [π-conjugated site containing a nitrogen atom] The first specific metal complex has a π-conjugated moiety containing a nitrogen atom. Here, it is preferable that the nitrogen atom is directly bonded to the metal atom in the first specific metal complex. The bond is not particularly limited, but it is preferably a coordinate bond. Furthermore, the π-conjugated moiety may have only one nitrogen atom or two or more. If it has two or more nitrogen atoms, it is preferable that one of them is directly bonded to a metal atom in the first specific metal complex. Here, the first specific metal complex may have only one π-conjugated site containing the nitrogen atom, or it may have two or more, but it is preferable to have one or two.

[0149] The π-conjugated moiety containing the nitrogen atom preferably has a structure represented by the following formula (1-1). [ka] In formula (1-1), X 1 ~X 3 Each of these independently represents -C(-*)= or -N=, where * represents a bonding site with another structure, and # represents a bonding site with a metal atom.

[0150] In formula (1-1), X 1 ~X 3 Each of these independently represents -C(-*)= or -N=, preferably at least one represents -C(-*)=, and more preferably at least two represent -C(-*)=.

[0151] In formula (1-1), the structures bonded to at least two *s may bond to form a ring structure. The ring structure may be an aliphatic ring structure or an aromatic ring structure, but an aromatic ring structure is preferred. Examples of embodiments that form such a ring structure include those represented by the following formulas (1-2) or (1-3). [ka] In formula (1-2), X 1 ~X 5 Each of these independently represents -C(-*)= or -N=, and # represents the bonding site with the metal atom. In formula (1-2), X 1 ~X 5 Preferably, at least one of them is -C(-*)=, more preferably at least three are -C(-*)=, and even more preferably at least four are -C(-*)=. Furthermore, an embodiment in which all are -C(-*)= is also one of the preferred embodiments of the present invention. In formula (1-3), X 1 ~X 7 Each of these independently represents -C(-*)= or -N=, and # represents the bonding site with the metal atom. In formula (1-3), X 1 ~X 7 Preferably, at least one of them is -C(-*)=, more preferably at least five are -C(-*)=, and even more preferably at least six are -C(-*)=. Furthermore, an embodiment in which all are -C(-*)= is also one of the preferred embodiments of the present invention.

[0152] Furthermore, the structure containing the substructure represented by formula (1-1) and the metal atom are bonded to parts other than those marked with # above, and the bonding sites of the above bond in the substructure are * 1 -O-* 2 , * 1 -S-* 2 or * 1 -C(=O)O-* 2 It is preferable that this be the case. * 1This is a bonding site with other structures, * 2 This is the bonding site with the metal atom. Furthermore, it is preferable that the structure including the substructure represented by formula (1-1) has one or two bonding sites with metal atoms in a part different from the # mentioned above. In this embodiment, the structure including the substructure represented by formula (1-1) may also preferably include structures represented by, for example, formulas (1-4), (1-5), or (1-6) below. [ka]

[0153] In formula (1-4), X 1 and X 2 Each of these independently represents -C(-*)= or -N=, * represents a bonding site with other structures, # represents a bonding site with a metal atom, and * 1 The symbol represents a bonding site with a carbon atom in an oxygen atom, sulfur atom, or -C(=O)O-, and the above oxygen atom, sulfur atom, or -C(=O)O- directly bonds with the metal atom in the first specific metal complex. In formula (1-4), structures bonded to at least two *s may bond to form a ring structure. The formed ring structure may be an aliphatic ring structure or an aromatic ring structure, but it is preferably an aromatic ring structure, and more preferably a benzene ring structure. Furthermore, the formed ring structure is preferably a 6-membered ring structure. One example of this type is X in equation (1-4). 2 Since -C(-*)=, this X 2 One example is a structure in which the * in the middle and the * bonded to the carbon atom to which *1 in formula (1-4) is bonded form a ring structure. Specifically, this is the configuration represented by the following formula (1-4-2). [ka] In formula (1-4-2), X 1 , #, * and * 1 These are the X in equations (1-4), respectively. 1 , #, * and * 1This is synonymous with the same as the preferred configuration. In formula (1-4-2), Cy represents a ring structure, preferably an aromatic ring structure, and more preferably a benzene ring structure. Furthermore, Cy is preferably a 6-membered ring structure. In formula (1-5), X 1 , X 2 and X 8 Each of these independently represents -C(-*)= or -N=, * represents a bonding site with other structures, # represents a bonding site with a metal atom, and * 1 The symbol represents a bonding site with a carbon atom in an oxygen atom, sulfur atom, or -C(=O)O-, and the above oxygen atom, sulfur atom, or -C(=O)O- directly bonds with the metal atom in the first specific metal complex. In formula (1-5), structures bonded to at least two *s may bond to form a ring structure. The formed ring structure may be an aliphatic ring structure or an aromatic ring structure, but it is preferably an aromatic ring structure, and more preferably a benzene ring structure. Furthermore, the formed ring structure is preferably a 6-membered ring structure. One example of such an embodiment is X in equation (1-5). 2 Since -C(-*)=, this X 2 The asterisk (*) in the middle and the X in equation (1-5) 2 One example is a configuration in which the structure bonded to the * on the side closer to the * forms a ring structure. Specifically, this is the configuration represented by the following formula (1-5-2). [ka] In formula (1-5-2), X 1 , X 8 , #, * and * 1 These are the X values ​​in equations (1-5), respectively. 1 , X 8 , #, * and * 1 This is synonymous with the same as the preferred configuration. In formula (1-5-2), Cy represents a ring structure, preferably an aromatic ring structure, and more preferably a benzene ring structure. Furthermore, Cy is preferably a 6-membered ring structure. Also, in (1-5-2), X 8Since -C(-*)=, this X 8 One possible configuration is one in which the * in the middle and the structure bonded to the * in formula (1-5-2) form a ring structure. Similarly, X in equation (1-5) 8 Since -C(-*)=, this X 8 The * inside and the structure bonded to the * in formula (1-5) may form a ring structure. In formula (1-6), X 2 , X 3 and X 4 Each of these independently represents -C(-*)= or -N=, and L 1 represents a single bond or a divalent linking group, * represents a bonding site with another structure, # represents a bonding site with a metal atom, and * 1 The symbol represents a bonding site with a carbon atom in an oxygen atom, sulfur atom, or -C(=O)O-, and the above oxygen atom, sulfur atom, or -C(=O)O- directly bonds with the metal atom in the first specific metal complex. * 1 When it bonds with an oxygen atom or a sulfur atom, L 1 It is preferably a methylene group, * 1 When it bonds with the carbon atom in -C(=O)O-, L 1 It is preferable that the bond is a single bond. In formula (1-6), structures bonded to at least two *s may bond to form a ring structure. The formed ring structure may be an aliphatic ring structure or an aromatic ring structure, but it is preferably an aromatic ring structure, and more preferably a benzene ring structure. Furthermore, the formed ring structure is preferably a 6-membered ring structure.

[0154] A preferred example of a structure containing the substructure represented by equation (1-1) is R in equation (2-1) described later. 2 and R 3 This is similar to the preferred embodiment.

[0155] The first specific metal complex is preferably a compound having a π-conjugated site containing a nitrogen atom and at least one group selected from the group consisting of a hydroxyl group, a mercapto group, and a carboxyl group on the same ligand. Here, it is preferable that the hydroxyl group, mercapto group, and carboxyl group are bonded to the metal atom as -O-, -S-, or -C(=O)-.

[0156] The first specific metal complex preferably includes a substructure represented by the following formula (3-1) as a structure containing a π-conjugated moiety that includes the nitrogen atom. [ka] In formula (3-1), R 1 ~R 4 and R 18 Each of these independently consists of a hydrogen atom, alkyl group, alkoxy group, allyloxy group, acyl group, phenyl group, acyloxy group, ester group, halogen atom, nitro group, cyano group, and -NR. 101 R 102 , -SR 103 -SO2NR 104 R 105 ,-CONR 106 R 107 or -NR 108 COR 109 Represents R 101 and R 102 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R 101 and R 102 They may be bonded together to form a ring, R 103 ~R 109 Each of these independently represents an alkyl group or an aryl group, L 1 represents a group represented by the following formula (L-1) or formula (L-2), and X 1 and X 2 Each of these independently represents -O- or -S-, and # represents the bonding site with the metal atom. [ka] In equations (L-1) and (L-2), R 14 ~R 17 Each of these independently consists of a hydrogen atom, alkyl group, alkoxy group, allyloxy group, acyl group, phenyl group, acyloxy group, ester group, halogen atom, nitro group, cyano group, and -NR. 101 R102 , -SR 103 -SO2NR 104 R 105 ,-CONR 106 R 107 or -NR 108 COR 109 Represents R 101 and R 102 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R 101 and R 102 They may be bonded together to form a ring, R 103 ~R 109 Each of these independently represents an alkyl group or an aryl group, and * represents X in formula (3-1). 1 The # represents the bonding site with the nitrogen atom in equation (3-1).

[0157] In formula (3-1), R 1 ~R 4 and R 18 If any of them is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 4 carbon atoms is more preferred, and a methyl group is even more preferred. In formula (3-1), R 1 ~R 4 and R 18 If any of them is an alkoxy group, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 4 carbon atoms is more preferred, and an ethoxy group is even more preferred. In formula (3-1), R 1 ~R 4 and R 18 If either of these is an allyloxy group, the aryl group in the allyloxy group is preferably an aromatic hydrocarbon group, and more preferably a phenyl group. Furthermore, if the above aryl group is an aromatic heterocyclic group, the heteroatom in the above heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. In formula (3-1), R 1 ~R 4 and R 18If either of them is an acyl group, it is preferably -COR or -SO2R, and more preferably -COR. R represents a monovalent organic group. R is preferably an alkyl group or an aryl group, and these preferred embodiments are described below. 101 ~R 109 This is similar to the preferred embodiment of the alkyl group or aryl group in the above. In formula (3-1), R 1 ~R 4 and R 18 If either of them is an acyloxy group, it is preferably -OCOR or -OSO2R, and more preferably -OCOR. R represents a monovalent organic group. Preferred embodiments of R are as described above. In formula (3-1), R 1 ~R 4 and R 18 If any of the groups is an ester group, it is preferably -COOR, -OCOR, -SO2OR, or -OSO2R, and more preferably -COOR. R represents a monovalent organic group. Preferred embodiments of R are as described above. In formula (3-1), R 1 ~R 4 and R 18 If any of these atoms is a halogen atom, it is preferably a fluorine atom, a chlorine atom, a bromine atom, or an elemental atom, and is preferably a fluorine atom or a chlorine atom. R 101 ~R 109 The number of carbon atoms in the alkyl group represented by is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1 or 2. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferred, and linear is more preferred. The alkyl group may have substituents insofar as the effects of the present invention are obtained. 101 ~R 109 The alkyl group represented is preferably a methyl group or an ethyl group. R 101 ~R 109The number of carbon atoms in the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have substituents insofar as the effects of the present invention are obtained. R 101 and R 102 They may be bonded together to form a ring. 101 and R 102 Examples of rings formed by the bonding of these molecules include pyrrolidine rings, piperidine rings, piperazine rings, and morpholine rings. R 101 and R 102 Each of these is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom, a methyl group, or an ethyl group. 103 ~R 114 Each of these is preferably an alkyl group, and more preferably a methyl group or an ethyl group.

[0158] In formula (3-1), from the viewpoint of the solubility of the specific metal complex in the solvent and the promotion of cyclization of the precursor of the cyclized resin when decomposed, L 1 It is preferable that represents the group represented by formula (L-2). Furthermore, in formula (3-1), from the viewpoint of the stability of the specific metal complex itself, L 1 It is preferable that represents the group represented by formula (L-1). In equations (L-1) and (L-2), R 14 ~R 17 Alkyl groups, alkoxy groups, allyloxy groups, acyl groups, acyloxy groups, ester groups, halogen atoms, and R 101 ~R 109 A preferred embodiment is R in formula (3-1). 1 ~R 4 and R 18 This is similar to the preferred embodiments of these bases in [the relevant context].

[0159] R in equation (3-1) 1 ~R 4 and R 18 , and R in formula (L-1) or formula (L-2) 14 ~R 17At least two of them may be bonded together to form a ring structure. In particular, R in formula (3-1) 1 ~R 4 and R 18 , and R in formula (L-1) or formula (L-2) 14 ~R 17 Two adjacent elements may join together to form a ring structure.

[0160] In formula (3-1), X 1 and X 2 Each of these independently represents -O- or -S-, with -O- being preferred.

[0161] From the viewpoint of achieving both solubility and storage stability of specific metal complexes, the above L 1 The group is represented by formula (L-2), and the above R 18 is a hydrogen atom, and the above R 1 , R 2 , R 3 , R 4 , R 14 , R 15 , R 16 , R 17 At least one of these is a methyl group, alkoxy group, allyloxy group, phenyl group, acyloxy group, acyl group, ester group, halogen atom, nitro group, cyano group, -NR 101 R 102 , -SR 103 -SO2NR 104 R 105 ,-CONR 106 R 107 or -NR 108 COR 109 Represents R 101 and R 102 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R 101 and R 102 They may be bonded together to form a ring, R 103 ~R 109 In which each of these independently represents an alkyl group or an aryl group, this is also one of the preferred embodiments of the present invention.

[0162] L in equation (3-1) 1If the group is represented by formula (L-1), then from the viewpoint of improving solubility in the composition of a specific metal complex, R in formula (3-1) 1 ~R 4 and R 18 Also, R in equation (L-1) 14 ~R 17 Preferably, at least one of these substituents is a substituent other than a hydrogen atom. The substituents are alkyl groups, aryl groups, -NR 101 R 102 alkoxy group, allyloxy group, -SR 103 , -COOR, -OCOR, -SO2R, -SO2NR 104 R 105 -SO2OR, -CONR 106 R 107 or -NR 108 COR 109 Preferably, it is an alkyl group, an aryl group, -NR 101 R 102 alkoxy group, allyloxy group, -SR 103 It is even more preferable that it be -COOR or -OCOR. However, R 101 and R 102 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R 101 and R 102 They may be bonded together to form a ring, R 103 ~R 109 Each of these independently represents an alkyl group or an aryl group, and in formula (3-1) R 1 ~R 4 and R in equation (L-1) 14 ~R 17 Two of these adjacent elements may be joined together to form a ring.

[0163] L in equation (3-1) 1 If the group is represented by formula (L-2), then from the viewpoint of improving the storage stability of the metal complex, R in formula (3-1) 1 ~R 4 and R 18 Also, R in equation (L-2) 14 ~R 17 Preferably, at least one of them is a substituent other than a hydrogen atom. Improving the storage stability of metal complexes can be divided into two categories: inhibiting ligand liberation and inhibiting ligand hydrolysis. Each of these can be independently inhibited by introducing substituents. To suppress ligand release, sterically bulky substituents are effective, and in formula (3-1) R 1 and R 4 Also, R in equation (L-2) 14 ~R 17 Preferably, at least one of the substituents is a hydrogen atom. The substituents are alkyl groups, aryl groups, -NR 101 R 102 alkoxy group, allyloxy group, -SR 103 , -COOR, -OCOR, -SO2R, -SO2NR 104 R 105 -SO2OR, -CONR 106 R 107 or -NR 108 COR 109 Preferably, it is an alkyl group, an aryl group, -NR 101 R 102 alkoxy group, allyloxy group, -SR 103 It is even more preferable that the group be -COOR or -OCOR. Preferred embodiments of these groups are as described above. Stereolithic substituents or electron-withdrawing groups are effective in inhibiting the hydrolysis of ligands. From the perspective of a sterically bulky substituent, R in formula (3-1) 1 and R 4 Also, R in equation (L-2) 14 ~R 17 Preferably, at least one of the substituents is a substituent other than hydrogen. The substituents are alkyl groups, aryl groups, -NR 101 R 102 alkoxy group, allyloxy group, -SR 103 , -COOR, -OCOR, -SO2R, -SO2NR 104 R 105 -SO2OR, -CONR 106 R 107 or -NR 108 COR 109 Preferably, it is an alkyl group, an aryl group, -NR101 R 102 alkoxy group, allyloxy group, -SR 103 It is even more preferable that the group be -COOR or -OCOR. Preferred embodiments of these groups are as described above. From the perspective of electron-withdrawing groups, R in formula (3-1) 1 ~R 4 and R 18 It is preferable that at least one of these groups is an electron-withdrawing group. It is even more preferable that the electron-withdrawing group is a halogen, a nitro group, an aryl group, or an ester group.

[0164] The first specific metal complex preferably includes a substructure represented by the following formula (4-1) as a structure containing a π-conjugated moiety that includes the nitrogen atom. [ka] In formula (4-1), R 1 ~R 7 Each of these independently consists of a hydrogen atom, alkyl group, alkoxy group, allyloxy group, acyl group, phenyl group, acyloxy group, ester group, halogen atom, nitro group, cyano group, and -NR. 101 R 102 , -SR 103 -SO2NR 104 R 105 ,-CONR 106 R 107 or -NR 108 COR 109 Represents R 101 and R 102 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R 101 and R 102 They may be bonded together to form a ring, R 103 ~R 109 Each of these independently represents an alkyl group or an aryl group, and X 1 and X 2 Each of these independently represents -O- or -S-, and # represents the bonding site with the metal atom.

[0165] In formula (4-1), R 1 ~R7 Alkyl groups, alkoxy groups, allyloxy groups, acyl groups, acyloxy groups, ester groups, halogen atoms, and R 101 ~R 109 A preferred embodiment is R in formula (3-1). 1 ~R 4 and R 18 This is similar to the preferred embodiments of these bases in [the relevant context].

[0166] In formula (4-1), from the viewpoint of improving the storage stability of the first specific metal complex, R 1 , R 2 , R 6 and R 7 Preferably, at least one of these substituents is a substituent other than a hydrogen atom. The substituents are alkyl groups, aryl groups, -NR 101 R 102 alkoxy group, allyloxy group, -SR 103 , -COOR, -OCOR, -SO2R, -SO2NR 104 R 105 -SO2OR, -CONR 106 R 107 or -NR 108 COR 109+ It is preferable that the group is an alkyl group or an aryl group, and more preferably an alkyl group or an aryl group. Preferred embodiments of these groups are as described above. Furthermore, from the perspective of improving the solubility of the first specific metal complex, R 1 , R 2 , R 6 and R 7 Preferably, at least one of them is a substituent other than a hydrogen atom.

[0167] The first specific metal complex may further have other structures distinct from the π-conjugated moiety containing the nitrogen atom. Other structures are not particularly limited and include structures consisting of known ligands. Examples of such ligands include monodentate alkoxide ligands, monodentate aryl oxide ligands, polydentate aryl oxide ligands, and cyclopentadienyl ligands, and these ligands may further have substituents. From the viewpoint of the stability of the first specific metal complex, substituted or unsubstituted cyclopentadienyl ligands are preferred.

[0168] The second specific metal complex is the compound represented by the following formula (2-1). The first specific metal complex is preferably a compound represented by the following formula (2-1). [ka] In equation (2-1), M is titanium, zirconium, or hafnium, l1 is an integer between 0 and 2, l2 is 0 or 1, l1 + l2 × 2 is an integer between 0 and 2, m is an integer between 0 and 4, n is an integer between 0 and 2, l1 + l2 + m + n × 2 = 4, R 11 Each of these is independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group, R 12 R is a substituted or unsubstituted hydrocarbon group, 2 Each of these is an independent group containing a structure represented by the following formula (2-2), and R 3 Each of these is an independent group containing a structure represented by the following formula (2-2), and X A Each of these is independently either an oxygen atom or a sulfur atom. [ka] In formula (2-2), X 1 ~X 3 Each of these independently represents -C(-*)= or -N=, where * represents a bonding site with another structure, and # represents a bonding site with a metal atom.

[0169] In formula (2-1), from the viewpoint of storage stability of the composition, M is preferably titanium. In equation (2-1), the embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention. In formula (2-1), m is preferably 2 or 4, and more preferably 2. In formula (2-1), n ​​is preferably 1 or 2, and more preferably 1. Here, it is also preferable that l1 and l2 are 0 in equation (2-1) and m is 0, 2, or 4.

[0170] In equation (2-1), from the viewpoint of the stability of the specific metal complex, R 11 A substituted or unsubstituted cyclopentadienyl ligand is preferred. Also, R 11 The cyclopentadienyl group, alkoxy group, and phenoxy group in the compound may be substituted, but an unsubstituted configuration is also a preferred embodiment of the present invention.

[0171] In formula (2-1), R 12 It is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. R 12 The hydrocarbon group in this compound may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred. As for the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferred, an aromatic hydrocarbon group having 6 to 10 carbon atoms is more preferred, and a phenylene group is even more preferred. R 12 The substituents in are preferably monovalent substituents, such as halogen atoms. 12 If the group is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. Among these, in equation (2-1), R 12 It is preferable that R is an unsubstituted phenylene group. 12 The phenylene group in this is preferably a 1,2-phenylene group.

[0172] In formula (2-1), R 2 and R 3 A preferred embodiment of the structure represented by formula (2-2) is the same as a preferred embodiment of formula (1-1) described above. R in the compound represented by formula (2-1) 3 and X A The structure formed by this can also preferably be represented by the above formula (3-1). In this case, X in formula (3-1) 1 and X 2 These are the X in equation (2-1) A This corresponds to X in equation (3-1). 1 and X 2 Structures other than R in equation (2-1) 3 This applies. R in the compound represented by formula (2-1) 3 and X A The structure formed by this can also preferably be represented by the above formula (4-1). In this case, X in formula (3-1) 1 and X 2 These are the X in equation (2-1) A This corresponds to X in equation (4-1). 1 and X 2 Structures other than R in equation (2-1) 3 This applies. In equation (2-1), m is 2 or greater, and R 2 If there are 2 or more of them, then 2 or more of those R 2 The structures of each may be the same or different. In equation (2-1), n ​​is 2 or greater, and R 3 If there are 2 or more of them, then 2 or more of those R 3 The structures of each may be the same or different.

[0173] R in equation (2-1) 2 Specific examples are given below, but this is not an exhaustive list. In the structure below, * represents X in equation (2-1). A The # represents the bonding site with M in equation (2-1). [ka]

[0174] R in equation (2-1) 3 Specific examples are given below, but this is not an exhaustive list. In the structure below, * represents X in equation (2-1). A The # represents the bonding site with M in formula (2-1). In this specification, Me represents a methyl group, Et represents an ethyl group, and n-Bu represents an n-butyl group. [ka] JPEG0007884058000049.jpg156162

[0175] Furthermore, the compound represented by formula (2-1) is also preferably the compound represented by the following formula (5-1). [ka]

[0176] In formula (2-1), M is titanium, zirconium, or hafnium, and R a1 ~R a4 and R a18 Each of these independently consists of a hydrogen atom, alkyl group, alkoxy group, allyloxy group, acyl group, phenyl group, acyloxy group, ester group, halogen atom, nitro group, cyano group, and -NR. 101 R 102 , -SR 103 -SO2NR 104 R 105 ,-CONR 106 R 107 or -NR 108 COR 109 Represents R 101 and R 102 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R 101 and R 102 They may be bonded together to form a ring, R 103 ~R 109Each of these independently represents an alkyl group or an aryl group, L a1 represents the group represented by the above formula (L-1) or formula (L-2), and X a1 and X a2 Each of these independently represents -O- or -S-, and R b1 ~R b7 Each of these independently consists of a hydrogen atom, alkyl group, alkoxy group, allyloxy group, acyl group, phenyl group, acyloxy group, ester group, halogen atom, nitro group, cyano group, and -NR. 101 R 102 , -SR 103 -SO2NR 104 R 105 ,-CONR 106 R 107 or -NR 108 COR 109 Represents R 101 and R 102 Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R 101 and R 102 They may be bonded together to form a ring, R 103 ~R 109 Each of these independently represents an alkyl group or an aryl group, and X b1 and X b2 Each of these independently represents either -O- or -S-, where a represents an integer between 0 and 2, b represents an integer between 0 and 2, and the sum of a and b is 2.

[0177] In formula (5-1), from the viewpoint of storage stability of the composition, M is preferably titanium. In formula (5-1), from the viewpoint of storage stability of the composition, R a1 ~R a4 , R a18 , L 1a , X 1a , X 2a These are R in equation (3-1), respectively. 1 ~R 4 , R 18 , L 1 , X 1 , X 2 This is synonymous with the same as the preferred configuration. In formula (5-1), from the viewpoint of storage stability of the composition, Rb1 ~R b7 , X 1b , X 2b These are R in equation (4-1), respectively. 1 ~R 7 , X 1 , X 2 This is synonymous with the same as the preferred configuration. In formula (5-1), by setting a to 1 or 2, the solubility of the specific metal complex in the solvent and the cyclization of the precursor of the cyclized resin when it decomposes can be promoted. In formula (5-1), the solubility of a specific metal complex can be improved by setting b to 1 or 2. In equation (5-1), when a is 2, R in the two ligands a1 ~R a4 , R a18 , L 1a , X 1a , X 2a These may be the same or different. In equation (5-1), when b is 2, R in the two ligands b1 ~R b7 , X 1b , X 2b These may be the same or different.

[0178] Furthermore, from the viewpoint of the stability of the specific metal complex, an embodiment in which the specific metal complex does not have monodentate ligands other than cyclopentadienyl is also a preferred embodiment of the present invention.

[0179] The specific metal complex preferably generates an amine when heated to 250°C. The above temperature is preferably 230°C, more preferably 200°C, and even more preferably 180°C. In the present invention, a specific metal complex is defined as generating amine at X°C if, when a solution is prepared by dissolving a specific metal complex in the same concentration as the resin composition of the present invention and in the same solvent as the resin composition of the present invention, and this solution is heated at X°C, an amount of amine of 10 mol% or more relative to the total molar amount of the specific metal complex is generated. Furthermore, from the viewpoint of the elongation at break of the resulting cured product, the pKa of the conjugate acid of the amine is preferably 3 or higher, and more preferably 6 or higher. There is no particular upper limit to the pKa of the conjugate acid, but it is preferably 30 or lower. Furthermore, from the viewpoint of storage stability, the pKa of the conjugate acid of the specific metal complex itself is preferably less than 3, preferably -5 or less, and more preferably -10 or less. pKa is the negative common logarithm of the equilibrium constant Ka, expressed as pKa, when considering a dissociation reaction in which hydrogen ions are released from an acid. In this specification, unless otherwise specified, pKa values ​​are calculated using ACD / ChemSketch®. If there are multiple pKa values ​​for the above-mentioned conjugate acids, it is preferable that at least one of them falls within the above range.

[0180] The dissolution parameter of a specific metal complex is preferably such that its SP (dissolution parameter) value is 9 or higher, and more preferably 10 or higher. The upper limit of the above SP value is not particularly limited; for example, it may be 30 or lower. In this specification, SP values ​​are determined by the Hoy method unless otherwise specified (HL.Hoy Journal of Painting, 1970, Vol.42, 76-118). Furthermore, although the units are omitted for SP values, the unit is cal. 1 / 2 cm -3 / 2 That is the case.

[0181] [Molecular weight] The molecular weight of the specific metal complex is preferably 200 to 2,000, more preferably 250 to 1,500, and even more preferably 300 to 1,000.

[0182] [Synthesis method] Specific metal complexes can be synthesized, for example, by reacting titanium alkoxide with a compound having an alkoxy group and a carboxyl group. Alternatively, they may be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.

[0183] Specific examples of specific metal complexes include, but are not limited to, A-1 to A-73 used in the examples.

[0184] The content of the specific metal complex relative to the total solid content of the resin composition of the present invention is preferably 0.05 to 20% by mass. The lower limit is more preferably 0.10% by mass or more, even more preferably 0.2% by mass or more, particularly preferably 0.5% by mass or more, and most preferably 1% by mass or more. The upper limit is more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less. The content of the specific metal complex per 100 parts by mass of the specific resin is preferably 0.05 to 20% by mass. The lower limit is more preferably 0.10% by mass or more, even more preferably 0.2% by mass or more, particularly preferably 0.5% by mass or more, and most preferably 1% by mass or more. The upper limit is more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less. A single specific metal complex may be used alone, or two or more may be used in combination. When two or more are used in combination, it is preferable that their total amount falls within the above range. Furthermore, the total amount of the colored specific metal complex and the colored organometallic complex described later, relative to the total solid content of the composition of the present invention, may be determined according to its application, but is preferably greater than 0% by mass and 30% by mass or less. The upper limit is more preferably 15% by mass or less, and even more preferably 10% by mass or less. In the present invention, "colored" means that the molar extinction coefficient at a wavelength of 400 to 800 nm is 10,000 L·mol -1 ·cm -1 This means that the above is true. The above molar extinction coefficient is 15,000 L·mol -1 ·cm -1 It is preferable that the above conditions are met.

[0185] <Organometallic complexes> The resin composition of the present invention may contain organometallic complexes from the viewpoint of chemical resistance. The term "organometallic complex" as used herein does not include compounds that fall under the category of the specific metal complexes mentioned above. An organometallic complex can be any organic complex containing a metal atom, but it is preferably a complex compound containing both a metal atom and an organic group, more preferably a compound in which the organic group is coordinated to the metal atom, and even more preferably a metallocene compound. In the present invention, a metallocene compound refers to an organometallic complex having two cyclic pentadienyl anion derivatives, which may have substituents, as η5-ligands. The above organic group is not particularly limited, but a hydrocarbon group or a group consisting of a hydrocarbon group and a heteroatom is preferred. The heteroatom is preferably an oxygen atom, a sulfur atom, or a nitrogen atom. In the present invention, it is preferable that at least one of the organic groups is a cyclic group, and more preferably that at least two are cyclic groups. The above-mentioned cyclic group is preferably selected from a 5-membered ring cyclic group and a 6-membered ring cyclic group, and more preferably a 5-membered ring cyclic group. The above cyclic group may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferred. A cyclopentadienyl group is preferred as the cyclic group of the 5-membered ring. Furthermore, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

[0186] The metal included in the organometallic complex is not particularly limited, but it is preferably a metal belonging to Group 4 elements, more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium, even more preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

[0187] Organometallic complexes may contain two or more metal atoms, or only one metal atom, but it is preferable 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 two or more types of metal atoms.

[0188] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound, or a hafnocene compound; more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound; even more preferably a titanocene compound or a zirconocene compound; and particularly preferably a titanocene compound.

[0189] An embodiment in which the organometallic complex has the ability to initiate photoradical polymerization is also one of the preferred embodiments of the present invention. In the present invention, having photo-radical polymerization initiation ability means being able to generate free radicals that can initiate radical polymerization upon irradiation with light. For example, the presence or absence of photo-radical polymerization initiation ability can be confirmed by irradiating a composition containing a radical crosslinking agent and an organometallic complex with light in a wavelength range in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light, and then checking whether or not the radical crosslinking agent disappears. An appropriate method can be selected depending on the type of radical crosslinking agent to check whether or not it disappears, but for example, it can be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high-performance liquid chromatography). When the organometallic complex has photoradical polymerization initiation ability, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, even more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound. If the organometallic complex does not have photoradical polymerization initiation ability, the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds and hafnocene compounds, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds and hafnocene compounds, even more preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds, and particularly preferably a titanocene compound.

[0190] The molecular weight of the organometallic complex is preferably 50 to 2,000, and more preferably 100 to 1,000.

[0191] Preferred organometallic complexes include compounds represented by the following formula (P). [ka] In formula (P), M is a metal atom, and R is a substituent, independently of each other. Preferably, each of the above R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

[0192] In formula (P), the metal atom represented by M is preferably an iron atom, a titanium atom, a zirconium atom, or a hafnium atom; more preferably a titanium atom, a zirconium atom, or a hafnium atom; even more preferably a titanium atom or a zirconium atom; and particularly preferably a titanium atom. Examples of aromatic groups in formula (P) include aromatic groups having 6 to 20 carbon atoms, with aromatic hydrocarbon groups having 6 to 20 carbon atoms being preferred, such as phenyl groups, 1-naphthyl groups, or 2-naphthyl groups. The alkyl group in R in formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples include methyl group, ethyl group, propyl group, octyl group, isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, etc. Examples of halogen atoms in R include F, Cl, Br, and I. The alkyl group constituting the alkylsulfonyloxy group in R above is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples include methyl group, ethyl group, propyl group, octyl group, isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, etc. The above R may have further substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, and diarylamino groups.

[0193] Specific examples of organometallic complexes, though not limited to them, include tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds. [ka]

[0194] Other compounds described in paragraphs 0078-0088 of International Publication No. 2018 / 025738 may also be used, but are not limited to these.

[0195] The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is more preferably 25% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. One or more organometallic complexes can be used. When using two or more, it is preferable that the total amount is within the above range.

[0196] <Polymerizable compound> The resin composition of the present invention preferably contains a polymerizable compound. Polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0197] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. Radical crosslinking agents are compounds having radical polymerizable groups. Preferred radical polymerizable groups are those containing ethylenically unsaturated bonds. Examples of such groups include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, maleimide groups, and (meth)acrylamide groups. Among these, the (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred as groups containing the ethylenically unsaturated bond, and the (meth)acryloyl group is more preferred from the viewpoint of reactivity.

[0198] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compounds having two or more ethylenically unsaturated bonds, compounds having 2 to 15 ethylenically unsaturated bonds are preferred, compounds having 2 to 10 ethylenically unsaturated bonds are more preferred, and compounds having 2 to 6 ethylenically unsaturated bonds are even more preferred. Furthermore, from the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-mentioned ethylenically unsaturated bonds.

[0199] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0200] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids with polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0201] Furthermore, radical crosslinking agents that have a boiling point of 100°C or higher under normal pressure are also preferred. Examples of compounds with a boiling point of 100°C or higher under normal pressure include those described in paragraph 0203 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0202] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204-0208 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0203] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0204] Examples of commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethylene oxy chains, manufactured by Sartomer; SR-209, 231, and 239, difunctional methacrylates with four ethylene oxy chains, also manufactured by Sartomer; DPCA-60, a hexafunctional acrylate with six pentylene oxy chains, manufactured by Nippon Kayaku Co., Ltd.; TPA-330, a trifunctional acrylate with three isobutylene oxy chains; and urethane. Examples include oligomers UAS-10 and UAB-140 (manufactured by Nippon Paper Industries), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0205] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Furthermore, compounds having an amino structure or a sulfide structure in the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0206] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0207] The preferred acid value of the radical crosslinking agent having an acid group is 0.1 to 300 mg KOH / g, and particularly preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing, as well as excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0208] Furthermore, as a radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") is also preferred. In this invention, the urea bond is defined as *-NR N -C(=O)-NR N -* is a combination represented by R N Each of the symbols independently represents a hydrogen atom or a monovalent organic group, and each of the symbols represents a bonding site with a carbon atom. In this invention, urethane bonding is defined as *-OC(=O)-NR N -* is a combination represented by R N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. The inclusion of crosslinking agent U in the resin composition may improve chemical resistance, resolution, and other properties. The mechanism by which the above effects are obtained is unknown, but for example, it is thought that when curing by heating, a portion of the crosslinking agent U decomposes thermally, generating amines, etc., and these amines, etc., promote the cyclization of precursors of cyclized resins such as polyimide precursors. The crosslinking agent U may have only one urea bond or one urethane bond, or it may have one or more urea bonds and one or more urethane bonds, or it may have two or more urea bonds without any urethane bonds, or it may have two or more urethane bonds without any urea bonds. The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. Furthermore, if the crosslinking agent U does not have urethane bonds, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. Furthermore, if the crosslinking agent U does not have urea bonds, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0209] The radical polymerizable group in the crosslinking agent U is not particularly limited, but examples include vinyl group, allyl group, (meth)acryloyl group, (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, maleimide group, etc. (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, or maleimide group are preferred, and (meth)acryloxy group is more preferred. If the crosslinking agent U has two or more radical polymerizable groups, the structures of each radical polymerizable group may be the same or different. The number of radical polymerizable groups in the crosslinking agent U may be only one, or two or more, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. The radical polymerizability value (mass of compound per mole of radical polymerizable groups) of the crosslinking agent U is preferably 150 to 400 g / mol. The lower limit of the radical polymerization value is more preferably 200 g / mol or more, even more preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, particularly preferably 240 g / mol or more, and most preferably 250 g / mol or more. The upper limit of the above-mentioned radical polymerization value is more preferably 350 g / mol or less, even more preferably 330 g / mol or less, and particularly preferably 300 g / mol or less. When the radical polymerization value is above the lower limit, the chemical resistance of the cured product tends to be good, and when it is below the upper limit, the developability tends to be good. In particular, the polymerizability value of the crosslinking agent U is preferably 210 to 400 g / mol, and more preferably 220 to 400 g / mol.

[0210] The crosslinking agent U is preferably a structure represented by the following formula (U-1). [ka] In formula (U-1), R U1 A is a hydrogen atom or a monovalent organic group, and A is -O- or -NR N - and R N is a hydrogen atom or a monovalent organic group, Z U1 is an m-valent organic group, Z U2 is an n+1 valent organic group, X is a radical polymerizable group, n is an integer greater than or equal to 1, and m is an integer greater than or equal to 1.

[0211] In formula (U-1), R U1 The group is preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group, with a hydrogen atom being more preferred. In formula (U-1), R N The group is preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group, with a hydrogen atom being more preferred. In formula (U-1), Z U1 These are hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O)2-, -NRN -, or a group in which two or more of these are bonded together is preferred, and is a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O)2-, and -NR N -A group bonded to at least one group selected from the group consisting of - is more preferable. The hydrocarbon group described above is preferably a hydrocarbon group having 20 or fewer carbon atoms, more preferably a hydrocarbon group having 18 or fewer carbon atoms, and even more preferably a hydrocarbon group having 16 or fewer carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by combinations of these. N represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group. In formula (U-1), Z U2 These are hydrocarbon groups, -O-, -C(=O)-, -S-, -S(=O)2-, -NR N -, or a group in which two or more of these are bonded together is preferred, and is a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O)2-, and -NR N -A group bonded to at least one group selected from the group consisting of - is more preferable. The hydrocarbon group described above is preferably a hydrocarbon group having 20 or fewer carbon atoms, more preferably a hydrocarbon group having 18 or fewer carbon atoms, and even more preferably a hydrocarbon group having 16 or fewer carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by combinations of these. In formula (U-1), X is not particularly limited, but examples include vinyl group, allyl group, (meth)acryloyl group, (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, maleimide group, etc., with (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, or maleimide group being preferred, and (meth)acryloxy group being more preferred. In formula (U-1), n ​​is preferably an integer between 1 and 10, more preferably an integer between 1 and 4, even more preferably 1 or 2, and particularly preferably 1. In formula (U-1), m is preferably an integer between 1 and 10, more preferably an integer between 1 and 4, and even more preferably 1 or 2.

[0212] The crosslinking agent U may also preferably have at least one of a hydroxyl group, an alkylene oxy group, an amide group, and a cyano group. From the viewpoint of the chemical resistance of the resulting cured product, the hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group, but an alcoholic hydroxyl group is preferable. From the viewpoint of the chemical resistance of the resulting cured product, alkylene oxy groups having 2 to 20 carbon atoms are preferred, alkylene oxy groups having 2 to 10 carbon atoms are more preferred, alkylene oxy groups having 2 to 4 carbon atoms are even more preferred, ethylene groups or propylene groups are even more preferred, and ethylene groups are particularly preferred. The alkylene oxy group may be included in the crosslinking agent U as a polyalkylene oxy group. In this case, the number of repeating alkylene oxy groups is preferably 2 to 10, and more preferably 2 to 6. The amide group is -C(=O)-NR N This refers to a bond represented by -. N As stated above, if the crosslinking agent U has an amide group, the crosslinking agent U is, for example, RC(=O)-NR N -A group represented by -*, or *-C(=O)-NR N It can be included as a group represented by -R. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group. The crosslinking agent U may have two or more structures selected from the group consisting of a hydroxyl group, an alkylene oxy group (however, if it constitutes a polyalkylene oxy group, it shall be a polyalkylene oxy group), an amide group, and a cyano group within the molecule, but having only one such structure within the molecule is also one of the preferred embodiments of the present invention. The above-mentioned hydroxyl group, alkylene oxy group, amide group, and cyano group may be located at any position on the crosslinking agent U. However, from the viewpoint of chemical resistance, one preferred embodiment of the present invention is that the crosslinking agent U is linked to at least one radical polymerizable group selected from the group consisting of the above-mentioned hydroxyl group, alkylene oxy group, amide group, and cyano group by a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1"). In particular, when the crosslinking agent U contains only one radical polymerizable group, it is preferable that the radical polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxyl group, an alkylene oxy group, an amide group, and a cyano group are linked by a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2"). When the crosslinking agent U contains an alkylene oxy group (however, if it constitutes a polyalkylene oxy group, then a polyalkylene oxy group) and has the above-mentioned linking group L2-1 or linking group L2-2, the structure that bonds to the side of the alkylene oxy group (however, if it constitutes a polyalkylene oxy group, then a polyalkylene oxy group) opposite to linking group L2-1 or linking group L2-2 is not particularly limited, but a hydrocarbon group, a radical polymerizable group, or a group represented by a combination thereof is preferred. As the hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is even more preferred. As the hydrocarbon group, examples include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by a combination thereof. Furthermore, the preferred embodiment of the radical polymerizable group is the same as the preferred embodiment of the radical polymerizable group in the crosslinking agent U described above. When the crosslinking agent U contains an amide group and has the linking group L2-1 or L2-2, the structure bonded to the side of the amide group opposite to linking group L2-1 or L2-2 is not particularly limited, but a hydrocarbon group, a radical polymerizable group, or a group represented by a combination thereof is preferred. As the hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is even more preferred. As the hydrocarbon group, examples include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, or groups represented by a combination thereof. Furthermore, the preferred embodiment of the radical polymerizable group is the same as the preferred embodiment of the radical polymerizable group in the crosslinking agent U described above. In addition, in the above embodiment, the carbon atom side of the amide group may be bonded to linking group L2-1 or L2-2, or the nitrogen atom side of the amide group may be bonded to linking group L2-1 or L2-2. Among these, from the viewpoint of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that the crosslinking agent U has a hydroxyl group.

[0213] From the viewpoint of compatibility with specific resins, the crosslinking agent U preferably contains aromatic groups. The above aromatic group is preferably directly bonded to a urea bond or urethane bond contained in the crosslinking agent U. If the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or a structure in which these groups form a fused ring, but it is preferable that it be an aromatic hydrocarbon group. The above aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group obtained by removing two or more hydrogen atoms from a benzene ring structure. The above aromatic heterocyclic group is preferably an aromatic heterocyclic group with a 5-membered ring or a 6-membered ring. Examples of aromatic heterocyclic groups include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine. These rings may be further fused with other rings, such as indole and benzimidazole. Furthermore, the heteroatoms included in the above aromatic heterocyclic group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms. The above aromatic group is preferably included in a linking group that links two or more radical polymerizable groups and includes a urea bond or a urethane bond, or in a linking group that links at least one selected from the group consisting of the above-mentioned hydroxyl group, alkylene oxy group, amide group, and cyano group with at least one radical polymerizable group contained in the crosslinking agent U.

[0214] The number of atoms (chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10. If the crosslinking agent U contains a total of two or more urea bonds or urethane bonds, or two or more radical polymerizable groups, or if it contains two or more urea bonds or urethane bonds and two or more radical polymerizable groups, then the minimum number of atoms (chain length) between the urea bonds or urethane bonds and the radical polymerizable groups must be within the above range. In this specification, "number of atoms (chain length) between a urea bond or urethane bond and a polymerizable group" refers to the shortest (minimum number of atoms) linking atomic chains on the path connecting two atoms or groups of atoms to be linked. For example, in the structure represented by the following formula, the number of atoms (chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2. [ka]

[0215] [Axis of Symmetry] It is also preferable that the crosslinking agent U is a compound with a structure that does not have an axis of symmetry. The statement that crosslinking agent U lacks an axis of symmetry means that it does not possess an axis that, when the entire compound is rotated, produces a molecule identical to the original molecule, and is therefore an asymmetrical compound. Furthermore, when the structural formula of crosslinking agent U is written on paper, the statement that crosslinking agent U lacks an axis of symmetry means that the structural formula of crosslinking agent U cannot be written in a form that exhibits an axis of symmetry. It is believed that the lack of a symmetry axis in the crosslinking agent U suppresses aggregation of the crosslinking agents U within the composition film.

[0216] [Molecular weight] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, preferably 150 to 1,500, and more preferably 200 to 900.

[0217] The method for producing the crosslinking agent U is not particularly limited, but for example, it can be obtained by reacting a radical polymerizable compound with a compound having an isocyanate group with a compound having at least one of a hydroxyl group or an amino group.

[0218] Specific examples of crosslinking agent U are shown below, but crosslinking agent U is not limited to these examples. [ka] [ka] [ka]

[0219] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6- Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the molecular weight of the polyethylene glycol chain is approximately 200. From the viewpoint of suppressing warping associated with controlling the elastic modulus of the pattern (cured product), the resin composition of the present invention preferably uses a monofunctional radical crosslinking agent. Preferred monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate, as well as N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl glycidyl ether. As a monofunctional radical crosslinking agent, compounds with a boiling point of 100°C or higher under normal pressure are also preferred in order to suppress volatilization before exposure. Other examples of bifunctional or more radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0220] If a radical crosslinking agent is included, its content is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0221] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, it is preferable that their total amount be within the above range.

[0222] [Other crosslinking agents] The resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. In the present invention, other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to the photoacid generator or photobase generator described above, and are preferably compounds having multiple groups in their molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or a base. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or photobase generator during the exposure process. Other preferred crosslinking agents include compounds having at least one group selected from the group consisting of acyloxymethyl, methylol, ethylol, and alkoxymethyl groups, and more preferably compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl, methylol, ethylol, and alkoxymethyl groups is directly bonded to a nitrogen atom. Other crosslinking agents include, for example, compounds having a structure obtained by reacting an amino group-containing compound such as melamine, glycoluryl, urea, alkylene urea, or benzoguanamine with formaldehyde or a formaldehyde-alcohol, and substituting the hydrogen atoms of the amino group with an acyloxymethyl group, methylol group, ethylol group, or alkoxymethyl group. The method for producing these compounds is not particularly limited, and any compound having a structure similar to that of the compounds produced by the above method is acceptable. Furthermore, oligomers formed by the self-condensation of methylol groups of these compounds may also be used. As for the amino group-containing compounds mentioned above, crosslinking agents using melamine are called melamine-based crosslinking agents, crosslinking agents using glycoluryl, urea, or alkylene urea are called urea-based crosslinking agents, crosslinking agents using alkylene urea are called alkylene urea-based crosslinking agents, and crosslinking agents using benzoguanamine are called benzoguanamine-based crosslinking agents. Among these, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of glycoluryl-based crosslinking agents and melamine-based crosslinking agents, as described later.

[0223] Examples of compounds containing at least one alkoxymethyl group and acyloxymethyl group in the present invention include compounds in which the alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of the urea structure described below, or on a triazine. The alkoxymethyl group or acyloxymethyl group in the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above compound is preferably 1500 or less, and more preferably 180 to 1200.

[0224] [ka]

[0225] R 100 This represents an alkyl group or acyl group. R 101 and R 102 Each of these independently represents a monovalent organic group and may be bonded to each other to form a ring.

[0226] Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted for an aromatic group include compounds with the following general formula.

[0227] [ka]

[0228] In the formula, X represents a single bond or a divalent organic group, and each R 104 Each independently represents an alkyl group or an acyl group, R 103This includes hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, aralkyl groups, or groups that decompose upon the action of an acid to produce alkali-soluble groups (for example, groups that are eliminated by the action of an acid, -C(R 4 ) 2COOR 5 The group represented by (R 4 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 This represents a group that is removed by the action of an acid. )) indicates. R 105 Each independently represents an alkyl group or an 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. Groups that decompose under the action of acid to produce alkali-soluble groups, groups that are eliminated under the action of acid, -C(R 4 ) 2COOR 5 R in the group represented by 5 For example, -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 Examples include: In the formula, R 36 ~R 39 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 These elements may be joined together to form a ring. The alkyl group described above is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group described above may be linear or branched. The above cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms. The above cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a fused ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group. The above aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms. The above-mentioned aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as those described above for preferred embodiments of alkyl and aryl groups. The above alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Furthermore, these groups may have known substituents within the range that the effects of the present invention can be obtained.

[0229] R 01 and R 02 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0230] The groups that decompose upon the action of an acid to produce alkali-soluble groups, or the groups that are eliminated upon the action of an acid, are preferably tertiary alkyl ester groups, acetal groups, cumyl ester groups, enol ester groups, etc. More preferably, they are tertiary alkyl ester groups and acetal groups.

[0231] Furthermore, as a compound having at least one group selected from the group consisting of acyloxymethyl group, methylol group, ethylol group, and alkoxymethyl group, a compound having at least one group selected from the group consisting of urea bond and urethane bond is also preferred. A preferred embodiment of the above compound is the same as the preferred embodiment of the crosslinking agent U described above, except that the polymerizable group is not a radical polymerizable group but at least one group selected from the group consisting of acyloxymethyl group, methylol group, ethylol group, and alkoxymethyl group.

[0232] The following structures are examples of compounds having at least one group selected from the group consisting of acyloxymethyl, methylol, and ethylol groups. Compounds having an acyloxymethyl group include those obtained by changing the alkoxymethyl group in the following compounds to an acyloxymethyl group. The following compounds are examples of compounds having an alkoxymethyl group or acyloxymethyl in their molecule, but are not limited to these.

[0233] [ka]

[0234] [ka]

[0235] [ka]

[0236] The compound containing at least one alkoxymethyl group and acyloxymethyl group may be a commercially available product or one synthesized by a known method. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or triazine ring are preferred.

[0237] Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexasubtoxicbutylmelamine.

[0238] Specific examples of urea-based crosslinking agents include, for example, glycoluryl-based crosslinking agents such as monohydroxymethylated glycoluryl, dihydroxymethylated glycoluryl, trihydroxymethylated glycoluryl, tetrahydroxymethylated glycoluryl, monomethoxymethylated glycoluryl, dimethoxymethylated glycoluryl, trimethoxymethylated glycoluryl, tetramethoxymethylated glycoluryl, monoethoxymethylated glycoluryl, diethoxymethylated glycoluryl, triethoxymethylated glycoluryl, tetraethoxymethylated glycoluryl, monopropoxymethylated glycoluryl, dipropoxymethylated glycoluryl, trippropoxymethylated glycoluryl, tetrapropoxymethylated glycoluryl, monobutoxymethylated glycoluryl, dibutoxymethylated glycoluryl, tripbutoxymethylated glycoluryl, or tetrabutoxymethylated glycoluryl; Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea. Ethylene urea-based crosslinking agents such as monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethylated ethyleneurea, monobutoxymethylated ethyleneurea, or dibutoxymethylated ethyleneurea. Propylene urea-based crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea. Examples include 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolidinone and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone.

[0239] Specific examples of benzoguanamine crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, trippropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tripbutoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0240] In addition, as compounds having at least one group selected from the group consisting of methylol groups and alkoxymethyl groups, compounds in which at least one group selected from the group consisting of methylol groups and alkoxymethyl groups is directly bonded to an aromatic ring (preferably a benzene ring) are also suitably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylidentris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylidene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, and the like.

[0241] Other crosslinking agents may be commercially available, and suitable commercially available products include 46DMOC, 46DMOEP (both manufactured by Asahi Organic Chemicals Co., Ltd.), 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, and TriML-35XL. Examples include TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), Nikarac (registered trademark, hereinafter the same) MX-290, Nikarac MX-280, Nikarac MX-270, Nikarac MX-279, Nikarac MW-100LM, Nikarac MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.).

[0242] Furthermore, the resin composition of the present invention may also preferably contain, as another crosslinking agent, at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds.

[0243] - Epoxy compounds (compounds containing epoxy groups) - The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at temperatures below 200°C, and since dehydration reactions resulting from crosslinking do not occur, film shrinkage is less likely to occur. Therefore, including an epoxy compound is effective in suppressing low-temperature curing and warping of the resin composition of the present invention.

[0244] The epoxy compound preferably contains polyethylene oxide groups. This further reduces the modulus of elasticity and suppresses warping. A polyethylene oxide group refers to a group with two or more repeating units of ethylene oxide, and preferably with 2 to 15 repeating units.

[0245] Examples of epoxy compounds include, but are not limited to, bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl(glycidyloxypropyl)siloxane.Specifically, Epiclon® 850-S, Epiclon® HP-4032, Epiclon® HP-7200, Epiclon® HP-820, Epiclon® HP-4700, Epiclon® HP-4770, Epiclon® EXA-830LVP, Epiclon® EXA-8183, Epiclon® EXA-8169, Epiclon® N- 660, Epiclon® N-665-EXP-S, Epiclon® N-740 (all product names, manufactured by DIC Corporation), Licaresin® BEO-20E, Licaresin® BEO-60E, Licaresin® HBE-100, Licaresin® DME-100, Licaresin® L-200 (product names, manufactured by Shin Nippon Rika Co., Ltd.), EP-4003S, EP-4000S, EP-4088 S, EP-3950S (product names, manufactured by ADEKA Corporation), Celoxide (registered trademark) 2021P, Celoxide (registered trademark) 2081, Celoxide (registered trademark) 2000, EHPE3150, Epolid (registered trademark) GT401, Epolid (registered trademark) PB4700, Epolid (registered trademark) PB3600 (product names, manufactured by Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-300 Examples include 0-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, and BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds are also suitably used.

[0246] [ka]

[0247] In the formula, n is an integer between 1 and 5, and m is an integer between 1 and 20.

[0248] Among the above structures, it is preferable that n is 1 to 2 and m is 3 to 7, in order to achieve both heat resistance and improved elongation.

[0249] -Oxetane compounds (compounds containing an oxetanyl group)- Examples of oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester. Specific examples include the Aronoxetane series manufactured by Toagosei Co., Ltd. (e.g., OXT-121, OXT-221), which can be used individually or in combination of two or more.

[0250] -Benzoxazine compounds (compounds containing a benzoxazolyl group)- Benzoxazine compounds are preferred because, due to the crosslinking reaction resulting from a ring-opening addition reaction, degassing does not occur during curing, and furthermore, thermal shrinkage is reduced, suppressing warping.

[0251] Preferred examples of benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (both trade names, manufactured by Shikoku Chemicals Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resin, and phenol novolac-type dihydrobenzoxazine compounds. These may be used individually or in combination of two or more.

[0252] The content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the resin composition of the present invention. The other crosslinking agents may be present by one type or by two or more types. If two or more other crosslinking agents are present, it is preferable that their total amount is within the above range.

[0253] [Polymerization initiator] The resin composition of the present invention preferably contains a polymerization initiator that can initiate polymerization by light and / or heat. It is particularly preferable that it contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that interacts with a photoexcited sensitizer to generate active radicals.

[0254] The photoradical polymerization initiator is present in a wavelength range of approximately 240-800 nm (preferably 330-500 nm) at a concentration of at least approximately 50 L·mol. -1 ·cm -1 It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer, Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0255] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165-0182 of Japanese Patent Publication No. 2016-027357 and paragraphs 0138-0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37 to 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 Publication No. 2019-043864, photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are also incorporated herein.

[0256] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0257] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0258] As α-hydroxyketone initiators, 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.

[0259] 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.

[0260] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs 0161-0163 of International Publication No. 2021 / 112189 can also be suitably used. This information is incorporated herein.

[0261] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0262] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent Publication No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, and compounds described in International Publication No. 2013 / 167515, the contents of which are incorporated herein by reference.

[0263] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In resin compositions, it is particularly preferable to use oxime compounds (oxime-based photoradical polymerization initiators) as photoradical polymerization initiators. Oxime-based photoradical polymerization initiators have a >C=NOC(=O)- linking group in their molecule.

[0264] [ka]

[0265] Commercially available options include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), and ADEKA optomer N-1919 (manufactured by ADEKA Corporation, a photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052). TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arcules NCI-730, NCI-831, and ADEKA Arcules NCI-930 (manufactured by ADEKA Corporation). Additionally, DFI-091 (manufactured by Daito Chemix Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can be used. Furthermore, oxime compounds with the following structures can also be used. [ka]

[0266] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs 0169-0171 of International Publication No. 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom may be used. These are incorporated herein by reference.

[0267] Furthermore, as photopolymerization initiators, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group substituent attached to a carbazole skeleton, as described in paragraphs 0208-0210 of International Publication No. 2021 / 020359, can also be used. These contents are incorporated herein by reference.

[0268] As a photopolymerization initiator, an aromatic ring group Ar, in which an electron-withdrawing group is introduced to the aromatic ring, is used. OX1An oxime compound having the above aromatic ring group Ar (hereinafter also referred to as oxime compound OX) can also be used. OX1 Examples of electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups. Acyl and nitro groups are preferred, acyl groups are more preferred because they easily form films with excellent light resistance, and benzoyl groups are even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, acyl groups, or amino groups. More preferred substituents are alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic oxy groups, alkylsulfanyl groups, arylsulfanyl groups, or amino groups. Even more preferred substituents are alkoxy groups, alkylsulfanyl groups, or amino groups.

[0269] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2). [ka] In the formula, R X1 This represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group, or sulfamoyl group. R X2This represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, or amino group. R X3 ~R X14 Each of these independently represents a hydrogen atom or a substituent. However, R X10 ~R X14 At least one of them is an electron-withdrawing group.

[0270] In the above formula, R X12 R is an electron-withdrawing group, X10 , R X11 , R X13 , R X14 It is preferable that it is a hydrogen atom.

[0271] Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent Publication No. 4600600, which are incorporated herein by reference.

[0272] The most preferred oxime compounds include oxime compounds having specific substituents as described in Japanese Patent Publication No. 2007-269779 and oxime compounds having a thioaryl group as described in Japanese Patent Publication No. 2009-191061, the details of which are incorporated herein by reference.

[0273] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-arylsubstituted coumarin compounds.

[0274] Further preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds, with at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds being even more preferred, and the use of a metallocene compound or an oxime compound being even more preferred.

[0275] Furthermore, as photoradical polymerization initiators, compounds described in paragraphs 0175-0179 of International Publication No. 2021 / 020359 may be used. This is incorporated herein by reference.

[0276] Furthermore, the photoradical polymerization initiator may be a compound described in paragraphs 0048-0055 of International Publication No. 2015 / 125469, which is incorporated herein by reference.

[0277] As the photoradical polymerization initiator, a bifunctional or trifunctional or higher photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time and improving the long-term stability of the resin composition. Specific examples of bifunctional or trifunctional or more photoradical polymerization initiators include dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds (E) and (G) described in JP 2013-522445, and International Publication No. 2016 / 0 Examples include Cmpd1-7 described in Patent No. 34963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators described in paragraphs 0020-0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) described in paragraphs 0017-0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0278] If a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, relative to the total solid content of the resin composition of the present invention. Only one type of photopolymerization initiator may be included, or two or more types may be included. If two or more types of photopolymerization initiators are included, it is preferable that the total amount is within the above range. Furthermore, since photopolymerization initiators can also function as thermal polymerization initiators, heating with an oven or hot plate may further accelerate the crosslinking process by the photopolymerization initiator.

[0279] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenones, Michlaz ketones, coumarins, pyrazole azos, anilino azos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, pyrazolotriazole azos, pyridone azos, cyanines, phenothiazines, pyrrolopyrazole azomethine, xanthenes, phthalocyanines, benzopyrans, and indigos. Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-Methoxycarbonyl-7-diethylaminocoumarin, 3-Ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-Phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-Tolyldiethanolamine, N-phenylethanolamine, 4-Morpholinobenzophenone, Isoamyl dimethylaminobenzoate, Isoamyl diethylaminobenzoate Examples include amyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details regarding the sensitizing dye, please refer to paragraphs 0161 to 0163 of Japanese Patent Publication No. 2016-027357, which are incorporated herein by reference.

[0280] If the resin composition contains a sensitizer, the sensitizer content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0281] [Chain transport agent] The resin composition of the present invention may contain a chain transfer agent. A chain transfer agent is defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in their molecules, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0282] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0283] If the resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0284] <Base Generator> The resin composition of the present invention may contain a base-generating agent. Here, a base-generating agent is a compound that can generate a base by physical or chemical action. Preferred base-generating agents for the resin composition of the present invention include thermal base-generating agents and photobase-generating agents. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition also contains a base generator. By including a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example by heating, resulting in a cured product with good mechanical properties and chemical resistance, and thus good performance as an interlayer insulating film for redistribution layers included in semiconductor packages. The base generator can be either an ionic or nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. There are no particular restrictions on the base-generating agent according to the present invention, and known base-generating agents can be used. Examples of known base-generating agents include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like. As nonionic base generators, for example, compounds represented by formula (B1) or formula (B2) described in paragraphs 0275 to 0285 of International Publication No. 2021 / 112189, compounds represented by formula (N1) described in paragraphs 0102 to 00162 of International Publication No. 2020 / 066416, or as base generators, the thermobase generators described in paragraphs 0013 to 0041 of International Publication No. 2020 / 054226 are preferred. These contents are incorporated herein.

[0285] If the resin composition of the present invention contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or 4 parts by mass or less. One or more types of base-generating agents may be used. When using two or more types, it is preferable that the total amount is within the above range.

[0286] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. Organic solvents are preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0287] 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, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), and 2-alkyloxy Suitable examples include alkyl cypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0288] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0289] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0290] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0291] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0292] Suitable amides include 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-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0293] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0294] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0295] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0296] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. Particularly preferred combinations include dimethyl sulfoxide and γ-butyrolactone, dimethyl sulfoxide and γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or N-methyl-2-pyrrolidone and ethyl lactate. Another preferred embodiment of the present invention is the addition of toluene to these combined solvents in an amount of about 1 to 10% by mass relative to the total mass of the solvent. In particular, from the viewpoint of storage stability of the resin composition, an embodiment containing γ-valerolactone as a solvent is also one of the preferred embodiments of the present invention. In such an embodiment, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, the upper limit of the above content is not particularly limited and may be 100% by mass. The above content may be determined by considering the solubility of components such as specific resins contained in the resin composition. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, it is preferable that the solvent contains 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide.

[0297] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method.

[0298] The resin composition of the present invention may contain only one solvent or two or more solvents. If two or more solvents are included, it is preferable that their total number is within the above range.

[0299] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion modifier to improve adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion modifiers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0300] [Silane coupling agent] Examples of silane coupling agents include the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Publication No. 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358. Furthermore, it is also preferable to use the following compounds as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group. In addition, R below represents a structure derived from the blocking agent in the blocked isocyanate group. The blocking agent can be selected according to the elimination temperature, but examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of wanting to set the elimination temperature to 160 to 180°C, caprolactam is preferred. Examples of commercially available compounds of this type include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0301] [ka]

[0302] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups can also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing repeating units represented by the following formula (S-1). [ka] In formula (S-1), R S1 represents a monovalent organic group, R S2 represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer between 0 and 2. R S1It is preferable that the structure includes polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, amino groups, etc. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, etc., with vinylphenyl groups, (meth)acrylamide groups, or (meth)acryloyloxy groups being preferred, vinylphenyl groups or (meth)acryloyloxy groups being more preferred, and (meth)acryloyloxy groups being even more preferred. R S2 It is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. n represents an integer between 0 and 2, and is preferably 1. Here, the structures of the repeating units represented by multiple formulas (S-1) in the oligomer-type compound may be identical. Here, it is preferable that at least one of the repeating units represented by the formula (S-1) contained in the oligomer-type compound has n = 1 or 2, more preferably that at least two have n = 1 or 2, and even more preferably that at least two have n = 1. Commercially available oligomeric compounds can be used for this purpose, and an example of such a product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0303] [Aluminum-based adhesive aid] Examples of aluminum-based adhesives include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0304] Furthermore, other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0305] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total content falls within the above range.

[0306] <Migration inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, it is possible to effectively suppress the movement of metal ions originating from the metal layer (metal wiring) into the film.

[0307] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0308] Alternatively, an ion trapping agent that captures anions such as halogen ions can be used.

[0309] Other migration inhibitors include, for example, the compounds described in paragraph 0304 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0310] Specific examples of migration inhibitors include the following compounds.

[0311] [ka]

[0312] If the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor 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, based on the total solid content of the resin composition of the present invention.

[0313] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0314] <Polymerization inhibitors> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0315] Specific polymerization inhibitor compounds include those described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-N,N-dioxide, and others. This information is incorporated herein by reference.

[0316] If the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor 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, based on the total solid content of the resin composition of the present invention.

[0317] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0318] <Other additives> The resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, anti-flocculation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. Furthermore, the resin composition of the present invention may further contain other components such as urea compounds. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101-0104, 0107-0109, etc., of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein. When these additives are incorporated, it is preferable that their total amount be 3% by mass or less of the solid content of the resin composition of the present invention.

[0319] [Surfactants] Various surfactants can be used, including fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0320] By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid properties (especially fluidity) when prepared as a coating solution are further improved, and the uniformity of the coating thickness and the amount of liquid used can be further improved. Specifically, when forming a film using a coating solution to which a composition containing a surfactant has been applied, the interfacial tension between the surface to be coated and the coating solution is reduced, improving wettability to the surface to be coated and improving coatability to the surface to be coated. Therefore, it is possible to more favorably form a film of uniform thickness with less thickness variation.

[0321] Examples of fluorinated surfactants include the compounds described in paragraph 0328 of International Publication No. 2021 / 112189. This information is incorporated herein by reference. Fluorine-based surfactants can also preferably be fluorine-containing polymer compounds that include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). The following compounds are also examples of fluorine-based surfactants used in the present invention. [ka]

[0322] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. Fluorine-based surfactants can also be obtained by using fluorine-containing polymers having ethylenically unsaturated groups in their side chains. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Commercially available products include, for example, Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0323] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

[0324] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include compounds described in paragraphs 0329-0334 of International Publication No. 2021 / 112189, respectively. These contents are incorporated herein by reference.

[0325] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0326] [Higher fatty acid derivative] In order to prevent polymerization inhibition caused by oxygen, the resin composition of the present invention may contain a higher fatty acid derivative such as behenic acid or behenic acid amide, which may be unevenly distributed on the surface of the resin composition during the drying process after application.

[0327] Furthermore, higher fatty acid derivatives may also be compounds described in paragraph 0155 of International Publication No. 2015 / 199219, which are incorporated herein by reference.

[0328] When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. There may be only one type of higher fatty acid derivative, or there may be two or more types. If there are two or more types of higher fatty acid derivatives, it is preferable that their total is within the above range.

[0329] [Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, and in particular may contain a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals in response to thermal energy, thereby initiating or promoting the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, thereby further improving solvent resistance. In addition, the photopolymerization initiators mentioned above may also have the function of initiating polymerization in response to heat, and may be added as thermal polymerization initiators.

[0330] Examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Publication No. 2008-063554, the contents of which are incorporated herein by reference.

[0331] If a thermal polymerization initiator is included, its content 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, relative to the total solid content of the resin composition of the present invention. Only one thermal polymerization initiator may be included, or two or more may be included. If two or more thermal polymerization initiators are included, it is preferable that the total amount is within the above range.

[0332] [Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.

[0333] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle diameter for inorganic particles is both the primary particle diameter and the volume-average particle diameter. The volume-average particle diameter can be measured by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission, X-ray transmission, or laser diffraction / scattering.

[0334] [UV absorber] The composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers that can be used include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers. Specific examples of ultraviolet absorbers include the compounds described in paragraphs 0341-0342 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0335] In the present invention, the above-mentioned ultraviolet absorbers may be used individually or in combination of two or more types. The composition of the present invention may or may not contain an ultraviolet absorber, but if it does, the amount of ultraviolet absorber 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, based on the total solid content mass of the composition of the present invention.

[0336] [Organotitanium compounds] The resin composition of this embodiment may contain an organotitanium compound. By including an organotitanium compound in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0337] Examples of usable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Among these, titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and yield a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), and titanium diisopropoxidebis(ethylacetoacetate). II) Tetraalkoxy titanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], etc. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedione), titanium oxide bis(tetramethylheptanedione), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0338] In particular, from the viewpoint of achieving better chemical resistance, the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds, and III) titanocene compounds. Titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are preferred.

[0339] When incorporating an organic titanium compound, the amount is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or more, good heat resistance, moisture resistance, and chemical resistance are more effectively expressed in the resulting cured pattern, while when it is 10 parts by mass or less, the storage stability of the composition is superior.

[0340] [Antioxidant] The composition of the present invention may contain an antioxidant. Including an antioxidant as an additive can improve the elongation properties of the cured film and its adhesion to metal materials. Examples of antioxidants include phenol compounds, phosphite compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348-0357 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0341] The amount of antioxidant added is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, relative to the resin. Adding 0.1 parts by mass or more makes it easier to obtain improved elongation properties and adhesion to metal materials even in high-temperature and high-humidity environments. Adding 10 parts by mass or less improves the sensitivity of the resin composition, for example, through interaction with the photosensitive agent. 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 falls within the above range.

[0342] [Anti-coagulation agent] The resin composition of this embodiment may optionally contain an anti-flocculation agent. Examples of anti-flocculation agents include sodium polyacrylate.

[0343] In the present invention, one type of anticoagulant may be used alone, or two or more types may be used in combination. The composition of the present invention may or may not contain an anti-flocculation agent. If it does contain an anti-flocculation agent, the amount of the anti-flocculation agent 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, based on the total solid content mass of the composition of the present invention.

[0344] [Phenol compounds] The resin composition of this embodiment may optionally contain phenolic compounds. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR-BIPC-F (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.).

[0345] In this invention, a single phenolic compound may be used alone, or two or more compounds may be used in combination. The composition of the present invention may or may not contain a phenolic compound. If it does contain a phenolic compound, the content of the phenolic compound 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, based on the total solid content of the composition of the present invention.

[0346] [Other polymer compounds] Other polymer compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified forms into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups have been introduced.

[0347] In this invention, the other polymer compounds may be used individually or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds. If other polymer compounds are included, the content of the other polymer compounds 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, based on the total solid content mass of the composition of the present invention.

[0348] <Properties of resin compositions> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm 2 / s~12,000mm 2 / s is preferred, and 2,000 mm 2 / s~10,000mm 2 / s is more preferable, 2,500mm 2 / s~8,000mm 2 / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm 2 If the rate is 1 / s or higher, it is easy to coat the film thickness required for, for example, as an insulating film for rewiring, and 12,000 mm 2 If the rate is less than or equal to / s, an excellent coating film can be obtained on the coated surface.

[0349] The maximum absorbance of the resin composition of the present invention at wavelengths of 400 to 800 nm is preferably 0.8 Abs or less, more preferably 0.4 Abs or less, and particularly preferably 0.2 Abs or less. The lower limit of the absorbance is not particularly limited and may be 0 Abs. However, the absorbance at a specific wavelength can be measured by dissolving 20 mg of the resin composition in 200 mL of dimethyl sulfoxide and using an ultraviolet-visible-infrared spectrophotometer (Hitachi High-Tech Science UH4150). Abs is the logarithm of the transmittance, where T is the transmittance. 10 This is the value of (1 / T), where T is the ratio of transmitted light I to incident light intensity I0 when the optical path length is 1 cm (I / I0).

[0350] <Restrictions on substances contained in resin compositions> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining moisture content include adjusting humidity during storage and reducing the porosity of the storage container.

[0351] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm (parts per million) 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 excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

[0352] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0353] When considering the application of the resin composition of the present invention as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. In particular, the amount of halogen atoms present in the form of halogen ions is preferably 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 halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above ranges. Methods for adjusting the halogen atom content include ion exchange treatment.

[0354] Conventional containers can be used as containers for the resin composition of the present invention. Furthermore, to suppress the incorporation of impurities into the raw materials and the resin composition of the present invention, it is also preferable to use a multilayer bottle with an inner wall made of six types of resin in six layers, or a bottle with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0355] <Cured product of resin composition> A cured product of the resin composition of the present invention can be obtained by curing the resin composition. The cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The curing of the resin composition is preferably by heating, more preferably within the range of 120°C to 400°C, even more preferably within the range of 140°C to 380°C, and particularly preferably within 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 according to the application, such as in the form of a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. Furthermore, by pattern processing of the resin composition, the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming via holes for conductivity, adjusting impedance, capacitance or internal stress, or providing heat dissipation functions. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate of the resin composition of the present invention upon curing is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the 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 - (Volume after hardening ÷ Volume before hardening) × 100

[0356] <Characteristics of cured resin compositions> When the aforementioned polyimide or polyimide precursor is used as the resin, the cured product of the resin composition of the present invention preferably has an imidization reaction rate (imidization rate) of 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties, and there is no particular upper limit. The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, even more preferably 50% or more, even more preferably 60% or more, and most preferably 65% ​​or more. The elongation at break of the cured product is not particularly limited, as a higher value indicates better elongation at break. The glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0357] The maximum absorbance of the cured product of the present invention at wavelengths of 400 to 800 nm is preferably 0.8 Abs or less, more preferably 0.4 Abs or less, and particularly preferably 0.2 Abs or less. The lower limit of the absorbance is not particularly limited and may be 0 Abs. However, the absorbance at a specific wavelength can be determined by forming a film of the resin composition on a glass substrate so that the film thickness after curing is 10 μm, and measuring it using an ultraviolet-visible-infrared spectrophotometer (Hitachi High-Tech Science UH4150). For example, the absorbance at a specific wavelength can be measured using a sample (film) formed on a glass substrate by the following method: The film is applied to a 10cm square glass substrate (Corning) by spin coating, dried at 100°C for 5 minutes to form a photosensitive film, and then measured using a stepper (Nikon Corporation, NSR1505 i6) at a wavelength of 365nm and a light intensity of 400mJ / cm². 2 Then expose the entire surface. Next, under a nitrogen atmosphere, the temperature is increased at a rate of 10°C / min until it reaches 230°C, and then maintained at 230°C for 180 minutes to form a film.

[0358] The content of the specific metal complex relative to the total mass of the cured product is preferably 0.05 to 20% by mass. The lower limit is more preferably 0.10% by mass or more, even more preferably 0.2% by mass or more, particularly preferably 0.5% by mass or more, and most preferably 1% by mass or more. The upper limit is more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less. Furthermore, if two or more specific metal complexes are included, it is preferable that the total amount of each complex is within the range described above.

[0359] <Preparation of resin composition> The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods. Mixing can be achieved using methods such as mixing with agitators, mixing with a ball mill, or mixing by rotating the tank itself. The mixing temperature is preferably 10-30°C, and more preferably 15-25°C.

[0360] Furthermore, it is preferable to perform filtration using a filter to remove foreign matter such as dirt and fine particles from the resin composition of the present invention. The filter pore size can be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. If the filter material is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter may be one that has been pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. As an example of a connection configuration, an HDPE filter with a pore size of 1 μm may be connected in series as the first stage, and an HDPE filter with a pore size of 0.2 μm may be connected in series as the second stage. In addition, various materials may be filtered multiple times. When filtering multiple times, circulating filtration may be used. In addition, filtration may be performed under pressure. When filtration is performed under pressure, the pressure applied may be, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtration using a filter, impurities may be removed using an adsorbent. A combination of filter filtration and impurity removal using an adsorbent may also be used. As the adsorbent, any known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. Furthermore, after filtration using a filter, the resin composition filled into the bottle may be subjected to a degassing process by placing it under reduced pressure.

[0361] (Method of manufacturing a cured product) The method for producing the cured product 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 producing a cured product of the present invention more preferably includes the above-mentioned film formation step, an exposure step for selectively exposing the film formed in the film formation step, and a developing step for developing the film exposed in the exposure step using a developer to form a pattern. The method for producing a cured product of the present invention is particularly preferably to include at least one of the above-mentioned film formation step, exposure step, development step, and a heating step for heating the pattern obtained in the development step and a post-development exposure step for exposing the pattern obtained in the development step. Furthermore, the manufacturing method of the present invention may also preferably include the above-mentioned film formation step and the step of heating the above-mentioned film. The details of each step are explained below.

[0362] <Film formation process> The resin composition of the present invention can be used in a film-forming process, where it is applied to a substrate to form a film. The method for producing the cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film.

[0363] [Base material] The type of substrate can be appropriately determined depending on the application, but examples include semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal, and substrates in which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass), TFT (thin-film transistor) array substrates, molded substrates, and electrode plates for plasma display panels (PDPs), and are not particularly limited. In the present invention, semiconductor fabrication substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred. Furthermore, these substrates may have layers on their surface, such as an adhesion layer or an oxidation layer, provided with hexamethyldisilazane (HMDS) or the like. Furthermore, the shape of the base material is not particularly limited and may be circular or rectangular. For the base material, if it is circular, for example, the diameter is 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, for example, the length of the shorter side is 100 to 1000 mm, preferably 200 to 700 mm. Furthermore, as the base material, for example, a plate-shaped, preferably panel-shaped, base material (substrate) is used.

[0364] Furthermore, when a resin composition is applied to the surface of a resin layer (for example, a layer made of a cured material) or a metal layer to form a film, the resin layer or metal layer serves as the substrate.

[0365] As a means of applying the resin composition of the present invention onto a substrate, coating is preferred.

[0366] Specific examples of application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating are more preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit 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 depending on the shape of the substrate; for circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a method can be applied in which a coating film, which has been previously applied and formed on a temporary support using the above application method, is transferred onto a substrate. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Publication No. 2006-047592 can be suitably used in the present invention as well. Furthermore, a process to remove excess film from the edges of the substrate may be performed. Examples of such processes include edge bead rinsing (EBR) and back rinsing. Alternatively, a pre-wetting process may be employed in which the substrate is coated with various solvents to improve its wettability before applying the resin composition to the substrate.

[0367] <Drying process> The above film may be subjected to a drying step (a process in which the formed film (layer) is dried in order to remove the solvent after the film formation step (layer formation step). In other words, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film formation step. Furthermore, it is preferable that the above drying step be performed after the film formation step and before the exposure step. The drying temperature of the film in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0368] <Exposure process> The above film may be subjected to an exposure process in which the film is selectively exposed. In other words, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film formation step. Selective exposure means exposing only a portion of a film. Selective exposure creates areas on the film that are exposed (exposed regions) and areas that are not exposed (unexposed regions). The exposure amount is not particularly defined as long as it can cure the resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm² in terms of exposure energy at a wavelength of 365 nm. 2 Preferably, 200-8,000 mJ / cm² 2 This is preferable.

[0369] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0370] In relation to the light source, the exposure wavelengths include (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (g, h, i-line wavelengths), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic 532nm and third harmonic 355nm of YAG lasers. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and among these, exposure with the i-line is preferred. This can result in particularly high exposure sensitivity. Furthermore, the exposure method is not particularly limited, and any method in which at least a portion of the film made of the resin composition of the present invention is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0371] <Post-exposure heating process> The above film may be subjected to a heating step after exposure (post-exposure heating step). In other words, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed by the exposure step is heated. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating process is preferably 1 to 12°C / min from the initial heating temperature to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. Furthermore, the heating rate may be changed as needed during the heating process. The heating means in the post-exposure heating process is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used. Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, or argon through the system.

[0372] <Developing process> The film after exposure may be subjected to a developing process in which it is developed using a developing solution to form a pattern. In other words, the method for producing a cured product of the present invention may include a developing step in which a film exposed in an exposure step is developed using a developing solution to form a pattern. During development, one of the exposed or unexposed areas of the film is removed, forming a pattern. Here, development in which the unexposed parts of the film are removed by the development process is called negative development, and development in which the exposed parts of the film are removed by the development process is called positive development.

[0373] [Developer] Examples of developing solutions used in the developing process include alkaline aqueous solutions or developing solutions containing organic solvents.

[0374] When the developer is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferably, TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and TMAH is more preferred. The content of basic compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, when using TMAH, for example.

[0375] If the developer contains an organic solvent, the organic solvent may be one of the compounds described in paragraph 0387 of International Publication No. 2021 / 112189. This is incorporated herein by reference. Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, triethylene glycol, etc., and suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

[0376] When the developer contains an organic solvent, one or more organic solvents can be used in mixture form. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.

[0377] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the above content may be 100% by mass.

[0378] The developing solution may contain other components as well. Other components include, for example, known surfactants and known defoaming agents.

[0379] [Method of supplying developing solution] There are no particular restrictions on the method of supplying the developer, as long as the desired pattern can be formed. These methods include immersing the substrate on which the film has been formed in the developer, paddle development where the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, and spray nozzles. From the viewpoint of developer penetration, removal of non-image areas, and manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying it with a spray nozzle is preferred, and from the viewpoint of developer penetration into the image area, the method of supplying with a spray nozzle is more preferred. Alternatively, the process may involve continuously supplying the developer solution through a straight nozzle, spinning the substrate to remove the developer solution from the substrate, spin-drying, and then continuously supplying the developer solution again through a straight nozzle, spinning the...

Claims

1. resin and A metal complex having one or more π-conjugated moieties containing a nitrogen atom, The metal complex includes a substructure represented by the following formula (1-2) or formula (1-3) as a structure containing a π-conjugated moiety that includes the nitrogen atom. Resin composition. 【Chemistry 1】 In equation (1-2), X1 to X5 each independently represent -C(-*)= or -N=, where * represents a bonding site with another structure and # represents a bonding site with a metal atom. In equations (1-3), X1 to X7 each independently represent -C(-*)= or -N=, where * represents a bonding site with other structures excluding aromatic rings, and # represents a bonding site with a metal atom.

2. The resin composition according to claim 1, further comprising a photoradical polymerization initiator.

3. The resin composition according to claim 1 or 2, wherein the metal complex is a compound having a π-conjugated moiety containing the nitrogen atom and at least one group selected from the group consisting of a hydroxyl group, a mercapto group, and a carboxyl group on the same ligand.

4. The resin composition according to claim 1, wherein the metal complex includes a substructure represented by the following formula (3-1) as a structure containing a π-conjugated moiety including the nitrogen atom. 【Chemistry 2】 In formula (3-1), R １ ~R ４ and R １８ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acyl group, a phenyl group, an acyloxy group, an ester group, a halogen atom, a nitro group, a cyano group, -NR １０１ R １０２ , -SR １０３ , -SO ２ NR １０４ R １０５ , -CONR １０６ R １０７ or -NR １０８ COR １０９ represents, R １０１ and R １０２ each independently represents a hydrogen atom, an alkyl group or an aryl group, R １０１ and R １０２ may combine to form a ring, R １０３ ~R １０９ each independently represents an alkyl group or an aryl group, L １ represents a group represented by the following formula (L-1) or formula (L-2), X １ and X ２ each independently represents -O- or -S-, and # represents a bonding site with a metal atom. 【Transformation 3】 In equations (L-1) and (L-2), R １４ ~R １７ Each of these independently consists of a hydrogen atom, alkyl group, alkoxy group, allyloxy group, acyl group, phenyl group, acyloxy group, ester group, halogen atom, nitro group, cyano group, and -NR １０１ R １０２ ,-SR １０３ , -SO ２ NR １０４ R １０５ , -CONR １０６ R １０７ or -NR １０８ COR １０９ Represents R １０１ and R １０２ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R １０１ and R １０２ They may be bonded together to form a ring, R １０３ ~R １０９ Each of these independently represents an alkyl group or an aryl group, and * represents X in formula (3-1). １ The # represents the bonding site with the nitrogen atom in formula (3-1).

5. Said L １ The group is represented by formula (L-2), and the R １８ is a hydrogen atom, and the R １ , R ２ , R ３ , R ４ , R １４ , R １５ , R １６ , R １７ At least one of these is a methyl group, alkoxy group, allyloxy group, phenyl group, acyloxy group, acyl group, ester group, halogen atom, nitro group, cyano group, -NR １０１ R １０２ ,-SR １０３ , -SO ２ NR １０４ R １０５ , -CONR １０６ R １０７ or -NR １０８ COR １０９ Represents R １０１ and R １０２ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R １０１ and R １０２ They may be bonded together to form a ring, R １０３ ~R １０９ The resin composition according to claim 4, wherein each of them independently represents an alkyl group or an aryl group.

6. The resin composition according to claim 1, wherein the metal complex includes a substructure represented by the following formula (4-1) as a structure containing a π-conjugated moiety that includes the nitrogen atom. 【Chemistry 4】 In formula (4-1), R １ ~R ７ Each of these independently consists of a hydrogen atom, alkyl group, alkoxy group, allyloxy group, acyl group, phenyl group, acyloxy group, ester group, halogen atom, nitro group, cyano group, and -NR １０１ R １０２ ,-SR １０３ , -SO ２ NR １０４ R １０５ , -CONR １０６ R １０７ or -NR １０８ COR １０９ Represents R １０１ and R １０２ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and R １０１ and R １０２ They may be bonded together to form a ring, R １０３ ~R １０９ Each of these independently represents an alkyl group or an aryl group, X １ and X ２ Each of these independently represents either -O- or -S-, and # represents the bonding site with the metal atom.

7. Said R １ , R ２ , R ６ and R ７ The resin composition according to claim 6, wherein at least one of them is a group other than a hydrogen atom.

8. resin and A compound represented by the following formula (2-1) is included: Resin composition. 【Transformation 5】 In equation (2-1), M is titanium, zirconium, or hafnium, l1 is an integer from 0 to 2, l2 is 0 or 1, l1 + l2 × 2 is an integer from 0 to 2, m is an integer from 0 to 4, n is an integer from 0 to 2, l1 + l2 + m + n × 2 = 4, R １１ Each of these is independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group, R １２ R is a substituted or unsubstituted hydrocarbon group, ２ Each of these is an independent group containing a structure represented by the following formula (1-2) or formula (1-3), R ３ Each of these is an independent group containing a structure represented by formula (1-2) or formula (1-3), X Ａ Each of these is independently either an oxygen atom or a sulfur atom. 【Transformation 6】 In equation (1-2), X1 to X5 each independently represent -C(-*)= or -N=, where * represents a bonding site with another structure and # represents a bonding site with a metal atom. In equations (1-3), X1 to X7 each independently represent -C(-*)= or -N=, where * represents a bonding site with other structures excluding aromatic rings, and # represents a bonding site with a metal atom.

9. The resin composition according to claim 8, wherein l1 and l2 in formula (2-1) are 0 and m is 0, 2, or 4.

10. The resin composition according to any one of claims 1, 2, and 4 to 9, wherein the resin is at least one resin selected from the group consisting of cyclized resins and their precursors.

11. The resin composition according to any one of claims 1, 2, and 4 to 9, wherein the resin is a polyimide or a polyimide precursor.

12. A resin composition according to any one of claims 1, 2, and 4 to 9, further comprising a polymerizable compound.

13. A resin composition according to any one of claims 1, 2, and 4 to 9, further comprising a photopolymerization initiator.

14. The resin composition according to any one of claims 1, 2, and 4 to 9, comprising a cyclized resin or a precursor thereof as the resin, and used for forming an interlayer insulating film for a redistribution layer.

15. A cured product obtained by curing the resin composition according to any one of claims 1, 2, and 4 to 9.

16. A laminate comprising two or more layers made of the cured material described in claim 15, wherein a metal layer is included between any of the layers made of the cured material.

17. A method for producing a cured product, comprising a film-forming step of applying a resin composition according to any one of claims 1, 2, and 4 to 9 onto a substrate to form a film.

18. A method for producing a cured product according to claim 17, comprising an exposure step of selectively exposing the film, a developing step of developing the film using a developer to form a pattern, and a heating step of heating the film at 50 to 450°C.

19. A method for manufacturing a laminate, comprising the method for manufacturing a cured product described in claim 17.

20. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product described in claim 17.

21. A semiconductor device comprising the cured product described in claim 15.

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