Cured product, laminate, and semiconductor device

Abstract

To provide a cured product which suppresses crack formation even when subjected to repeated moisture resistance tests, a laminate including the cured product, and a semiconductor device including the cured product.SOLUTION: The present invention provides a cured product, a laminate containing the cured product, and a semiconductor device containing the cured product. The cured product is obtained by curing a curable resin composition containing at least one resin B selected from the group consisting of a polyimide and a polyimide precursor and a photosensitive agent, in which the Young modulus of the cured product is 2.5 to 6.0 GPa, and the cured product contains a nitrogen-containing heterocyclic compound. A resin A formed after the curing of the resin composition has a repeating unit represented by formula (A-1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cured product, a laminate, and a semiconductor device. [Background technology]

[0002] BACKGROUND ART Nowadays, resin materials produced from resin compositions containing resins are being utilized in various fields. For example, cured products containing heterocycle-containing polymers such as polyimides have excellent heat resistance and insulating properties, and are therefore used in a variety of applications. Examples of such applications include, but are not limited to, insulating films, sealing materials, or protective films for semiconductor devices used for packaging. They are also used as base films or coverlays for flexible substrates.

[0003] For example, Patent Document 1 describes a polyimide precursor having a structure derived from an amine compound containing a siloxane bond, and a hybrid bonding insulating film forming material containing the polyimide precursor and a solvent. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2023-151490 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, insulating films for redistribution layers (RDLs) used in semiconductor packages are required to exhibit stable performance even in harsh operating environments.

[0006] An object of the present invention is to provide a cured product that suppresses the occurrence of cracks even when subjected to repeated moisture resistance tests, a laminate including the cured product, and a semiconductor device including the cured product. [Means for solving the problem]

[0007] Examples of typical embodiments of the present invention are given below. <1> At least one resin B selected from the group consisting of polyimides and polyimide precursors; A cured product obtained by curing a curable resin composition containing a photosensitizer, the Young's modulus of the cured product is 2.5 to 6.0 GPa, The cured product contains a nitrogen-containing heterocyclic compound, Furthermore, the resin A formed after curing of the resin composition has a repeating unit represented by the following formula (A-1): cured product. [ka] In formula (A-1), X A1 is a structure represented by formula (X-A1), and Y A1 is a divalent linking group. [ka] In formula (X-A1), * represents the bonding site with the carbonyl group in formula (A-1). <2> The resin A is a resin having a repeating unit represented by the following formula (A-2): <1> The cured product according to claim 1. [ka] In formula (A-2), X A2 is a tetravalent organic group, and Y A2 is a divalent linking group and satisfies at least one of the following conditions 1 and 2: Condition 1:X A2 is a structure represented by the following formula (X-A2) Condition 2: Y A2 is a structure represented by the following formula (Y-A2): [ka] In formula (X-A2), * represents the bonding site with the carbonyl group in formula (A-2). [ka] In formula (Y-A2), * represents the bonding site with the nitrogen atom in formula (A-2). <3> The resin A is a resin having a repeating unit represented by the following formula (A-3): <1> or <2> The cured product according to claim 1. [ka] In formula (A-2), X A3 is a tetravalent organic group, and Y A3 is a divalent linking group and satisfies at least one of the following conditions 3 and 4. Condition 3:X A3 is a structure represented by the following formula (X-A3) Condition 4: Y A3 is a structure represented by any one of the following formulas (Y-A3) to (Y-A5): [ka] In formula (X-A3), * represents the bonding site with the carbonyl group in formula (A-3). [ka] In formulae (Y-A3) to (Y-A5), * represents the bonding site with the nitrogen atom in formula (A-3). <4> The weight average molecular weight of the resin B is 15,000 to 40,000. <1> ~ <3> 10. The cured product according to any one of the above. <5> The resin composition contains a titanium complex compound. <1> ~ <4> 10. The cured product according to any one of the above. <6> The photosensitizer further contains an oxime compound. <1> ~ <5> 10. The cured product according to any one of the above. <7> The resin composition further contains an antioxidant. <1> ~ <6> 10. The cured product according to any one of the above. <8> The resin composition further contains an aniline compound. <1> ~ <7> 10. The cured product according to any one of the above. <9> The resin composition further contains a dialkyl urea compound. <1> ~ <8> 10. The cured product according to any one of the above. <10> In the resin B, the molar ratio of the amic acid ester structure to the total molar amount of the amic acid structure and the amic acid ester structure is 90 to 99.9%. <1> ~ <9> 10. The cured product according to any one of the above. <11> the amount of acidic functional groups contained in the resin B, the neutralization point of which has a pH in the range of 7.0 to 12.0, is 0.0010 to 0.3000 mmol / g; <1> ~ <10> 10. The cured product according to any one of the above. <12> The amine value of the resin B is 0.001 to 0.300 mmol / g. <1> ~ <11> 10. The cured product according to any one of the above. <13> The imidization rate of the resin B is 3 to 40%. <1> ~ <12> 10. The cured product according to any one of the above. <14> The resin B contains a structure represented by the following formula (1), and the molar amount of the structure represented by formula (1) relative to the total solid content of the resin composition is 0.01 to 1.0 mmol / g: <1> ~ <13> 10. The cured product according to any one of the above. [ka] In formula (1), R 1 and R 2 each independently represents a saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms; X 1 represents an oxygen atom or a sulfur atom, and L 1 represents -C(=O)- or -S(=O)2-, * 1 and* 2 each independently represents a binding site to another structure, and R 1 , R 2 , * 1 A structure that binds to * 2 At least two of the structures bonded to may be bonded to form a ring structure. <15> <1> ~ <14> 1. A laminate comprising two or more layers each made of the cured product according to any one of 1 to 8, and a metal layer between any two adjacent layers made of the cured product. <16> <1> ~ <14> A semiconductor device comprising the cured product according to any one of the above items. [Effects of the Invention]

[0008] According to the present invention, there are provided a cured product that suppresses the occurrence of cracks even when subjected to repeated moisture resistance tests, a laminate including the cured product, and a semiconductor device including the cured product. DETAILED DESCRIPTION OF THE INVENTION

[0009] The main embodiments of the present invention will be described below, but the present invention is not limited to the embodiments explicitly described. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower limit and upper limit, respectively. In this specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps, so long as the intended effect of the step can be achieved. In the description of groups (atomic groups) in this specification, when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents. For example, the term "alkyl group" encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups). Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation. In this specification, "(meth)acrylate" means either or both of "acrylate" and "methacrylate", "(meth)acrylic" means either or both of "acrylic" and "methacrylic", and "(meth)acryloyl" means either or both of "acryloyl" and "methacryloyl". In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the term "total solids content" refers to the total mass of all components of the composition excluding the solvent, and the term "solids concentration" refers to the mass percentage of the components excluding the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220GPC (manufactured by Tosoh Corporation) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is not suitable as the eluent, such as when the solubility is low, THF (tetrahydrofuran) can also be used. Unless otherwise specified, detection in GPC measurements is performed using a UV (ultraviolet) ray (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that there is another layer above or below the reference layer among the multiple layers being considered. In other words, 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 with each other. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "above," or, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "above," and the opposite direction is referred to as "below." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "above" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, a composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Unless otherwise specified, the content of each component in the 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. As used herein, combinations of preferred embodiments are more preferred embodiments.

[0010] (cured product) The cured product of the present invention is obtained by curing a curable resin composition containing at least one resin B selected from the group consisting of polyimides and polyimide precursors and a photosensitizer, wherein the cured product has a Young's modulus of 2.5 to 6.0 GPa, contains a nitrogen-containing heterocyclic compound, and further, resin A formed after curing of the resin composition has a repeating unit represented by formula (A-1).

[0011] The cured product of the present invention can be used, for example, as an insulating film for semiconductor devices, an interlayer insulating film for rewiring layers, a stress buffer film, etc., and is preferably used as an interlayer insulating film for rewiring layers.

[0012] The cured product of the present invention is prevented from cracking even when subjected to repeated humidity resistance tests. The repeated moisture resistance test may be a test in which the moisture resistance test under Condition 1 below and the heating process under Condition 2 are alternately repeated three times. Condition 1 (humidity resistance test) 130°C, 85% relative humidity (RH), 96 hours Condition 2 (heating process) 175°C, 50% relative humidity (RH), 96 hours The mechanism by which the above effects are obtained is unknown, but is speculated as follows.

[0013] The inventors have found that in order to prevent cracks from occurring after repeated moisture resistance tests, three elements must function properly: suppressing moisture penetration; suppressing corrosion of the metal (preferably copper or an alloy containing copper, more preferably copper) surface, which is accelerated when moisture penetrates; and appropriately alleviating the interfacial stress that occurs when the metal corrodes. It is believed that it is effective for the Young's modulus to be within a specific range (2.5 GPa or more) and for Resin A to contain a structure represented by formula (X-A1). If the Young's modulus is 2.5 GPa or more, distortion is less likely to occur when moisture penetrates into the cured product, and since the structure represented by formula (X-A1) is a hydrophobic structure, it is presumed to have the effect of suppressing moisture penetration in a moisture resistance test. Next, regarding the inhibition of metal corrosion, it is believed that the presence of a nitrogen-containing heterocyclic compound and the inclusion of a structure represented by formula (X-A1) in Resin A are effective. It is presumed that the specific biphenyl structure forms a weak charge-transfer interaction with the nitrogen-containing heterocyclic compound, thereby distributing the nitrogen-containing heterocyclic compound nearly uniformly within the film. Furthermore, a specific range of Young's modulus (6.0 GPa or less) is thought to be effective in alleviating the interfacial stress that occurs when metals corrode. If the Young's modulus exceeds 6.0 GPa, brittle fracture is more likely to occur, and it is thought that even slight metal corrosion can cause cracks.

[0014] However, Patent Document 1 does not describe a cured product that corresponds to the cured product of the present invention.

[0015] The cured product of the present invention will be described in detail below.

[0016] <Characteristics of the cured product> The cured product of the present invention is a cured product obtained by curing a resin composition described below. The resin composition is preferably cured by heating, with the heating temperature being more preferably 120°C to 400°C, even more preferably 140°C to 380°C, and particularly preferably 170°C to 350°C. The form of the cured product is not particularly limited, and can be selected depending on the application, such as a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By patterning the resin composition, the form of the cured product can be selected depending on the application, such as forming a protective film on the wall surface, forming via holes for electrical continuity, adjusting impedance, capacitance, or internal stress, or imparting a heat dissipation function. 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 percentage of the resin composition upon curing is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage percentage refers to the percentage of volume change before and after curing of the resin composition, and can be calculated using the following formula. Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

[0017] The elongation at break of the cured product of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0018] <Young's modulus> The cured product of the present invention has a Young's modulus of 2.5 to 6.0 GPa. The Young's modulus is preferably 3.0 GPa or more, and more preferably 3.5 GPa or more. The Young's modulus is preferably 5.0 GPa or less, and more preferably 4.5 GPa or less. In the present invention, the Young's modulus of the cured product is calculated as follows. The Young's modulus of the cured product is measured in the longitudinal direction of the sample using a tensile tester (Instron Model 5965) at a crosshead speed of 300 mm / min, with a width of 2 mm and a length of 30 mm, in accordance with JIS-K7127:1999 at 23°C and 50% RH. The sample is prepared using a punching machine. The evaluation is carried out five times and the arithmetic average value is used.

[0019] <Resin A> [Repeating unit represented by formula (A-1)] The cured product of the present invention contains Resin A formed after curing of the resin composition. Resin A is a resin obtained by modifying resin B, such as by imidization, and preferably has a structure after polymerization when resin B has a polymerizable group. Also, when resin B has a polymerizable group and the resin composition contains a polymerizable compound, it preferably has a structure formed by polymerization of resin B and the polymerizable compound. Furthermore, resin A may contain a structure derived from a component contained in the resin composition, such as a photopolymerization initiator.

[0020] Resin A has a repeating unit represented by the following formula (A-1). [ka] In formula (A-1), X A1 is a structure represented by formula (X-A1), and Y A1 is a divalent linking group. [ka] In formula (X-A1), * represents the bonding site with the carbonyl group in formula (A-1).

[0021] -X A1 - X A1Formula (A-1) containing the above is preferably a structure represented by the following formula (A-1-2), and more preferably a structure represented by the following formula (A-1-3). [ka] In formula (A-1-2) and formula (A-1-3), Y A1 is a divalent linking group. In formula (A-1-2) and formula (A-1-3), Y A1 A preferred embodiment of the formula (A-1) is Y A1 This is the same as the preferred embodiment of the above.

[0022] -Y A1 - Y A1 The number of carbon atoms in the alkyl group is preferably 4 or more, more preferably 4 to 50, and even more preferably 4 to 40. In formula (A-1), Y A1 may be a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulae (V-1) to (V-10). The group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-10) improves the chemical resistance and flatness of the cured product. [ka] In formula (V-2), R X1 are each independently a hydrogen atom, an alkyl group, or a halogenated alkyl group. In formula (V-3), R X2 and R X3 each independently represents a hydrogen atom or a substituent, R X2 and R X3 may be bonded to form a ring structure. In formula (V-8), R X5 are each independently a hydrogen atom, an alkyl group, or a halogenated alkyl group.

[0023] In formula (V-2), R X1are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom has been substituted with a halogen atom. As the halogen atom, F or Cl is preferred, and F is more preferred. In formula (V-3), R X2 and R X3 are each preferably independently a hydrogen atom. X2 and R X3 When they are bonded to form a ring structure, R X2 and R X3 The structure formed by bonding is preferably a single bond, -O-, or -C(R)2-, more preferably -O- or -C(R)2-, and even more preferably -O-. R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom. In formula (V-8), R X5 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom has been substituted with a halogen atom. As the halogen atom, F or Cl is preferred, and F is more preferred.

[0024] Y A1 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-1), Y A1 is preferably a group represented by the following formula (V-1-2): In the following formula, * represents Y in formula (A-1). A1 represents the bonding site to the two nitrogen atoms to which n is bonded, and n1 represents an integer of 1 to 5. Furthermore, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0025] Y A1 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-2), Y A1 is preferably a group represented by the following formula (V-2-3) or formula (V-2-4), and from the viewpoint of reducing the dielectric constant of the cured product, it is preferably a group represented by formula (V-2-4). X1 represents a single bond or -O-, and * represents Y in formula (A-1). A1 represents the bonding site between the two nitrogen atoms. X1 The definitions and preferred embodiments of are as described above. In addition, the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0026] Y A1 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-3), Y A1 is preferably a group represented by the following formula (V-3-3) or formula (V-3-4), and from the viewpoint of reducing the dielectric constant of the cured product, it is preferably a group represented by formula (V-3-3). In the following formulas, * represents Y in formula (A-1). A1 represents the bonding site between the two nitrogen atoms. X2 and R X3 The definitions and preferred embodiments of are as described above. In addition, the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0027] Y A1 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-4), Y A1is preferably a group represented by the following formula (V-4-2) or formula (V-4-3): In the following formulas, * represents Y in formula (A-1). A1 represents the bonding site to the two nitrogen atoms to which n1 is bonded, and n1 represents an integer of 0 to 5. An embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. Furthermore, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, halogenated alkyl groups, and halogen atoms. [ka]

[0028] Y A1 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-5), Y A1 is preferably a group represented by the following formula (V-5-2): In the following formula, * represents Y in formula (A-1). A1 represents the bonding site between the two nitrogen atoms to which the two are bonded. The hydrogen atoms in formula (V-5-2) may be further substituted with known substituents such as hydrocarbon groups. Known substituents include alkyl groups, halogenated alkyl groups, and halogen atoms. However, it is also preferred that none of the hydrogen atoms in the structure represented by (V-5-2) are substituted. [ka]

[0029] Y A1 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-6), Y A1 is preferably a group represented by the following formula (V-6-2): In the following formula, * represents Y in formula (A-1). A1 represents the bonding site between the two nitrogen atoms to which the hydrogen atoms are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0030] Y A1 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-7), Y A1 is preferably a group represented by the following formula (V-7-2): In the following formula, * represents Y in formula (A-1). A1 represents the bonding site between the two nitrogen atoms to which the hydrogen atoms are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0031] Y A1 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-8), Y A1 is preferably a group represented by the following formula (V-8-2): In the following formula, * represents Y in formula (A-1). A1 represents the bonding site between the two nitrogen atoms. X5 The definition and preferred embodiments of are as described above. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0032] Y A1 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-9), Y A1 is preferably a group represented by the following formula (V-9-2): In the following formula, * represents Y in formula (A-1). A1 represents the bonding site between the two nitrogen atoms to which the hydrogen atoms are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0033] Y A1is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-10), Y A1 is preferably a group represented by the following formula (V-10-2): In the following formula, * represents Y in formula (A-1). A1 represents the bonding site between the two nitrogen atoms to which the hydrogen atoms are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0034] Others, Y A1 may be a group described in paragraphs 0042 to 0053 of JP-A No. 2023-003421. Also, Y A1 It is preferable that the structure does not contain an imide structure. Also, Y A1 It is preferable that the structure does not contain a urethane bond, a urea bond, or an amide bond. Furthermore, Y A1 It is preferable that the structure does not contain an ester bond. Among these, Y A1 It is preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0035] [Repeating unit represented by formula (A-2)] Resin A preferably has a repeating unit represented by the following formula (A-2). Here, the repeating unit represented by formula (A-2) is a repeating unit that does not fall under the repeating unit represented by formula (A-1) above. [ka] In formula (A-2), X A2 is a tetravalent organic group, and Y A2 is a divalent linking group and satisfies at least one of the following conditions 1 and 2: Condition 1:XA2 is a structure represented by the following formula (X-A2) Condition 2: Y A2 is a structure represented by the following formula (Y-A2): [ka] In formula (X-A2), * represents the bonding site with the carbonyl group in formula (A-2). [ka] In formula (Y-A2), * represents the bonding site with the nitrogen atom in formula (A-2).

[0036] -X A2 - If condition 1 is met, X A2 Formula (A-2) containing the above is preferably a structure represented by the following formula (A-2-2), and more preferably a structure represented by the following formula (A-2-3). [ka] In formula (A-2-2) and formula (A-2-3), Y A2 is a divalent linking group. In formula (A-2-2) and formula (A-2-3), Y A2 A preferred embodiment of the formula (A-2) is Y A2 This is the same as the preferred embodiment of the above.

[0037] If condition 1 is not met (only condition 2 is met), X A2 is a tetravalent organic group, and the tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or (6). In formula (5) or formula (6), * each independently represents a bonding site to another structure. [ka] In formula (5), R 112represents a single bond or a divalent linking group, and is preferably a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, a group selected from -O-, -CO-, -S-, -SO2-, and -NHCO-, or a combination thereof, more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, a group selected from -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-.

[0038] X A2 The number of carbon atoms in the alkyl group is preferably 4 or more, more preferably 4 to 50, and even more preferably 4 to 40.

[0039] Among these, X A2 is an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-10), the chemical resistance and flatness of the cured product are improved. Also, X A2 is an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-5), which can provide effects such as suppressing the generation of development residues, lowering the dielectric constant of the cured product, and reducing the thermal expansion coefficient. The organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-6) to (V-10) provides the following advantages: the pattern of the cured product is less likely to become tapered due to improved ultraviolet light transmittance; and the tolerance for exposure dose is wide.

[0040] X A2 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-1), X A2 is preferably a group represented by the following formula (V-1-1): In the following formula, * represents X in formula (A-2). A2represents the bonding site with the four carbonyl groups to which n1 is bonded, and n1 represents an integer of 1 to 5, and is also preferably an integer of 1 to 3. Furthermore, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0041] X A2 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-2), X A2 is preferably a group represented by the following formula (V-2-1) or formula (V-2-2), and from the viewpoint of lowering the amine value in the resin, it is preferably a group represented by formula (V-2-2). In this specification, a bond crossing a side of a ring structure means that it substitutes one of the hydrogen atoms in the ring structure. In the following formula, L X1 represents a single bond or -O-, and * represents X in formula (A-2). A2 represents the bonding site with the four carbonyl groups. X1 The definitions and preferred embodiments of are as described above. In addition, the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0042] X A2 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-3), X A2 is preferably a group represented by the following formula (V-3-1) or formula (V-3-2), and from the viewpoint of reducing the dielectric constant of the cured product, is preferably a group represented by formula (V-3-2). In the following formulas, * represents X in formula (A-2). A2 represents the bonding site with the four carbonyl groups. X2 and R X3 The definitions and preferred embodiments of are as described above. In addition, the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0043] X A2 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-4), X A2 is preferably a group represented by the following formula (V-4-1). In the following formula (V-4-1), * represents X in formula (A-2). A2 represents the bonding sites with the four carbonyl groups to which n1 is bonded, and n1 represents an integer of 0 to 5. Furthermore, the hydrogen atoms in formula (V-4-1) may be further substituted with known substituents such as hydrocarbon groups. Known substituents include alkyl groups, halogenated alkyl groups, and halogen atoms. However, it is also preferred that none of the hydrogen atoms in the structure represented by (V-4-1) are substituted. [ka]

[0044] X A2 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-5), X A2 is preferably a group represented by the following formula (V-5-1): In the following formula, * represents X in formula (A-2). A2 represents the bonding sites with the four carbonyl groups to which the carbonyl groups are bonded. The hydrogen atoms in formula (V-5-1) may be further substituted with known substituents such as hydrocarbon groups. Known substituents include alkyl groups, halogenated alkyl groups, and halogen atoms. However, it is also preferred that none of the hydrogen atoms in the structure represented by (V-5-1) are substituted. [ka]

[0045] X A2 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-6), X A2is preferably a group represented by the following formula (V-6-1): In the following formula, * represents X in formula (A-2). A2 represents the bonding sites with the four carbonyl groups to which the carbonyl groups are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0046] X A2 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-7), X A2 is preferably a group represented by the following formula (V-7-1): In the following formula, * represents X in formula (A-2). A2 represents the bonding sites with the four carbonyl groups to which the carbonyl groups are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0047] X A2 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-8), X A2 is preferably a group represented by the following formula (V-8-1): In the following formula, * represents X in formula (A-2). A2 represents the bonding site with the four carbonyl groups to which R is attached. X5 The definition and preferred embodiments of are as described above. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0048] X A2 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-9), X A2 is preferably a group represented by the following formula (V-9-1): In the following formula, * represents X in formula (A-2). A2represents the bonding sites with the four carbonyl groups to which the carbonyl groups are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0049] X A2 is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-10), X A2 is preferably a group represented by the following formula (V-10-1): In the following formula, * represents X in formula (A-2). A2 represents the bonding sites with the four carbonyl groups to which the carbonyl groups are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. [ka]

[0050] Other, X A2 may be a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic acid dianhydride described in paragraphs 0055 to 0057 of JP-A No. 2023-003421.

[0051] Also, X A2 It is preferable that the structure does not contain an imide structure. Also, X A2 It is preferable that the structure does not contain a urethane bond, a urea bond, or an amide bond. In the present invention, the urethane bond is *-OC(=O)-NR N - is a bond represented by *, and R N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. N is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom. In the present invention, the urea bond is *-NR N -C(=O)-NR N - is a bond represented by *, and R NR each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. N The preferred embodiments are as described above. Furthermore, X A2 It is preferable that the structure does not contain an ester bond. In the present invention, the ester bond is a bond represented by *--O--C(.dbd.O)--*. Among these, X A2 It is preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0052] In addition, X in formula (A-2) A2 may have a structure represented by the following formula (X-2). [ka] In formula (X-2), X 2 each independently represents a trivalent linking group; L 3 represents a divalent linking group, and * represents a bonding site to another structure.

[0053] In formula (X-2), X 2 is exemplified by a straight-chain or branched-chain aliphatic group, a cyclic aliphatic group, and an aromatic group, or a group in which two or more of these are linked together via a single bond or a linking group, and is preferably a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched-chain 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 in which two or more of these are combined together via a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined together via a single bond or a linking group. The linking group is preferably -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group 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 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. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The 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.

[0054] Also, X 2 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The halogenation is preferably chlorination. In the present invention, a compound having three carboxy groups is called a tricarboxylic acid compound. Two of the three carboxy groups of the tricarboxylic acid compound may be converted into acid anhydrides. Examples of the tricarboxylic acid compound which may be halogenated include branched aliphatic, cyclic aliphatic, and aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0055] X 2 It is preferable that the structure does not contain an imide structure. Also, X 2It is preferable that the structure does not contain a urethane bond, a urea bond, or an amide bond. Furthermore, X 2 It is preferable that the structure does not contain an ester bond. Among these, X 2 It is preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0056] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing 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 in which two or more of these are combined via a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0057] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, -CH2-, -C(CH3)2-, -C(CF3)2-, -SO2-, or a phenylene group. These compounds may be compounds in which two carboxy groups are anhydrides (for example, trimellitic anhydride), or may be compounds in which at least one carboxy group is halogenated (for example, trimellitic anhydride chloride).

[0058] In formula (X-2), L 3is exemplified by a straight-chain or branched-chain aliphatic group, a cyclic aliphatic group, an aromatic group, or a group in which two or more of these are linked together via a single bond or a linking group, and is preferably a straight-chain aliphatic group having 2 to 20 carbon atoms, a branched-chain 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 in which two or more of these are combined together via a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined together via a single bond or a linking group. The linking group is preferably -O-, -S-, -C(=O)-, -S(=O)2-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group 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 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. Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The 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.

[0059] Also, X A2 may have a structure represented by the following formula (X-3). [ka] In formula (X-3), X 2 each independently represents a trivalent linking group; L 3 represents a divalent linking group, and * represents a bonding site to another structure. In formula (X-3), X 2 and L 3 A preferred embodiment of the formula (X-2) is 2 and L 3 This is the same as the preferred embodiment of the above.

[0060] X A2 Specific examples of the X include tetracarboxylic acid residues remaining after removal of the anhydride groups from tetracarboxylic dianhydride. A2 As a structure corresponding to the above, only one type of tetracarboxylic dianhydride residue may be contained, or two or more types may be contained. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [ka] In formula (O), R 115 represents a tetravalent organic group. 115 The preferred range of X in formula (A-2) is A2 The preferred range is the same as that of the above.

[0061] 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, 2,2 ',3,3'-Diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-C6 alkyl and C1-C6 alkoxy derivatives thereof.

[0062] Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017 / 038598 are also preferred examples.

[0063] -Y A2 - If condition 2 is met, Y A2is a structure represented by formula (Y-A2). If condition 2 is not met (only condition 1 is met), Y A2 A preferred embodiment of the formula (A-1) is A1 This is the same as the preferred embodiment of the above.

[0064] In addition, it is also a preferred embodiment that the resin A contains a repeating unit represented by formula (A-2) that satisfies conditions 1 and 2.

[0065] [Repeating unit represented by formula (A-3)] Resin A preferably has a repeating unit represented by the following formula (A-3). Here, the repeating unit represented by formula (A-3) is a repeating unit that does not fall into either the repeating unit represented by formula (A-1) or the repeating unit represented by formula (A-2) described above. [ka] In formula (A-3), X A3 is a tetravalent organic group, and Y A3 is a divalent linking group and satisfies at least one of the following conditions 3 and 4. Condition 3:X A3 is a structure represented by the following formula (X-A3) Condition 4: Y A3 is a structure represented by any one of the following formulas (Y-A3) to (Y-A5): [ka] In formula (X-A3), * represents the bonding site with the carbonyl group in formula (A-3). [ka] In formulae (Y-A3) to (Y-A5), * represents the bonding site with the nitrogen atom in formula (A-3).

[0066] -X A3 - If condition 3 is met, X A3 Formula (A-3) containing the following is preferably a structure represented by formula (A-3-2): [ka]

[0067] If condition 3 is not met (only condition 4 is met), X A3 A preferred embodiment of the formula (A-2) is X when the condition 1 in the formula (A-2) is not satisfied. A2 This is the same as the preferred embodiment of the above.

[0068] -Y A3 - If condition 4 is met, Y A3 is a structure represented by any one of the following formulas (Y-A3) to (Y-A5). If condition 4 is not met (only condition 3 is met), Y A3 A preferred embodiment of the formula (A-2) is Y when the condition 2 in the formula (A-2) is not satisfied. A2 This is the same as the preferred embodiment of the above.

[0069] In addition, it is also a preferred embodiment that the resin A contains a repeating unit represented by formula (A-3) that satisfies conditions 3 and 4.

[0070] [Other repeating units] Resin A may further have other repeating units. Other repeating units include those represented by the following formula (A-4). The repeating unit represented by formula (A-4) is a repeating unit that does not fall into any of the repeating units represented by formula (A-1), formula (A-2), and formula (A-3). [ka] In formula (A-4), X A4 is a tetravalent organic group, and Y A4 is a divalent linking group. XA4 A preferred embodiment of the formula (A-2) is X when the condition 1 in the formula (A-2) is not satisfied. A2 This is the same as the preferred embodiment of the above. Y A4 A preferred embodiment of the formula (A-2) is Y when the condition 2 in the formula (A-2) is not satisfied. A2 This is the same as the preferred embodiment of the above. However, X A4 does not become a structure represented by formula (X-A2) or a structure represented by formula (X-A3), and Y A4 does not become a structure represented by any of formulas (Y-A2) to (Y-A5).

[0071] In one embodiment of Resin A, the total content of repeating units represented by Formula (A-1), Formula (A-2), Formula (A-3), or Formula (A-4) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular upper limit to the total content, and all repeating units in Resin A except for the terminal repeating units may be repeating units represented by Formula (A-1), Formula (A-2), Formula (A-3), or Formula (A-4).

[0072] In another embodiment of Resin A in the present invention, the content of the repeating units represented by formula (A-1) is preferably 20 to 100 mol % of all repeating units, more preferably 30 to 100 mol % of all repeating units, and even more preferably 40 to 80 mol % of all repeating units. In another embodiment of Resin A in the present invention, the total content of the repeating units represented by Formula (A-1) and the repeating units represented by Formula (A-2) is preferably 20 to 100 mol % of all repeating units, more preferably 30 to 100 mol % of all repeating units, and even more preferably 40 to 100 mol % of all repeating units. In another embodiment of Resin A in the present invention, the total content of the repeating units represented by Formula (A-1) and the repeating units represented by Formula (A-3) is preferably 20 to 100 mol % of all repeating units, more preferably 30 to 100 mol % of all repeating units, and even more preferably 40 to 100 mol % of all repeating units. In another embodiment of Resin A in the present invention, the total content of the repeating units represented by Formula (A-1), the repeating units represented by Formula (A-2), and the repeating units represented by Formula (A-3) is preferably 50 to 100 mol % of all repeating units, more preferably 60 to 100 mol % of all repeating units, and even more preferably 70 to 100 mol % of all repeating units.

[0073] From the viewpoint of adhesiveness, it is also preferable that Resin A is substantially free of fluorine atoms. Here, "substantially free" means that the amount of fluorine atoms relative to the total mass of Resin A is less than 5% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, and even more preferably less than 0.01% by mass. There is no particular lower limit for the amount of fluorine atoms, and it may be 0% by mass.

[0074] The content of Resin A is preferably from 70 to 99.9 parts by mass, more preferably from 80 to 99.8 parts by mass, based on the total mass of the cured product. Only one type of resin A may be used, or two or more types may be used. When two or more types are used, the total amount thereof preferably falls within the above range.

[0075] <Nitrogen-containing heterocyclic compounds> The cured product of the present invention contains a nitrogen-containing heterocyclic compound. As the nitrogen-containing heterocyclic compound, a compound containing a nitrogen atom as a ring member in an aromatic ring is preferred. For example, by including a nitrogen-containing heterocyclic compound in the resin composition for forming the cured product, a composition containing a nitrogen-containing heterocyclic compound can be obtained.

[0076] The nitrogen-containing heterocyclic compound is not particularly limited, and examples thereof include compounds having a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, and a triazine ring. 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 are preferably used. Among these, the cured product preferably contains 8-azaadenine.

[0077] When the cured product contains a nitrogen-containing heterocyclic compound, the content of the nitrogen-containing heterocyclic compound is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, relative to the total mass of the cured product.

[0078] The nitrogen-containing heterocyclic compound may be one kind or two or more kinds. When two or more kinds of nitrogen-containing heterocyclic compounds are used, the total amount thereof is preferably within the above range.

[0079] <Antioxidants> The cured product of the present invention may contain an antioxidant. In the present invention, the antioxidant refers to a compound that has the function of preventing oxidation of metals, and examples thereof include phenolic compounds, phosphite ester compounds, and thioether compounds. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at the position adjacent to the phenolic hydroxy group (ortho position) are preferred. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Furthermore, preferred antioxidants include compounds having a phenol group and a phosphite ester group in the same molecule. It is believed that the antioxidant prevents oxidation of the metal, and therefore, the cured product containing the antioxidant has excellent adhesion. Furthermore, since the antioxidant inhibits polymerization of the polymerizable compound during storage of the resin composition, it is believed that a resin composition containing an antioxidant has excellent storage stability and excellent resolution of the resulting cured product.

[0080] The antioxidant preferably has an isocyanuric acid skeleton, and more preferably is a hindered phenol compound having an isocyanuric acid skeleton.

[0081] Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and the compound represented by formula (3).

[0082] [ka]

[0083] In general formula (3), R 5 represents a hydrogen atom or an alkyl group having one or more carbon atoms, and R 6 represents an alkylene group having 1 or more carbon atoms, an alkylenecarbonyl group having 2 or more carbon atoms, or an alkylenecarbonyloxy group having 2 or more carbon atoms; R 7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having two or more carbon atoms, an O atom, and an N atom; i represents an integer of 1 to 4; j represents an integer of 0 to 4; i+j is an integer of 1 to 4; and k represents an integer of 1 to 4.

[0084] By including the compound represented by general formula (3), oxidation of the metal is inhibited, and oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups of the resin is inhibited.

[0085] R 5 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. R 6When is an alkylene group, it is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. R 6 When R is an alkylenecarbonyl group, it is preferably an alkylenecarbonyl group having 3 to 6 carbon atoms, more preferably a methyl group. 7 It is preferred that the ATP is present at the binding site with the ATP. R 6 When is an alkylenecarbonyloxy group, it is preferably an alkylenecarbonyloxy group having 3 to 4 carbon atoms, more preferably a methyl group. R 7 Examples of the alkyl group include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, alkyl ether, -NH- and isocyanuric rings are preferred from the viewpoint of developability and metal adhesion, and isocyanuric rings are more preferred from the viewpoint of interaction with resins and metal adhesion due to metal complex formation.

[0086] i is preferably 1 or 2, and more preferably 1. j is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. k is more preferably an integer of 2 to 4.

[0087] Examples of the compound represented by the following general formula (3) include, but are not limited to, the following structures.

[0088] [ka]

[0089] [ka]

[0090] [ka] [ka]

[0091] [ka]

[0092] Other examples of antioxidants include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0093] Specific examples of these compounds include the compounds described in paragraph 0310 of WO 2021 / 112189, p-hydroquinone, o-hydroquinone, p-methoxyphenol, 2-nitroso-1-naphthol, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc., the contents of which are incorporated herein by reference.

[0094] Alternatively, phosphorus-based antioxidants may be suitably used, such as tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Commercially available antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (all manufactured by ADEKA Corporation). The compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants. The composition of the present invention may also contain a latent antioxidant, if necessary. Examples of latent antioxidants include compounds in which the moiety functioning as an antioxidant is protected with a protecting group, and which function as an antioxidant upon heating at 100 to 250°C or at 80 to 200°C in the presence of an acid / base catalyst, whereby the protecting group is eliminated. Examples of latent antioxidants include compounds described in International Publication Nos. 2014 / 021023, 2017 / 030005, and JP-A No. 2017-008219. Commercially available latent antioxidants include ADEKA ARCLES GPA-5001 (manufactured by ADEKA Corporation).

[0095] The amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, based on the total mass of the cured product. The antioxidant may be used alone or in combination of two or more kinds. When two or more kinds are used, the total amount thereof is preferably within the above range.

[0096] <Other compounds> The cured product of the present invention may further contain other components. Examples of other components include components contained in the resin composition described below, and components obtained by chemically modifying components contained in the resin composition described below, such as components obtained after polymerization of the polymerizable compound described below.

[0097] <Resin composition> The cured product of the present invention is obtained by curing a resin composition containing at least one resin B selected from the group consisting of polyimides and polyimide precursors, and a polymerization initiator. A preferred embodiment of the resin composition will now be described.

[0098] [Resin B]

[0099] -Repeating unit represented by at least one of formula (B1-1) and formula (B2-1)- Resin B preferably has a repeating unit represented by at least one of the following formula (B1-1) and formula (B2-1). [ka] In formula (B1-1), A B1 and A B2 each independently represents -O- or -NR Z - and R Z is a hydrogen atom or a monovalent organic group, and R B1 and R B2 are each independently a hydrogen atom or a monovalent organic group, and X B1 is a structure represented by formula (X1-B1), and Y B1 is a divalent linking group. In formula (B2-1), X B2 is a structure represented by formula (X2-B1), and Y B2 is a divalent linking group. [ka] In formula (X2-B1), * represents the bonding site with the carbonyl group in formula (B1-1). [ka] In formula (X2-B1), * represents the bonding site with the carbonyl group in formula (B2-1).

[0100] Resin B preferably contains a polymerizable group, and more preferably contains a radically polymerizable group. Furthermore, the resin composition preferably satisfies at least one of the following conditions: (1) Resin B has a polymerizable group; and (2) Resin B further contains a polymerizable compound that does not fall under the category of Resin B. When the resin B has a radical polymerizable group, the resin composition preferably contains a radical polymerization initiator, more preferably contains both a radical polymerization initiator and a radical crosslinking agent. If necessary, the resin composition may further contain a sensitizer. For example, a negative photosensitive film can be formed from such a resin composition. Furthermore, the resin B may have a polarity conversion group such as an acid-decomposable group. When Resin B has an acid-decomposable group, the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive or negative photosensitive film is formed.

[0101] -A B1 and A B2 - In formula (B1-1), A B1 and A B2 are each independently preferably -O-. B1 and A B2 At least one of the following is -NR Z -If R Z is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0102] -R B1 and R B2 - In formula (B1-1), R B1 and R B2Each of R independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. B1 and R B2 Preferably, at least one of R contains a polymerizable group, and more preferably, both of R B1 and R B2 It is also preferable that at least one of the groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a radically polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group contained in the polyimide precursor is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.

[0103] [ka]

[0104] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site to another structure. In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH2CH(OH)CH2-, a cycloalkylene group, or a polyalkyleneoxy group. Suitable R 201Examples of the alkylene group include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene; 1,2-butanediyl, 1,3-butanediyl, -CHCH(OH)CH-; and polyalkyleneoxy groups. Of these, alkylene groups such as ethylene and propylene, -CHCH(OH)CH-, cyclohexyl, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups are even more preferred. In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When the polyalkyleneoxy group contains multiple types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, still more preferably 2 to 5, still more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2. The alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6. As the polyalkyleneoxy group, from the viewpoint of solvent solubility and solvent resistance, a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is preferred, a polyethyleneoxy group or a polypropyleneoxy group is more preferred, and a polyethyleneoxy group is even more preferred. In the group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiments of the number of repetitions of the ethyleneoxy groups etc. in these groups are as described above.

[0105] In formula (B1-1), R B1 is a hydrogen atom, or R B2 When 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.

[0106] In formula (B1-1), R B1 and R B2 At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0107] In formula (B1-1), X B1 A preferred embodiment of the formula (A-1) is A1 This is the same as the preferred embodiment of the above. In formula (B1-1), Y B1 A preferred embodiment of the formula (A-1) is A1 This is the same as the preferred embodiment of the above.

[0108] In formula (B2-1), X B2 A preferred embodiment of the formula (A-1) is A1 This is the same as the preferred embodiment of the above. In formula (B2-1), Y B2 A preferred embodiment of the formula (A-1) is A1 This is the same as the preferred embodiment of the above.

[0109] -Repeating unit represented by at least one of formula (B1-2) and formula (B2-2)- The resin B is preferably a resin having a repeating unit represented by at least one of the following formulas (B1-2) and (B2-2). [ka] In formula (B1-2), A B3 and A B4 each independently represents -O- or -NR Z - and R Z is a hydrogen atom or a monovalent organic group, and R B3 and R B4 are each independently a hydrogen atom or a monovalent organic group, and X B3 is a tetravalent organic group, and Y B3 is a divalent linking group and satisfies at least one of the following conditions 5 and 6. In formula (B2-2), X B4 is a tetravalent organic group, and Y B4 is a divalent linking group and satisfies at least one of the following conditions 7 and 8. Condition 5:X B3 is a structure represented by the following formula (X1-B2) Condition 6: YB3 is a structure represented by the following formula (Y1-B2): Condition 7:X B4 is a structure represented by the following formula (X2-B2) Condition 8: Y B4 is a structure represented by the following formula (Y2-B2): [ka] In formula (X1-B2), * represents the bonding site with the carbonyl group in formula (B1-2). [ka] In formula (Y1-B2), * represents the bonding site with the nitrogen atom in formula (B1-2). [ka] In formula (X2-B2), * represents the bonding site with the carbonyl group in formula (B2-2). [ka] In formula (Y2-B2), * represents the bonding site to the nitrogen atom in formula (B2-2).

[0110] In formula (B1-2), A B3 , A B4 , R B3 and R B4 A preferred embodiment of the formula (B1-1) is B1 , A B2 , R B1 and R B2 This is the same as the preferred embodiment of the above. In formula (B1-2), X B3 and Y B3 A preferred embodiment of the formula (A-2) is A2 and Y A2 This is the same as the preferred embodiment of the above.

[0111] In formula (B2-2), X B4 and Y B4A preferred embodiment of the formula (A-2) is A2 and Y A2 This is the same as the preferred embodiment of the above.

[0112] -Repeating unit represented by at least one of formula (B1-3) and formula (B2-3)- Resin B is preferably a resin having a repeating unit represented by at least one of the following formula (B1-3) and formula (B2-3). The repeating unit represented by formula (B1-3) is a repeating unit that does not fall under the category of the repeating unit represented by formula (B1-1) or the repeating unit represented by formula (B1-2). The repeating unit represented by formula (B2-3) is a repeating unit that does not fall under the category of the repeating unit represented by formula (B2-1) or the repeating unit represented by formula (B2-2). [ka] In formula (B1-3), A B5 and A B6 each independently represents -O- or -NR Z - and R Z is a hydrogen atom or a monovalent organic group, and R B5 and R B6 are each independently a hydrogen atom or a monovalent organic group, and X B5 is a tetravalent organic group, and Y B5 is a divalent linking group and satisfies at least one of the following conditions 9 and 10. In formula (B2-3), X B6 is a tetravalent organic group, and Y B6 is a divalent linking group and satisfies at least one of the following conditions 11 and 12. Condition 9:X B5 is a structure represented by the following formula (X1-B3) Condition 10: Y B5 is a structure represented by any one of the following formulas (Y1-B3) to (Y1-B5): Condition 11:X B6 is a structure represented by the following formula (X2-B3) Condition 12: Y B6is a structure represented by any one of the following formulas (Y2-B3) to (Y2-B5): [ka] In formula (X1-B3), * represents the bonding site with the carbonyl group in formula (B1-3). [ka] In formulae (Y1-B3) to (Y1-B5), * represents the bonding site with the nitrogen atom in formula (B1-3). [ka] In formula (X2-B3), * represents the bonding site with the carbonyl group in formula (B2-3). [ka] In formulae (Y2-B3) to (Y2-B5), * represents the bonding site with the nitrogen atom in formula (B2-3).

[0113] In formula (B1-3), A B5 , A B6 , R B5 and R B6 A preferred embodiment of the formula (B1-1) is B1 , A B2 , R B1 and R B2 This is the same as the preferred embodiment of the above. In formula (B1-3), X B5 and Y B5 A preferred embodiment of the formula (A-3) is A3 and Y A3 This is the same as the preferred embodiment of the above.

[0114] In formula (B2-3), X B6 and Y B6 A preferred embodiment of the formula (A-3) is A3 and Y A3 This is the same as the preferred embodiment of the above.

[0115] -Repeating unit represented by at least one of formula (B1-4) and formula (B2-4)- Resin B is preferably a resin having a repeating unit represented by at least one of the following formula (B1-4) and formula (B2-4). The repeating unit represented by formula (B1-4) is a repeating unit that does not fall under the repeating unit represented by formula (B1-1), the repeating unit represented by formula (B1-2), or the repeating unit represented by formula (B1-3). The repeating unit represented by formula (B2-4) is a repeating unit that does not fall under the repeating units represented by formula (B2-1), formula (B2-2) or formula (B2-3). [ka] In formula (B1-4), A B7 and A B8 each independently represents -O- or -NR Z - and R Z is a hydrogen atom or a monovalent organic group, and R B7 and R B8 are each independently a hydrogen atom or a monovalent organic group, and X B7 is a tetravalent organic group, and Y B7 is a divalent linking group. In formula (B2-4), X B8 is a tetravalent organic group, and Y B8 is a divalent linking group.

[0116] In formula (B1-4), A B7 , A B8 , R B7 and R B8 A preferred embodiment of the formula (B1-1) is B1 , A B2 , R B1 and R B2 This is the same as the preferred embodiment of the above. In formula (B1-4), X B7 and Y B7 A preferred embodiment of the formula (A-4) is A4 and Y A4 This is the same as the preferred embodiment of the above.

[0117] In formula (B2-4), X B8 and Y B8 A preferred embodiment of the formula (A-4) is A4 and Y A4 This is the same as the preferred embodiment of the above.

[0118] In one embodiment of Resin B, the total content of repeating units represented by Formula (B1-1), Formula (B2-1), Formula (B1-2), Formula (B2-2), Formula (B1-3), Formula (B2-3), Formula (B1-4), or Formula (B2-4) is 50 mol% or more of all repeating units. This total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably greater than 90 mol%. There is no particular upper limit to this total content, and all repeating units in Resin B, excluding terminal repeating units, may be repeating units represented by Formula (B1-1), Formula (B2-1), Formula (B1-2), Formula (B2-2), Formula (B1-3), Formula (B2-3), Formula (B1-4), or Formula (B2-4).

[0119] In another embodiment of Resin B of the present invention, the total content of repeating units represented by formula (B1-1) or formula (B2-1) is preferably 20 to 100 mol % of all repeating units, more preferably 30 to 100 mol % of all repeating units, and even more preferably 40 to 80 mol % of all repeating units. In another embodiment of Resin B of the present invention, the total content of repeating units represented by formula (B1-1), formula (B2-1), formula (B1-2) or formula (B2-2) is preferably 30 to 100 mol % of all repeating units, more preferably 40 to 100 mol % of all repeating units, and even more preferably 50 to 100 mol % of all repeating units. In another embodiment of Resin B of the present invention, the total content of repeating units represented by Formula (B1-1), Formula (B2-1), Formula (B1-3) or Formula (B2-3) is preferably 30 to 100 mol % of all repeating units, more preferably 40 to 100 mol % of all repeating units, and even more preferably 50 to 100 mol % of all repeating units. In another embodiment of Resin B of the present invention, the total content of repeating units represented by Formula (B1-1), Formula (B2-1), Formula (B1-2), Formula (B2-2), Formula (B1-3) or Formula (B2-3) is preferably 50 to 100 mol % of all repeating units, more preferably 60 to 100 mol % of all repeating units, and even more preferably 70 to 100 mol % of all repeating units.

[0120] From the viewpoint of adhesiveness, it is also preferable that Resin B contains substantially no fluorine atoms. Here, "substantially no fluorine atoms" means that the amount of fluorine atoms relative to the total mass of Resin B is less than 5% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, and even more preferably less than 0.01% by mass. There is no particular lower limit for the amount of fluorine atoms, and it may be 0% by mass.

[0121] [Imidization rate] The imidization rate of Resin B is preferably 3 to 40%. From the viewpoint of elongation at break, the imidization rate is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more. From the viewpoint of resolution, the imidization rate is preferably 35% or less, more preferably 30% or less, and even more preferably 25% or less.

[0122] In the present invention, the imidization rate is a value calculated by the following method. The resin is dissolved in γ-butyrolactone, diluted to a viscosity of 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in γ-butyrolactone, the solvent may be changed to another solvent. Examples of other solvents include solvents contained in the resin composition, such as NMP. The viscosity may also be adjusted as needed. The silicon wafer with the resulting resin layer applied is dried on a hot plate at 110°C for 5 minutes to obtain a uniform resin layer with a film thickness of approximately 15 μm on the silicon wafer. If only a low-viscosity resin solution is obtained, making it difficult to obtain a resin layer with a film thickness of 15 μm, the film thickness may be adjusted as needed. For example, a film thickness of 5 μm or more will result in a similar imidization rate. The resin layer was measured by the ATR method using a NicoletiS20 (manufactured by Thermofisher) in the measurement range of 4000 to 700 cm -1 , 50 measurements are taken. 1380cm -1 Around (1350~1450cm -1 (If there are multiple peaks, the peak with the highest intensity) and 1500 cm -1 Around (1460~1550cm -1 The imidization index B is calculated in the same manner for a film that has been heated at a rate of 10°C / min in a nitrogen atmosphere and then heated at 350°C for 1 hour, and the imidization rate of the resin is calculated by dividing the imidization index A by the imidization index B. In measuring the imidization rate, the resin to be measured can be obtained from the composition by, for example, the following method: A solution of 1 g of the composition and 2 g of tetrahydrofuran is added to 50 g of methanol or water to cause crystallization, and the resin is precipitated and filtered. The residue is recovered, dissolved in 3.0 g of THF (tetrahydrofuran), and added to 50 g of methanol or water to cause crystallization. The crystallized resin is filtered and dried at 45°C for 20 hours to obtain the resin. Hereinafter, when measuring the physical properties of Resin B, such as the acid value and amine value, the resin can be obtained and measured in the same manner.

[0123] [Acid value] The acid value of Resin B is preferably 0.0010 to 0.3000 mmol / g, more preferably 0.02 to 0.150 mmol / g, and even more preferably 0.03 to 0.100 mmol / g. The acid value is measured by a known method, for example, under the following conditions. Conditions: 0.300 g of resin was dissolved in 80 mL of NMP, then 5 mL of water was added and titrated with a 0.01 mol / L KOH aqueous solution. Whether the resin has dissolved or not can be confirmed by visual inspection that no residue remains. If the above amount of resin does not completely dissolve in NMP, the amount of resin may be appropriately reduced and measurement may be performed at a concentration at which the resin completely dissolves.

[0124] Furthermore, from the viewpoint of adhesion, the amount of acidic functional groups in Resin B, at which the pH of the neutralization point is in the range of 7.0 to 12.0, is preferably 0.0010 to 0.3000 mmol / g, more preferably 0.02 to 0.150 mmol / g, and even more preferably 0.03 to 0.100 mmol / g. The amount of acidic functional groups at the neutralization point in the pH range of 7.0 to 12.0 is measured by the same method as described in the Examples below. Specifically, 0.30 g of resin is dissolved in 80 mL of NMP, and 5 mL of water is added to prepare a measurement solution. The solution is titrated with a 0.01 N (0.01 mol / L) aqueous potassium hydroxide (KOH) solution, and the amount of acidic functional groups is calculated from the peak in the pH range of 7.0 to 12.0.

[0125] [Amine value] From the viewpoint of storage stability of the composition, the amine value of Resin B is preferably 0.001 to 0.300 mmol / g or less, more preferably 0.01 to 0.200 mmol / g, and even more preferably 0.03 to 0.100 mmol / g. The amine value is measured by dissolving 0.60 g of resin in 50 mL of diglyme, adding 10 mL of acetic acid to prepare a measurement solution, and titrating the solution with a 0.01 N (0.01 mol / L) perchloric acid solution in acetic acid to detect the neutralization point.

[0126] Resin B preferably contains a structure represented by the following formula (1), and more preferably the molar content of the structure represented by formula (1) relative to the total solid content of the resin composition is 0.01 to 1.0 mmol / g. The molar amount contained is preferably 0.015 to 0.5 mmol / g, and more preferably 0.02 to 0.3 mmol / g. [ka] In formula (1), R 1 and R 2 each independently represents a saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms; X 1 represents an oxygen atom or a sulfur atom, and L 1 represents -C(=O)- or -S(=O)2-, * 1 and* 2 each independently represents a binding site to another structure, and R 1 , R 2 , * 1 A structure that binds to * 2 At least two of the structures bonded to may be bonded to form a ring structure.

[0127] In formula (1), R 1 and R 2 are each independently preferably a saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms. The saturated aliphatic hydrocarbon group is more preferably an isopropyl group or a cyclohexyl group. The hydrogen atoms of the above aliphatic hydrocarbon groups may be substituted with known substituents, but in one preferred embodiment of the present invention, the groups have no substituents. The substituent on the phenyl group is preferably a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 5 to 10 carbon atoms, more preferably a branched alkyl group having 3 to 6 carbon atoms, and particularly preferably an isopropyl group. The number of the above-mentioned substituents is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 2.

[0128] In formula (1), X 1 is preferably an oxygen atom.

[0129] In formula (1), L 1 is preferably —C(═O)—.

[0130] In formula (1), R 1 , R 2 , * 1 A structure that binds to * 2 At least two of the structures bonded to may be bonded to form a ring structure. Examples of the ring structure that is formed include, but are not limited to, a hydantoin ring and an N-acylimidazolidinone ring. In the present invention, R 1 , R 2 , * 1 A structure that binds to * 2 In another preferred embodiment, none of the structures bonded to form a ring structure.

[0131] Resin B preferably contains a structure represented by the following formula (1-5) as a structure having a structure represented by formula (1). [ka] In formula (1-5), R 51 each independently represents a saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms; R 52 is a hydrogen atom or an organic group, and * represents the bonding site with the resin structure. In formula (1-5), R 51A preferred embodiment of the formula (1) is 1 This is the same as the preferred embodiment of the above. In formula (1-5), R 52 is preferably a hydrogen atom. 52 In a preferred embodiment, when R is an organic group, 51 This is the same as the preferred embodiment of the above.

[0132] The structure represented by formula (1-5) may be present at the end of the main chain of the resin, or may be present in a side chain. For example, R in formula (B1-1) B1 , A B1 and a carbonyl group, R B2 , A B2 and a carbonyl group, R in formula (B1-2) B3 , A B3 and a carbonyl group, R B4 , A B4 and a carbonyl group, R in formula (B1-3) B5 , A B5 and a carbonyl group, R B6 , A B6 and a carbonyl group, R in formula (B1-4) B7 , A B7 and a carbonyl group, and R B8 , A B8 and at least one of the carbonyl groups constitutes a structure represented by formula (1-5). As the structure represented by formula (1-5), for example, resin B preferably has a structure represented by the following formula (1-5-1) or formula (1-5-2). [ka] In formula (1-5-1), A 2 -O- or -NR Z - and R Z is a hydrogen atom or a monovalent organic group, and R 2 is a hydrogen atom or a monovalent organic group, and X 2 is a tetravalent organic group, and R A is a group represented by the above formula (1-5), and * is a bonding site to other structures. In formula (1-5-2), A 41 and A 42 each independently represents -O- or -NR Z - and R Z is a hydrogen atom or a monovalent organic group, and R 41 and R 42 are each independently a hydrogen atom or a monovalent organic group, and X 4 is a tetravalent organic group, and R A is a group represented by the above formula (1-5), and * is a bonding site to other structures. In formula (1-5-1), A 2 , R Z and R 2 A preferred embodiment of the formula (B1-1) is B1 , R Z and R B1 This is the same as the preferred embodiment of the above. In formula (1-5-1), X 2 A preferred embodiment of the formula (B2-1) is X B2 , X in formula (B2-2) B4 , X in formula (B2-3) B6 , X in formula (B2-4) B8 This is similar to any of the preferred embodiments. In formula (1-5-2), A 41 , A 42 , R Z , R 41 and R 42 A preferred embodiment of the formula (B1-1) is B1 , A B2 , R Z , R B1 and R B2 This is the same as the preferred embodiment of the above. In formula (1-5-2), X 4 A preferred embodiment of the formula (B1-1) is X B1 , X in formula (B1-2) B3 , X in formula (B1-3) B5 , X in formula (B1-4) B7 This is similar to any of the preferred embodiments.

[0133] The content of the structure represented by formula (1-5) in Resin B is, for example, preferably 0.01 to 1.0 mmol / g, and more preferably 0.01 to 0.85 mmol / g. The content of the structure represented by formula (1-5) in the total solid content of the resin composition is, for example, preferably 0.01 to 0.5 mmol / g, and more preferably 0.01 to 0.4 mmol / g.

[0134] Furthermore, the ratio of the molar amount of amic acid ester structures to the total molar amount of amic acid structures and amic acid ester structures in Resin B (esterification rate) is preferably 90 to 99.9% or more, more preferably 92 to 99.5%, and even more preferably 95 to 99%. The esterification rate can be estimated from the acid value and structure of the resin.

[0135] The weight average molecular weight (Mw) of Resin B is preferably 120,000 or less, more preferably 50,000 or less, and even more preferably 40,000 or less. Furthermore, the Mw is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more. The number average molecular weight (Mn) of Resin B is preferably 40,000 or less, more preferably 30,000 or less, and even more preferably 20,000 or less. Furthermore, the Mn is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more. The molecular weight dispersity of the resin B is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit for the molecular weight dispersity of the resin B, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the molecular weight dispersity is a value calculated by weight average molecular weight / number average molecular weight. When the resin composition contains multiple types of resin B, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of resin B are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple types of resin B as one resin are each within the above ranges.

[0136] [Method for producing resin B] Resin B can be produced, for example, by the method described in paragraphs 0134 to 0136 of WO 2022 / 145355. The above description is incorporated herein by reference. Alternatively, resin B can be synthesized by referring to other known methods.

[0137] [Content] The content of resin B in the resin composition 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. The content of resin B in the resin composition 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 may contain only one type of resin B, or may contain two or more types of resin B. When two or more types are contained, the total amount preferably falls within the above range.

[0138] [Other resins] The resin composition may contain the above-mentioned resin B and another resin different from resin B (hereinafter, simply referred to as "another resin"). Examples of other resins include polyimide precursors not corresponding to Resin B, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamides not corresponding to polyimide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described later, a polymerizable compound having a weight average molecular weight of 20,000 or less and a high polymerizable group value (for example, a polymerizable compound having a molar content of 1×10 per 1 g of resin) may be used. -3 By adding a (meth)acrylic resin (having a molecular weight of 1000 to 1000 mol / g or more) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0139] When the resin composition 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, still more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total solid content of the resin composition. When the resin composition contains other resins, the content of the other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the resin composition. A preferred embodiment of the resin composition may have a low content of other resins. In this embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, and may be 0% by mass or more. The resin composition may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0140] <Antioxidants> The resin composition preferably contains an antioxidant. The definition and preferred embodiments of the antioxidant are the same as the preferred embodiments of the antioxidant contained in the first cured product described above.

[0141] The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, based on the total solid content of the resin composition. The antioxidant may be used alone or in combination of two or more kinds. When two or more kinds are used, the total amount thereof is preferably within the above range.

[0142] [Polymerizable compound] The resin composition preferably contains a polymerizable compound. The polymerizable compound may be a radical crosslinking agent or other crosslinking agent.

[0143] [Radical crosslinking agent] The resin composition preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group. Among these, a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

[0144] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds, and may also have three or more ethylenically unsaturated bonds. The compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds. From the viewpoint of the film strength of the resulting pattern (cured product), it is also preferable that the resin composition contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0145] 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.

[0146] 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.), their esters, and amides. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyamine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl group, amino group, or sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogeno group or a tosyloxy group with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, it is also possible to use a compound group in which the above-mentioned unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, etc. For specific examples, see paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0147] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0148] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0149] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), and dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), as well as compounds in which the (meth)acryloyl groups are bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these compounds can also be used.

[0150] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates having four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, a trifunctional acrylate having three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers such as Examples of such an agent include UAS-10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).

[0151] Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, and urethane compounds having an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418. Compounds having an amino structure or a sulfide structure in the molecule, such as those described in JP-A Nos. 63-277653, 63-260909, and 1999-105238, can also be used as radical crosslinking agents.

[0152] The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound. Particularly preferred is a radical crosslinking agent in which an acid group is provided by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers such as M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0153] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH / g, more preferably 1 to 100 mgKOH / g. When the acid value of the radical crosslinking agent is within the above range, the agent has excellent handleability in production and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0154] The radical crosslinking agent is preferably a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U"). When the resin composition contains the crosslinking agent U, the chemical resistance, resolution, etc. may be improved. Examples of the crosslinking agent U include compounds described in paragraphs 0133 to 0143 of WO 2023 / 190064, the contents of which are incorporated herein by reference.

[0155] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a difunctional methacrylate or acrylate for 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, EO (ethylene oxide) adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO (propylene oxide) 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, other bifunctional acrylates having urethane bonds, 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 with a formula weight of about 200 for the polyethylene glycol chain. From the viewpoint of suppressing warpage of the pattern (cured product), the resin composition preferably uses a monofunctional radical crosslinking agent as the radical crosslinking agent. Examples of the monofunctional radical crosslinking agent 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; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds having a boiling point of 100°C or higher under normal pressure are also preferred as the monofunctional radical crosslinking agent. Other examples of the bifunctional or higher functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0156] When a radical crosslinking agent is contained, the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass relative to the total solid content of the resin composition. 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.

[0157] The radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.

[0158] [Other crosslinking agents] The resin composition preferably contains a crosslinking agent other than the above-mentioned radical crosslinking agent. The other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by a photoacid generator or a photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof. The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step. Other cross-linking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022 / 145355, which are incorporated herein by reference.

[0159] [Photosensitizer] The resin composition includes a photosensitizer. Examples of the photosensitizer include a photopolymerization initiator and a photoacid generator, and a photopolymerization initiator is preferred.

[0160] [Photopolymerization initiator] The resin composition preferably contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0161] The photoradical polymerization initiator has a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm) and a concentration of at least about 50 L·mol -1 ·cm -1Preferably, the composition contains at least one compound having a molar absorption coefficient of 0.01 g / L. The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0162] Any known photoradical polymerization initiator can be used. 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, hexaarylbiimidazoles, oxime compounds such as 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, organic boron compounds, and iron arene complexes. For details, see paragraphs

[0165] to

[0182] of JP 2016-027357 A and paragraphs

[0138] to

[0151] of WO 2015 / 199219 A, the contents of which are incorporated herein by reference. Further, paragraphs 0065 to 0111 of JP 2014-130173 A, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol.19, No.3,2019 described peroxide-based photopolymerization initiators, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A are mentioned, the contents of which are incorporated herein by reference.

[0163] Examples of ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0164] In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, or an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 or an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.

[0165] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

[0166] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF).

[0167] As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of WO 2021 / 112189 can also be suitably used. The contents of this specification are incorporated herein by reference.

[0168] As the photoradical polymerization initiator, an oxime compound is more preferably used. By using an oxime compound, it is possible to more effectively improve the exposure latitude. An oxime compound is particularly preferred because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.

[0169] Specific examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232) compounds described in, compounds described in JP-A-2000-066385, compounds described in JP-T-2004-534797, compounds described in JP-A-2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in WO 2015 / 152153, compounds described in WO 2017 / 051680, compounds described in JP-A-2017-198865, compounds described in paragraphs 0025 to 0038 of WO 2017 / 164127, compounds described in WO 2013 / 167515, and the like, the contents of which are incorporated herein by reference.

[0170] Preferred oxime compounds include, for example, compounds having the following structure: 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-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one. In resin compositions, it is particularly preferred to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group >C=NOC(=O)- within the molecule.

[0171] [ka]

[0172] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, and IRGACURE OXE 05 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemistry Co., Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Oxime compounds having the following structure can also be used. [ka] [ka]

[0173] As the photoradical polymerization initiator, for example, an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of WO 2021 / 112189, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, or an oxime compound having a fluorine atom can be used. In addition, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group-containing substituent bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of WO 2021 / 020359, the contents of which are incorporated herein by reference.

[0174] In addition, compounds described in paragraphs 0113 to 0117 of JP-A No. 2023-058585 can also be used as the photopolymerization initiator, the disclosure of which is incorporated herein by reference.

[0175] When the resin composition contains a photopolymerization initiator, the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.

[0176] [Aniline compounds] From the viewpoint of resolution, the resin composition preferably contains an aniline compound. The aniline compound is preferably a compound that acts as a sensitizer, and more preferably a compound that has a sensitizing effect on a photoradical polymerization initiator. The sensitizer absorbs specific actinic radiation and enters an electronically excited state. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and undergoes actions such as electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiator or the photoradical polymerization initiator undergoes a chemical change and decomposes, generating a radical, an acid, or a base. Furthermore, if a portion of the aniline compound remains in the cured product, it may quench acids generated within the cured product or acids brought in from outside the cured product, thereby suppressing oxidation of the metal and resulting in improved adhesion.

[0177] Preferred examples of the aniline compound include compounds containing a benzene ring structure having a dialkylamino group or a dihydroxyalkylamino group as a substituent.

[0178] Examples of aniline compounds include Michler'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-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 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, 3-benzyloxycarbonyl-7- Dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, dimethylaniline, bis(4-dimethylaminophenyl) Examples include methane, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 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, 3',4'-dimethylacetanilide, and those described in the examples below.

[0179] Among these, the aniline compound is preferably a compound represented by the following formula (AN-1) or (AN-2) (hereinafter also referred to as "compound A"). [ka] In formula (AN-1), R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group, R 11 and R 12 At least one of the groups represented by formula (R-1) contains a group represented by Ar 1 represents an aromatic ring structure which may have a substituent or a fused ring, n1 represents an integer of 2 or more, when n1 is 2, X represents a single bond or a divalent linking group, and when n1 is 3 or more, X represents an n1-valent linking group. In formula (AN-2), R 21 and R 22 each independently represents a hydrogen atom or a monovalent organic group, R 21 and R 22 At least one of the groups represented by formula (R-1) contains a group represented by Ar 2 represents an aromatic ring structure which may have a substituent or a condensed ring, and n2 represents an integer of 1 or more. [ka] In formula (R-1), R R1 and R R2 each independently represents a hydrogen atom or a monovalent organic group, and m R R1 may be the same or different, and m R R2 may be the same or different, m represents an integer of 2 or more, and * represents a bonding site to another structure.

[0180] In formula (AN-1), R 11 and R 12 are preferably groups represented by formula (R-1). R 11 and R 12 is a hydrogen atom or a monovalent organic group other than the group represented by formula (R-1), R11 and R 12 One of the groups is preferably a monovalent organic group different from the group represented by formula (R-1). Examples of the monovalent organic group different from the group represented by formula (R-1) include an alkyl group and an aryl group, with an alkyl group being preferred and a methyl group being more preferred.

[0181] In the group represented by formula (R-1), R R1 and R R2 each independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group. R1 and R R2 In one preferred embodiment, all of are hydrogen atoms. In formula (R-1), m represents an integer of 2 or more, preferably an integer of 2 to 4, more preferably 2 or 3, and even more preferably 2. Specific examples of the group represented by formula (R-1) are listed below, but the present invention is not limited thereto. In the following specific examples, * has the same meaning as * in formula (R-1). [ka]

[0182] In formula (AN-1), Ar 1 represents an aromatic ring structure which may have a substituent or a condensed ring. In formula (AN-1), Ar 1 The aromatic ring structure in may be either an aromatic hydrocarbon ring structure or an aromatic heterocyclic structure, but is preferably an aromatic hydrocarbon ring structure, and more preferably a benzene ring structure. Examples of the substituent include an alkyl group, an aryl group, and a halogen atom, with an alkyl group being preferred and a methyl group being more preferred. The fused ring may be a cycloalkane, an aromatic ring, or the like, with a cyclopropane ring being preferred.

[0183] In formula (AN-1), n1 represents an integer of 2 to 4, preferably 2 or 3, and more preferably 2.

[0184] In formula (AN-1), when n1 is 2, X represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, a haloalkylene group, an arylene group, or a group represented by a combination thereof. The hydrogen atoms in these groups may be substituted with known substituents such as hydroxyl groups and halogen atoms. The alkylene group is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group, an ethylene group, or an isopropylene group. The arylene group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group, and more preferably a phenylene group.

[0185] In formula (AN-1), when n1 is 3 or more, X represents an n1-valent linking group. The n1-valent linking group is preferably an aliphatic hydrocarbon group, an aromatic group, or a group represented by a combination thereof. The hydrogen atoms in these groups may be substituted with known substituents such as a hydroxyl group. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aromatic group is preferably an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group having 6 carbon atoms.

[0186] In formula (AN-2), R 21 and R 22 A preferred embodiment of the formula (AN-1) is 11 and R 12 This is the same as the preferred embodiment of the above.

[0187] In formula (AN-2), Ar 2 represents an aromatic ring structure which may have a substituent or a condensed ring. Examples of the aromatic ring structure include a benzene ring structure, a carbazole ring structure, and a fluorene ring structure. Examples of the substituent include an alkyl group, an aryl group, and a halogen atom, with an alkyl group being preferred and a methyl group being more preferred. The fused ring may be a cycloalkane, an aromatic ring, or the like, with a cyclopropane ring being preferred. Below, Ar 2 Specific examples are listed below, but the present invention is not limited to these. In the specific examples below, * represents the bonding site with the nitrogen atom in formula (AN-2). [ka]

[0188] In formula (AN-2), n2 is preferably an integer of 1 to 3, and more preferably 1 or 2.

[0189] Among these, the compound A is a compound represented by the formula (AN-1), and R 11 and R 12 are all groups represented by formula (R-1), and an embodiment in which m in formula (R-1) is 2 is preferred. Preferred embodiments of the other symbols in the above embodiment are as described in the explanation of formula (AN-1) above.

[0190] The molecular weight of compound A is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less. The lower limit of the molecular weight is not particularly limited, but is preferably 150 or more, and more preferably 200 or more.

[0191] When the resin composition contains an aniline compound, the content of the aniline compound is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition. The aniline compound may be used alone or in combination of two or more types.

[0192] Other sensitizing dyes may also be used as the sensitizer. For details about the sensitizing dye, please refer to the description in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

[0193] [Chain transfer agent] The resin composition may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include compounds having -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These donate hydrogen to low-activity radicals to generate radicals, or can generate radicals by being oxidized and then deprotonated. Thiol compounds are particularly preferred.

[0194] In addition, the chain transfer agent may be a compound described in paragraphs 0152 to 0153 of WO 2015 / 199219, the contents of which are incorporated herein by reference.

[0195] When the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the resin composition. The chain transfer agent may be one type, or two or more types. When two or more types of chain transfer agents are used, the total amount thereof is preferably within the above range.

[0196] In addition, it is one of the preferred embodiments of the present invention that the resin composition contains two or more types of polymerization initiators. Specifically, the resin composition preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or contains the above-mentioned photoradical polymerization initiator and a photoacid generator.

[0197] By including a photopolymerization initiator and a thermal polymerization initiator described below, pattern formation by exposure becomes possible, and radical polymerization also becomes more likely to proceed during curing by a heating step described below, which may improve performance such as chemical resistance. When a photopolymerization initiator and a thermal polymerization initiator described below are contained, the content of the thermal polymerization initiator is preferably 20 to 70 mass %, more preferably 30 to 60 mass %, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0198] By including a photoradical polymerization initiator and a photoacid generator, performance such as resolution may be improved in some cases. When a photopolymerization initiator and a photoacid generator are contained, the content ratio of the photoacid generator relative to the total content of the photopolymerization initiator and the photoacid generator is preferably 20 to 70 mass %, more preferably 30 to 60 mass %.

[0199] [Thermal polymerization initiator] Examples of the thermal polymerization initiator include a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes the polymerization reaction of a polymerizable compound. Addition of the thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance.

[0200] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554, the contents of which are incorporated herein by reference.

[0201] When a thermal polymerization initiator is contained, its content is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. The resin composition may contain only one type of thermal polymerization initiator, or may contain two or more types. When two or more types of thermal polymerization initiators are contained, the total amount is preferably within the above range.

[0202] [Organotitanium Compounds] By including an organotitanium compound in the resin composition, for example, a cured product having excellent chemical resistance can be formed even when cured at low temperatures.

[0203] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organotitanium compound are shown below in I) to VII): I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are preferred because they provide good storage stability to the resin composition and produce a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxytitanium 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 tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)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-pyrrol-1-yl)phenyl)titanium, and the like. IV) Monoalkoxytitanium compounds: For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate.

[0204] Among them, from the viewpoint of better chemical resistance, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0205] It is also preferable to contain a compound represented by the following formula (T-1) as the organotitanium compound or in place of the organotitanium compound. [ka] In formula (T-1), M is titanium, zirconium, or hafnium, l1 is an integer of 0 to 2, l2 is 0 or 1, l1+l2×2 is an integer of 0 to 2, m is an integer of 0 to 4, n is an integer of 0 to 2, l1+l2+m+n×2=4, and 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 12is a substituted or unsubstituted hydrocarbon group, R 2 are each independently a group containing a structure represented by the following formula (T-2), and R 3 are each independently a group containing a structure represented by the following formula (T-2), and X A are each independently an oxygen atom or a sulfur atom. [ka] In formula (T-2), X 1 ~X 3 each independently represents -C(-*)= or -N=, * represents a bonding site to another structure, and # represents a bonding site to a metal atom.

[0206] In the formula (T-1), M is preferably titanium from the viewpoint of storage stability of the composition. In formula (T-1), an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention. In formula (T-1), m is preferably 2 or 4, and more preferably 2. In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1. Here, it is also preferred that l1 and l2 are 0 and m is 0, 2 or 4 in formula (T-1).

[0207] In formula (T-1), from the viewpoint of the stability of the specific metal complex, R 11 is preferably a substituted or unsubstituted cyclopentadienyl ligand. Also, R 11 The cyclopentadienyl group, alkoxy group and phenoxy group in the formula (I) may be substituted, but an embodiment in which they are unsubstituted is also one of the preferred embodiments of the present invention.

[0208] In formula (T-1), R 12 is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. R 12The hydrocarbon group in may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but is preferably an aromatic hydrocarbon group. 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. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group. R 12 The substituent in R is preferably a monovalent substituent, such as a halogen atom. 12 When is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. Among these, in formula (T-1), R 12 is preferably an unsubstituted phenylene group. 12 The phenylene group in is preferably a 1,2-phenylene group.

[0209] In formula (T-1), m is 2 or more, and R 2 If two or more are included, then two or more R 2 The structures may be the same or different. In formula (T-1), n ​​is 2 or more, and R 3 If two or more are included, then two or more R 3 The structures may be the same or different.

[0210] In formula (T-2), X 1 ~X 3 each independently represents -C(-*)= or -N=, and it is preferable that at least one represents -C(-*)=, and it is more preferable that at least two represent -C(-*)=.

[0211] Among these compounds, from the viewpoint of improving adhesion and resolution, the resin composition preferably contains a compound corresponding to a metal complex, and more preferably a compound corresponding to a titanium complex.

[0212] When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 part by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is improved.

[0213] [Base Generator] The resin composition may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. By including a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in good performance as an interlayer insulating film for a rewiring layer included in, for example, a semiconductor package. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of non-ionic base generators include the compounds described in paragraphs 0249 to 0275 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0214] Examples of the base generator include, but are not limited to, the following compounds:

[0215] [ka]

[0216] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0217] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0218] Specific examples of ammonium salts include, but are not limited to, the following compounds: [ka]

[0219] Furthermore, the base generator is preferably an amine in which the amino group is protected with a t-butoxycarbonyl group, from the viewpoints of storage stability and generating a base by deprotection during curing.

[0220] Examples of amine compounds protected by a t-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. alcohol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine Aminoamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis(3-aminopropyl)ethanol Examples of the tert-butoxycarbonyl protecting agent include, but are not limited to, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or a derivative thereof is protected with a t-butoxycarbonyl group.

[0221] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition. The lower limit is 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, still more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. The base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.

[0222] 〔solvent〕 The resin composition preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0223] 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, γ-valerolactone, alkyl alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 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.)), 2-alkoxypropionates, alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.), ... methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc.), alkyl 3-alkoxy Suitable alkyloxypropionic acid alkyl esters include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, and propyl 2-alkyloxypropionates (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, and diethyl malonate.

[0224] Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0225] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0226] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0227] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0228] Preferred examples of the amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0229] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0230] 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, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

[0231] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0232] In the present invention, preferred is 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-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents. Particularly preferred are a combination of dimethyl sulfoxide and γ-butyrolactone, a combination of dimethyl sulfoxide and γ-valerolactone, a combination of 3-methoxy-N,N-dimethylpropanamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropanamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass based on the total mass of the solvents. In particular, from the viewpoint of storage stability of the resin composition, an embodiment in which γ-valerolactone is contained as a solvent is 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. The upper limit of the content is not particularly limited and may be 100% by mass. The content may be determined taking into consideration the solubility of components such as resin B contained in the resin composition, etc. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably 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, relative to the total mass of the solvent.

[0233] From the viewpoint of coatability, the content of the solvent is preferably an amount that results in a total solids concentration of the resin composition of 5 to 80 mass%, more preferably an amount that results in 5 to 75 mass%, even more preferably an amount that results in 10 to 70 mass%, and even more preferably an amount that results in 20 to 70 mass%. The content of the solvent may be adjusted depending on the desired thickness of the coating film and the coating method. When two or more solvents are contained, the total amount thereof is preferably within the above range.

[0234] [Metal adhesion improver] The resin composition preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, and an amino compound.

[0235] [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 Application Laid-Open 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 Application Laid-Open No. 2011-128358. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group. Furthermore, the following R represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent may be selected depending on the desorption temperature, and examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, caprolactam is preferred from the viewpoint of achieving a desorption temperature of 160 to 180°C. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0236] [ka]

[0237] 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 of suitable silanes 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-isocyanatepropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These may be used alone or in combination of two or more. Furthermore, an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent. Such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1). [ka] In formula (S-1), R S1 represents a monovalent organic group, and R S2 represents a hydrogen atom, a hydroxy group or an alkoxy group, and n represents an integer of 0 to 2. R S1is preferably a structure containing a polymerizable group. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group. A vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, a vinylphenyl group or a (meth)acryloyloxy group is more preferred, and a (meth)acryloyloxy group is even more preferred. R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. n represents an integer of 0 to 2, and is preferably 1. Here, the structures of the repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same. Here, among the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, it is preferable that n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. As such oligomer type compounds, commercially available products can be used, and examples of commercially available products include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0238] Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A No. 2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A No. 2013-072935, the contents of which are incorporated herein by reference.

[0239] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of Resin B. By ensuring that the content is equal to or greater than the lower limit, the adhesion between the pattern and the metal layer is improved, and by ensuring that the content is equal to or less than the upper limit, the heat resistance and mechanical properties of the pattern are improved. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0240] [Nitrogen-containing heterocyclic compound] The resin composition preferably further contains a nitrogen-containing heterocyclic compound, which can effectively suppress the migration of metal ions derived from the metal layer (or metal wiring) into the film when the resin composition is applied to the metal layer (or metal wiring) to form a film.

[0241] The nitrogen-containing heterocyclic compound is not particularly limited, and examples thereof include compounds having a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, and a triazine ring. 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 are preferably used. Among these, the resin composition preferably contains 8-azaadenine.

[0242] When the resin composition contains a nitrogen-containing heterocyclic compound, the content of the nitrogen-containing heterocyclic compound is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, relative to the total solid content of the resin composition.

[0243] The nitrogen-containing heterocyclic compound may be one kind or two or more kinds. When two or more kinds of nitrogen-containing heterocyclic compounds are used, the total amount thereof is preferably within the above range.

[0244] [Other migration inhibitors] The resin composition may contain other migration inhibitors.

[0245] Other migration inhibitors include thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, hydrazide derivative compounds, rust inhibitors described in paragraph 0094 of JP 2013-015701 A, compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, compounds described in paragraph 0052 of JP 2011-059656 A, compounds described in paragraphs 0114, 0116 and 0118 of JP 2012-194520 A, compounds described in paragraph 0166 of WO 2015 / 199219 A, and the like can be used, the contents of which are incorporated herein by reference. As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0246] When the resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, relative to the total solid content of the resin composition.

[0247] The migration inhibitor may be one type only, or two or more types may be used. When two or more types of migration inhibitors are used, the total amount thereof is preferably within the above range.

[0248] [Urea compounds, carbodiimide compounds, isourea compounds] From the viewpoint of breaking elongation and adhesion to a metal or resin layer, the resin composition may contain at least one compound (hereinafter also referred to as "urea compound, etc.") selected from the group consisting of compounds having a urea bond (urea compound), compounds having a carbodiimide structure (carbodiimide compound), and compounds having an isourea bond (isourea compound). Among these, it is preferable that the resin composition further contains a compound having a urea bond. The urea compounds and the like referred to here do not include the above-mentioned polymerizable compounds and compounds corresponding to silane coupling agents. Examples of the urea compound include the compounds described in paragraphs 0334 to 0339 of WO 2022 / 070730. Among these, the resin composition preferably contains a dialkyl urea compound. The alkyl group in the dialkyl urea compound is preferably a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 5 to 10 carbon atoms, and more preferably an isopropyl group or a cyclohexyl group.

[0249] Specific examples of the urea compound include, but are not limited to, dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea.

[0250] The total content of the urea compounds and the like is preferably 0.01 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and even more preferably 1.0 to 6.0 parts by mass, relative to 100 parts by mass of Resin B. The urea compounds etc. may be used alone or in combination of two or more. When two or more bases are used in combination in the base-containing treatment liquid, it is preferable that the total content thereof is within the above range.

[0251] [Light absorber] The resin composition also preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of which are incorporated herein by reference.

[0252] It is also preferable to include a compound having the following structure as the light absorber. [ka]

[0253] The content of the light absorber relative to the total solid content of the resin composition is not particularly limited, but is preferably 0.1 to 20 mass %, more preferably 0.5 to 10 mass %, and even more preferably 1 to 5 mass %.

[0254] [Other additives] The resin composition may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, photoacid generators, anti-aggregation agents, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, as long as the effects of the present invention are achieved. By appropriately incorporating these components, film properties and other characteristics can be adjusted. For details of these components, see, for example, paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104 and 0107-0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are incorporated, their total content is preferably 3% by mass or less of the solid content of the resin composition.

[0255] [Characteristics of Resin Composition] The viscosity of the resin composition can be adjusted by the solid content concentration of the resin composition. 2 / s~12,000mm 2 / s is preferred, 2,000 mm 2 / s~10,000mm 2 / s is more preferable, 2,500 mm 2 / s~8,000mm 2 / s is more preferable. Within the above range, it is easy to obtain a highly uniform coating film. 2 / s or more, it is easy to apply it to a thickness required for an insulating film for rewiring, for example, and it is 12,000 mm 2 If the viscosity is less than / s, a coating film with excellent surface condition can be obtained.

[0256] [Restrictions on substances contained in resin compositions] The water content of the resin composition 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 the water content is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.

[0257] From the viewpoint of insulating properties, the metal content of the resin composition is preferably less than 5 ppm by mass (parts per million), 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 metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, the total amount of these metals is preferably within the above range.

[0258] Furthermore, examples of methods for reducing metal impurities unintentionally contained in a resin composition include selecting raw materials with a low metal content as raw materials for constituting the resin composition, filtering the raw materials for constituting the resin composition, and lining the inside of an apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

[0259] Considering the use of the resin composition as a semiconductor material, the content of halogen atoms 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. Among them, those present in the form of halogen ions are 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 of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range. A preferred method for adjusting the content of halogen atoms is ion exchange treatment.

[0260] A conventionally known container can be used as the container for storing the resin composition. For the purpose of preventing impurities from being mixed into the raw materials or the resin composition, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure made of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.

[0261] <Preparation of Resin Composition> The resin composition can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be carried out by a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.

[0262] Filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the resin composition. The filter pore size is, for example, preferably 5 μm or less, more preferably 1 μm or less, even 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. When the filter material is polyethylene, HDPE (high density polyethylene) is more preferable. Examples of filters include the filters described in paragraph 0287 of WO 2023 / 190064. The above content is incorporated herein by reference.

[0263] (Method of producing cured product) The method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate to form a film. The method for producing a cured product more preferably includes the above-mentioned film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern. It is particularly preferable that the method for producing a cured product includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained in the development step and a post-development exposure step of exposing the pattern obtained in the development step. The method for producing a cured product preferably includes the film-forming step and the step of heating the film. Each step will be described in detail below.

[0264] <Film formation process> The resin composition can be used in a film-forming process in which the resin composition is applied onto a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate to form a film.

[0265] [Base material] The type of substrate can be appropriately determined depending on the application and is not particularly limited. Examples of substrates include semiconductor production substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal and substrates on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, and electrode plates for plasma display panels (PDPs). The substrate is particularly preferably a semiconductor production substrate, and more preferably a silicon substrate, a Cu substrate, or a mold substrate. These substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface. The shape of the substrate is not particularly limited, and may be circular or rectangular. The size of the substrate is preferably, for example, 100 to 450 mm in diameter, more preferably 200 to 450 mm, if it is circular, and preferably, 100 to 1000 mm in short side length, more preferably 200 to 700 mm, if it is rectangular. As the substrate, for example, a plate-shaped, preferably a panel-shaped substrate (substrate) is used.

[0266] When a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer made of a cured product) or the surface of a metal layer, the resin layer or the metal layer serves as the substrate.

[0267] The resin composition is preferably applied to a substrate by coating. Specific examples of the coating method 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 the film thickness, spin coating, slit coating, spray coating, and inkjet coating are preferred, and from the viewpoint of uniformity of the film thickness and productivity, spin coating and slit coating are more preferred. A film of the desired thickness can be obtained by adjusting the solid content concentration of the resin composition and coating conditions depending on the coating method. 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. Spin coating can be applied, for example, at a rotation speed of 500 to 3,500 rpm for approximately 10 seconds to 3 minutes. Alternatively, a coating film may be formed by applying the coating to a temporary support in advance using the above-mentioned application method, and then transferred onto the substrate. As for the transfer method, the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. Additionally, a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinsing (EBR) or back rinsing. Before applying the resin composition to the substrate, a pre-wetting step may be employed in which the substrate is coated with various solvents to improve the wettability of the substrate, and then the resin composition is applied.

[0268] <Drying process> After the film-forming step (layer-forming step), the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent. That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step. The drying step is preferably carried out after the film-forming step and before the exposure step. The drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0269] <Exposure process> The film may be subjected to an exposure step to selectively expose the film to light. The method for producing a cured product may include an exposure step of selectively exposing the film formed in the film formation step to light. Selective exposure means that only a portion of the film is exposed, resulting in exposed and unexposed areas of the film. The exposure dose is not particularly limited as long as it can cure the resin composition, but for example, it is 50 to 10,000 mJ / cm in terms of exposure energy at a wavelength of 365 nm. 2 is preferred, and 200 to 8,000 mJ / cm 2 is more preferred.

[0270] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0271] Examples of exposure wavelengths, in relation to the light source, include (1) semiconductor lasers (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet light (EUV) (wavelength 13.6 nm), (6) electron beams, and (7) YAG lasers, second harmonic 532 nm and third harmonic 355 nm. For resin compositions, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited as long as it is a method that exposes at least a part of the film made of the resin composition, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0272] <Post-exposure baking process> The film may be subjected to a step of heating after exposure (post-exposure baking step). That is, the method for producing a cured product of the present invention may include a post-exposure baking step in which the film exposed in the exposure step is heated. The post-exposure baking step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure baking step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, more preferably from 1 minute to 10 minutes. The temperature rise rate in the post-exposure heating step from the heating start temperature to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The temperature rise rate may be changed during heating as needed. The heating means in the post-exposure baking step is not particularly limited, and known means such as a hot plate, an oven, and an infrared heater can be used. It is also preferable to carry out the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0273] <Developing process> After exposure, the film may be subjected to a development step in which it is developed with a developer to form a pattern. That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed with a developer to form a pattern. Development removes either the exposed or unexposed portions of the film, forming a pattern. Here, development in which the non-exposed portions of the film are removed by the development process is called negative development, and development in which the exposed portions of the film are removed by the development process is called positive development.

[0274] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0275] When the developer is an alkaline aqueous solution, examples of the basic compound that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Examples of the basic compound include the compounds described in paragraph 0300 of WO 2023 / 190064. The contents of the above are incorporated herein by reference. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

[0276] When the developer contains an organic solvent, the organic solvent may be a compound described in paragraph 0387 of WO 2021 / 112189, the contents of which are incorporated herein by reference. Suitable examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol, and suitable examples of amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0277] When the developer contains an organic solvent, the organic solvent may be used alone or in combination. 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 particularly preferred.

[0278] 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, and may be 100% by mass.

[0279] The developer may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0280] In the development step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a rinse liquid may be supplied before the developer in contact with the pattern is completely dried.

[0281] [Rinse solution] When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid. When the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0282] When the rinse liquid contains an organic solvent, examples of the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent. The organic solvent contained in the rinse liquid is preferably different from the organic solvent contained in the developer, and more preferably an organic solvent that has a lower solubility for the pattern than the organic solvent contained in the developer.

[0283] When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The organic solvent is preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.

[0284] When the rinse solution contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more of the total mass of the rinse solution, or may account for 100% by mass of the total mass of the rinse solution.

[0285] The rinse liquid may contain at least one of a basic compound and a base generator. Although not particularly limited, when the developer contains an organic solvent, one preferred embodiment of the present invention is one in which the rinse liquid contains an organic solvent and at least one of a basic compound and a base generator. Examples of the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained in the above-mentioned developer containing an organic solvent, and preferred embodiments are also the same. The basic compound and base generator contained in the rinse solution may be selected in consideration of the solubility in the solvent in the rinse solution.

[0286] When the rinse solution contains at least one of a basic compound and a base generator, the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the rinse solution. The lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more. When the basic compound or base generator is solid in the environment in which the rinse solution is used, the content of the basic compound or base generator is preferably 70 to 100 mass % based on the total solid content of the rinse solution. When the rinse solution contains at least one of a basic compound and a base generator, the rinse solution may contain only one kind of at least one of a basic compound and a base generator, or may contain two or more kinds. When there are two or more kinds of at least one of a basic compound and a base generator, the total amount thereof is preferably within the above range.

[0287] The rinse solution may further contain other ingredients. Examples of other components include known surfactants and known defoaming agents.

[0288] [Method of supplying rinse liquid] The method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like. From the viewpoints of the permeability of the rinse liquid, the removability of non-image areas, and production efficiency, the rinse liquid can be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, a spray nozzle, etc. That is, the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle. The method of supplying the rinse liquid in the rinsing step may include a step of continuously supplying the rinse liquid to the substrate, a step of keeping the rinse liquid substantially stationary on the substrate, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, and a combination of these steps.

[0289] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0290] The developing step may include a step of contacting the pattern with a treatment liquid after treatment with a developer or after washing the pattern with a rinse liquid. Alternatively, a method may be employed in which the treatment liquid is supplied before the developer or rinse liquid in contact with the pattern is completely dried.

[0291] <Heating process> The pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step. The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without performing a development step, or a film obtained in the film-forming step. In the heating step, Resin B undergoes cyclization to form a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in Resin B or in a crosslinking agent other than Resin B also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, still more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0292] The heating step is preferably a step in which the cyclization reaction of the resin B is promoted within the pattern by the action of the base generated from the base generator due to heating. Heating in the heating step can be carried out, for example, by the method described in paragraphs 0327 to 0332 of WO 2023 / 190064, the disclosure of which is incorporated herein by reference.

[0293] <Metal layer formation process> The pattern obtained by the development step (which is preferably subjected to at least one of the heating step and the post-development exposure step) may be subjected to a metal layer forming step in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained in the development step (preferably subjected to at least one of a heating step and a post-development exposure step).

[0294] The metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

[0295] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, the methods described in JP 2007-157879 A, ​​JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used. Examples of suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations thereof. More specifically, examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating. Preferred plating methods include electroplating using a copper sulfate or copper cyanide plating solution.

[0296] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0297] <Application> The cured product manufacturing method of the present invention and the fields to which the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and the etching of insulating films for packaging applications such as those mentioned above. For details of these applications, see, for example, Science & Technology Co., Ltd.'s "High Performance Polyimide and Application Technology" (April 2008), edited by Masaaki Kakimoto, CMC Technical Library's "Fundamentals and Development of Polyimide Materials" (November 2011), and the Japan Polyimide and Aromatic Polymer Research Association's "Latest Polyimides: Fundamentals and Applications" (NTS, August 2010).

[0298] The method for producing the cured product of the present invention, or the cured product of the present invention, can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, for producing protective lacquers and dielectric layers in electronics, especially microelectronics, etc.

[0299] (Laminate and method for manufacturing laminate) The laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention. The laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers. Of the two or more layers made of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.

[0300] That is, the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.

[0301] The laminate of the present invention preferably includes two or more layers each made of the cured product of the present invention, and a metal layer between any two of the layers made of the cured product. The metal layer is preferably formed by the metal layer-forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on the layer made of the cured product, between the steps for producing a cured product that are performed multiple times. Preferred aspects of the metal layer-forming step are as described above. As the laminate, for example, a laminate including at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order, can be mentioned as a preferred example. It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention. The resin composition used to form the layer made of the first cured product and the resin composition used to form the layer made of the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0302] <Lamination process> The method for producing the laminate of the present invention preferably includes a lamination step. The lamination process is a series of processes including (a) a film-forming process (layer-forming process), (b) an exposure process, (c) a development process, and (d) at least one of a heating process and a post-development exposure process, which are performed again on the surface of the pattern (resin layer) or metal layer in this order. However, at least one of the (a) film-forming process and the (d) heating process and the post-development exposure process may be repeated. Furthermore, at least one of the (d) heating process and the post-development exposure process may be followed by the (e) metal layer-forming process. Needless to say, the lamination process may further include the drying process and the like as appropriate.

[0303] When a further lamination step is performed after the lamination step, a surface activation treatment step may be further performed after the exposure step, the heating step, or the metal layer forming step. An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.

[0304] The lamination step is preferably carried out 2 to 20 times, and more preferably 2 to 9 times. For example, a structure of 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred. The above layers may be the same or different in composition, shape, film thickness, etc.

[0305] In the present invention, a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition is further formed so as to cover the metal layer. Specific examples include an embodiment in which the following steps are repeated in this order: (a) a film-forming step, (b) an exposure step, (c) a development step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer-forming step; or an embodiment in which the following steps are repeated in this order: (a) a film-forming step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer-forming step. By alternately performing the lamination step of laminating resin composition layers (resin layers) and the metal layer-forming step, resin composition layers (resin layers) and metal layers can be alternately laminated.

[0306] (Surface activation treatment process) The method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment. The surface activation treatment step is usually carried out after the metal layer formation step, but the surface activation treatment step may be carried out on the resin composition layer after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) and then the metal layer formation step may be carried out. The surface activation treatment may be performed on at least a portion of the metal layer, or on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure. The surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the resin composition layer is formed. In this way, by performing the surface activation treatment on the surface of the metal layer, it is possible to improve the adhesion with the resin composition layer (film) formed on the surface. It is preferable to perform the surface activation treatment on a part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with a metal layer or a resin layer provided on the surface that has been surface-activated. In particular, when negative development is performed, etc., if the resin composition layer is cured, it is less susceptible to damage due to the surface treatment, and adhesion is likely to be improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0307] (Semiconductor device and its manufacturing method) The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention. The present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product of the present invention or the method for producing the laminate. For specific examples of semiconductor devices using a resin composition to form an interlayer insulating film for a rewiring layer, please refer to the descriptions in paragraphs 0213 to 0218 and Figure 1 of JP 2016-027357 A, the contents of which are incorporated herein by reference. [Example]

[0308] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0309] <Polymer synthesis> [Synthesis Example P-1: Synthesis of Resin (P-1)] 93.07 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 62.04 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) were placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added. 79.1 g of pyridine was added with stirring at room temperature to obtain a reaction mixture. After the heat generated by the reaction had subsided, the mixture was allowed to cool to room temperature and then allowed to stand for an additional 16 hours. Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 96.0 g of 4,4'-diaminodiphenyl ether suspended in 350 mL of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature (23°C) for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour. Then, 400 mL of γ-butyrolactone was added. The precipitate that formed in the reaction mixture was collected by filtration to obtain a reaction solution. The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was filtered and dissolved in 1.5 L of tetrahydrofuran to produce a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried to produce powdered resin P-1. Resin P-1 has a structure containing a repeating unit represented by the following formula (P-1): 1 The resin P-1 was confirmed by H-NMR. The weight average molecular weight, imidization rate, esterification rate, amine value, and acid value are shown in the table below. The symbols A and B in parentheses represent the molar ratio of each structure, and the values ​​are shown in the table below.

[0310] [Method for measuring weight average molecular weight] In the above and following synthesis examples, unless otherwise specified, the weight average molecular weight and number average molecular weight were measured by the following methods. GPC measurements were performed using a high-speed GPC system (HLC-8420GPC, manufactured by Tosoh Corporation) with a TSK guard column Super AW-H (4.6 mm × 35 mm) and two TSKgel Super AWM-H (4.6 mm × 150 mm) columns connected in series. A 0.01 mol / L solution of lithium bromide in NMP (N-methyl-2-pyrrolidone) was used as the eluent.

[0311] [Method for measuring imidization rate] Each resin was dissolved in γ-butyrolactone, diluted to 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. The silicon wafer with the resulting resin layer applied was dried on a hot plate at 110°C for 5 minutes, yielding a resin layer with a uniform thickness of approximately 15 μm after film formation on the silicon wafer. The resin layer was measured by the ATR method using a NicoletiS20 (manufactured by Thermofisher) in the measurement range of 4000 to 700 cm -1 The measurement was carried out 50 times. -1 Around (1350~1450cm -1 (If there are multiple peaks, the peak with the highest intensity) and 1500 cm -1 Around (1460~1550cm -1 The imidization index B was calculated in the same manner for a film that was heated at a heating rate of 10°C / min in a nitrogen atmosphere and heated at 350°C for 1 hour, and the imidization rate of the resin was calculated by dividing the imidization index A by the imidization index B.

[0312] [Method for determining the esterification rate] The esterification rate of the resin used in each example or comparative example was measured by the following method. Dissolve 0.09 g of resin in 0.9 g of DMSO-d6 (dimethyl sulfoxide-d6). 1 H-NMR was measured, and the content of the amic acid ester structure (esterification rate) relative to the total molar amount of the amic acid structure and the amic acid ester structure in the resin was calculated.

[0313] [Method for determining acid value] The acid value of the resin used in each example or comparative example was measured by the following method. 0.30 g of resin was dissolved in 80 mL of NMP, and 5 mL of water was added to prepare a measurement solution. The acid value of the resin was measured by titrating the solution with 0.01 N (0.01 mol / L) potassium hydroxide (KOH) aqueous solution to detect the neutralization point. The measurement results for each resin are shown in the column "resin acid value (mmol / g)" in the table.

[0314] [Method for determining amine value] The amine value of the resin used in each example or comparative example was measured by the following method. 0.60 g of resin was dissolved in 50 mL of diglyme, and 10 mL of acetic acid was added to prepare a measurement solution. The solution was titrated with a 0.01 N (0.01 mol / L) perchloric acid solution in acetic acid to detect the neutralization point, thereby measuring the amine value of the resin. The measurement results for each resin are shown in the "amine value (mmol / g)" column in the table.

[0315] [Method for quantifying specific structure content] The content of the specific structure below in the resin composition was measured by the following method. [ka] In formula (1), R 1 and R 2 each independently represents a saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms; X 1 represents an oxygen atom or a sulfur atom, and L 1 represents -C(=O)- or -S(=O)2-, * 1 and* 2 each independently represents a binding site to another structure, and R 1 , R 2 , * 1 A structure that binds to * 2 At least two of the structures bonded to may be bonded to form a ring structure. The resin used in each example or comparative example was dissolved in d6-DMSO. 1The content of the specific structure contained in the resin was quantified by H-NMR analysis. For each component listed in the table below, the total amount of components other than the solvent was defined as the total solid content, and the specific structure was assumed to be contained only in the resin component. The content of the specific structure in the total solid content was calculated from the relationship between the content of the specific structure in the resin quantified above and the content of the resin in the total solid content. The measurement results are shown in the column "Specific structure content (mmol / g)" in the table. [ka]

[0316] [Synthesis Examples P-2 to P-37: Synthesis of Resins (P-2) to (P-44)] Resins (P-2) to (P-44) were synthesized in the same manner as for Resin (P-1), except that the types and charging ratios of the raw materials, acid anhydrides and diamines, used in Synthesis Example P-1 were appropriately changed. Furthermore, in the synthesis of Resin (P-3), dicyclohexylcarbodiimide (DCC) was replaced with diisopropylcarbodiimide. Resins (P-2) to (P-44) are resins having repeating units represented by the following formulas (P-2) to (P-44), respectively. In the following structures, the symbols in parentheses represent the values ​​listed in the table below, and represent the molar ratio of each structure. The structure of each repeating unit is: 1 The weight average molecular weight (Mw), imidization rate, esterification rate, acid value, amine value, and specific structure content of these resins are shown in the table below. Resins with the same structure but different Mw, imidization rate, esterification rate, acid value, amine value, and specific structure content were obtained by appropriately changing the amount of raw materials used, the reaction temperature and reaction time after adding HEMA, and the reaction temperature and reaction time after adding diamine. For example, by setting the reaction temperature after adding HEMA to 5°C, a resin with an esterification rate of 88% such as P-5 was obtained. Furthermore, by setting the reaction temperature after adding diamine to 40°C, a resin with an imidization rate of 35% such as P-16 was obtained. [ka]

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[0317]

Table 1

[0318] <Examples and Comparative Examples> The resin compositions used in the examples and comparative examples were each obtained by mixing the components shown in the table below. Specifically, the content of each component shown in the table was the amount (parts by mass) shown in the "parts by mass" column of each column in the table. The obtained resin compositions and comparative compositions were pressure-filtered using a polytetrafluoroethylene filter with a pore size of 0.8 μm. The evaluation results for each resin composition are shown in the table below.

[0319] [Table 2]

[0320] [Table 3]

[0321] [Table 4]

[0322] [Table 5]

[0323] [Table 6]

[0324] 〔resin〕 P-1 to P-44: Resins (P-1) to (P-44) synthesized above

[0325] [Aniline compounds] B-1: N-phenyldiethanolamine B-2: Compound of the following structure B-3: Compound of the following structure [ka]

[0326] [Polymerizable compound] C-1: NK Ester 4G (Shin-Nakamura Chemical Co., Ltd.) C-2: NK Ester TMPT (Shin-Nakamura Chemical Co., Ltd.) C-3: Dipentaerythritol hexaacrylate (TCI) C-4: Compound with the following structure C-5: Compound with the following structure [ka]

[0327] [Photopolymerization initiator] D-1: Compound with the following structure D-2: IRGACURE OXE 01 (BASF) D-3: Compound with the following structure D-4: Compound with the following structure [ka]

[0328] [Sensitizer] E-1: Compound with the following structure E-2: Compound with the following structure [ka]

[0329] [Antioxidants] F-1: Compound with the following structure F-2: Compound with the following structure F-3: Compound with the following structure F-4: Compound with the following structure [ka]

[0330] [Metal adhesion improver] G-1: Compound with the following structure G-2: Compound with the following structure [ka]

[0331] [Migration inhibitor] H-1: Compound with the following structure H-2: Compound with the following structure H-3: Compound with the following structure H-4: Compound with the following structure [ka]

[0332] [Metal Complexes] I-1: Compound having the following structure (where iPr represents an isopropyl group): I-2: Compound with the following structure [ka]

[0333] [Thermal base generator] J-1: Compound with the following structure J-2: Compound with the following structure J-3: Compound with the following structure [ka]

[0334] [Urea compounds] U-1: 1,3-dicyclohexylurea U-2: 1,3-diisopropylurea

[0335] 〔solvent〕 L-1: γ-valerolactone L-2: Ethyl lactate L-3: Dimethyl sulfoxide L-4: γ-butyrolactone L-5: N-methyl-2-pyrrolidone L-6: 3-Methoxy-N,N-dimethylpropanamide L-7: 3-Butoxy-N,N-dimethylpropanamide

[0336] <Measurement of physical properties of cured product> [Young's modulus measurement] In each of the Examples and Comparative Examples, each resin composition or comparative composition was applied in the form of a layer on a silicon wafer by spin coating to form a composition layer. The silicon wafer to which the obtained composition layer was applied was dried on a hot plate at 100°C for 5 minutes to form a resin composition layer having a thickness of 15 µm on the silicon wafer. The resin composition layer on the silicon wafer was exposed to a broadband exposure machine (UX-1000SN-EH01 manufactured by Ushio Inc.) at the exposure dose (mJ / cm) shown in the table. 2 The exposed resin composition layer was heated at a temperature increase rate of 5°C / min under a nitrogen atmosphere and heated under the conditions described in the "Cure Conditions" column of the table. The cured resin layer was immersed in a 3% by mass hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film. The Young's modulus of the obtained resin film was measured in the longitudinal direction of the sample using a tensile tester (Instron Model 5965) at a crosshead speed of 300 mm / min, a width of 2 mm, and a length of 30 mm, in accordance with JIS-K7127:1999, under an environment of 23°C and 50% RH. The sample was prepared using a punching machine. The evaluation was carried out five times, and the arithmetic average value was used. The results are shown in the "Young's modulus (GPa)" column in the table.

[0337] <Evaluation> [Adhesion evaluation after repeated heating cycle tests] The resin compositions or comparative compositions prepared in the examples and comparative examples were applied in the form of a layer on a copper substrate by spin coating, respectively, to form a resin composition layer or a comparative composition layer. The copper substrate on which the resulting resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes, leaving a resin composition layer or comparative composition layer with a uniform thickness of 20 µm on the copper substrate. The resin composition layer or comparative composition layer on the copper substrate was then exposed to light using a stepper (Nikon NSR 2005 i9C) at the exposure dose (mJ / cm) shown in the table. 2The film was exposed to i-rays using a photomask with a 100 μm square unmasked area formed at the exposure dose described in "," followed by development with cyclopentanone for 60 seconds and rinsing with PGMEA for 30 seconds to obtain a 100 μm square resin layer. The film was then heated in a nitrogen atmosphere under the conditions described in the "Cure Conditions" column of the table to form a resin layer. Next, the copper substrate having the obtained resin layer was subjected to a moisture resistance test under the following condition 1 and a heating process under the following condition 2, which were repeated three times each. Condition 1 (humidity resistance test) 130°C, 85% relative humidity (RH), 96 hours Condition 2 (heating process) 175°C, 50% relative humidity (RH), 96 hours After the above test, the resin layer on the substrate was observed under an optical microscope to determine whether or not cracks had occurred. Observation was performed in an area of ​​1 cm square per location, for a total of 10 locations. The observation results were evaluated according to the following evaluation criteria. (Evaluation criteria) A: No cracks were observed in any of the 10 locations. B: Cracks were observed in 1 to 5 places. C: Cracks were observed in 6 to 9 places. D: Cracks were observed in all 10 locations.

[0338] [Evaluation of resolution] The resin composition or comparative composition prepared in each Example or Comparative Example was applied in the form of a layer by spin coating to the surface of the thin copper layer of a resin substrate having a thin copper layer formed on its surface, and dried at 110°C for 5 minutes to form a resin composition layer having a thickness of 4 μm after film formation. The obtained resin composition layer was then irradiated with 100 to 800 mJ / cm using an i-line stepper (Canon: FPA-3000i5, NA=0.5, σ=0.7) using a square via mask having a pattern formed in 0.5 μm increments from 0.5 to 10 μm. 2 in the range of 50 mJ / cm 2The film was exposed to each exposure dose, then developed with cyclopentanone until the unexposed areas were removed, rinsed with PGMEA for 30 seconds, and heated at a rate of 10°C / min under a nitrogen atmosphere under the conditions listed in the "Cure Conditions" column in the table. The minimum opening mask diameter of the obtained cured product was determined by observing the cross section of the opening pattern portion with a scanning microscope S-4800 (manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following evaluation criteria. The minimum opening mask diameter was defined as the smallest mask diameter among those in which an opening pattern was formed with at least one of the above exposure doses. In addition, the minimum opening mask diameter was determined by observing the cross section of the opening pattern with at least one of the above exposure doses at 400 mJ / cm. 2 The remaining film ratio (%, film thickness after development / film thickness before development × 100) was calculated from the film thickness before and after development when exposed to light at 100°C. If the remaining film ratio is less than 80%, it is not preferable for forming a rewiring layer, regardless of the opening mask size. (Evaluation criteria) A: The minimum opening mask diameter was 3 μm or less, and the residual film rate after development was 90% or more. B: The minimum opening mask diameter was more than 3 μm and 4 μm or less, and the residual film rate after development was 90% or more. C: The minimum opening mask diameter was more than 4 μm and 5 μm or less, and the residual film rate after development was 90% or more. D: The minimum opening mask diameter was more than 5 μm or the residual film rate after development was less than 80%.

[0339] [Chemical resistance] The resin composition or comparative composition prepared in each Example or Comparative Example was applied to a silicon wafer in the form of a layer by spin coating, and dried at 110°C for 5 minutes to form a resin composition layer having a film thickness of 15 μm after film formation. Next, the resin composition layer was exposed to a broadband exposure machine (UX-1000SN-EH01 manufactured by Ushio Inc.) at the exposure dose (mJ / cm2) shown in the table. 2)." Next, a heat treatment was carried out in a clean oven (KOYO, CLH-21) under an N2 atmosphere under the conditions described in the "Cure Conditions" column of the table, to obtain a cured film of the resin composition or comparative composition. The obtained cured film was immersed in the following chemicals under the following immersion conditions, and the remaining film ratio (film thickness after immersion / film thickness before immersion × 100 (%)) was calculated from the film thickness before and after immersion. Evaluation was carried out according to the following evaluation criteria, and the evaluation results are shown in the "Chemical Resistance" column. It can be said that the higher the remaining film ratio, the better the chemical resistance. Chemical: 90:10 mixture of dimethyl sulfoxide (DMSO) and 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) Immersion conditions: 60°C for 30 minutes -Evaluation criteria- A: The remaining film rate was 95% or more. B: The residual film rate was 80% or more and less than 95%.

[0340] [Film forming property] The resin compositions or comparative compositions prepared in each Example or Comparative Example were each applied to a silicon wafer by spin coating at 3000 rpm in an environment of 23°C and 50% humidity. The film surface was visually observed immediately after spin coating and after leaving it to stand for 5 minutes after spin coating, and evaluated according to the following evaluation criteria. The evaluation results are shown in the "Film Formability" column in the table. -Evaluation criteria- A: No cloudiness was observed in the film immediately after spin coating or after standing. B: No clouding of the film was observed immediately after spin coating, but clouding of the film was observed after standing.

[0341] [Storage stability] The resin compositions or comparative compositions prepared in each example or comparative example were stored in a thermostatic chamber at 23°C for 168 hours, and the occurrence of precipitation and the rate of viscosity change = |((viscosity after storage / viscosity before storage) x 100)| were evaluated according to the following evaluation criteria. Viscosity measurements were carried out at 23°C using a TV-100E viscometer (manufactured by Toki Sangyo Co., Ltd.). The evaluation results are shown in the "Storage stability" column in the table. -Evaluation criteria- A: The viscosity change rate was less than 2% and no precipitation was observed. B: The viscosity change rate was 2% or more and less than 5%, and no precipitation was observed. C: The viscosity change rate was 5% or more and less than 10%, and no precipitation was observed.

[0342] The above results show that the use of the resin composition of the present invention suppresses the occurrence of cracks after repeated humidity resistance tests. In contrast, when the resin does not have a specific biphenyl structure, when the cured product does not contain a nitrogen-containing heterocyclic compound, or when the Young's modulus of the cured product is outside the specified range, the occurrence of cracks after repeated humidity resistance tests is significantly reduced.

[0343] Furthermore, by using the resin composition according to the present invention, a cured film excellent in insulating properties, elongation at break, residual stress, and moisture resistance reliability was obtained.

Claims

1. At least one resin B selected from the group consisting of polyimides and polyimide precursors; A cured product obtained by curing a curable resin composition containing a photosensitizer, the Young's modulus of the cured product is 2.5 to 6.0 GPa; the cured product contains a nitrogen-containing heterocyclic compound, Furthermore, the resin A formed after curing of the resin composition has a repeating unit represented by the following formula (A-1): cured product. 【Chemical 1】 In formula (A-1), X Ａ１ is a structure represented by formula (X-A1), and Y Ａ１ is a divalent linking group. 【Chemistry 2】 In formula (X-A1), * represents the bonding site with the carbonyl group in formula (A-1).

2. The cured product according to claim 1, wherein the resin A is a resin having a repeating unit represented by the following formula (A-2): 【Chemistry 3】 In formula (A-2), X Ａ２ is a tetravalent organic group, and Y Ａ２ is a divalent linking group and satisfies at least one of the following conditions 1 and 2: Condition 1:X Ａ２ is a structure represented by the following formula (X-A2): Condition 2: Y Ａ２ is a structure represented by the following formula (Y-A2): 【Chemistry 4】 In formula (X-A2), * represents the bonding site with the carbonyl group in formula (A-2). 【Chemistry 5】 In formula (Y-A2), * represents the bonding site with the nitrogen atom in formula (A-2).

3. The cured product according to claim 1 or 2, wherein the resin A is a resin having a repeating unit represented by the following formula (A-3): 【Chemistry 6】 In formula (A-2), X Ａ３ is a tetravalent organic group, and Y Ａ３ is a divalent linking group and satisfies at least one of the following conditions 3 and 4: Condition 3: X Ａ３ is a structure represented by the following formula (X-A3): Condition 4: Y Ａ３ is a structure represented by any one of the following formulas (Y-A3) to (Y-A5): 【Chemistry 7】 In formula (X-A3), * represents the bonding site with the carbonyl group in formula (A-3). 【Chemistry 8】 In formulae (Y-A3) to (Y-A5), * represents the bonding site with the nitrogen atom in formula (A-3).

4. The cured product according to claim 1 or 2, wherein the weight average molecular weight of the resin B is 15,000 to 40,000.

5. The cured product according to claim 1 or 2, wherein the resin composition comprises a titanium complex compound.

6. The cured product according to claim 1 or 2, further comprising an oxime compound as the photosensitizer.

7. The cured product according to claim 1 or 2, wherein the resin composition further comprises an antioxidant.

8. The cured product according to claim 1 or 2, wherein the resin composition further comprises an aniline compound.

9. The cured product according to claim 1 or 2, wherein the resin composition further comprises a dialkyl urea compound.

10. 3. The cured product according to claim 1, wherein the ratio of the molar amount of the amic acid ester structure contained in the resin B to the total molar amount of the amic acid structure and the amic acid ester structure is 90 to 99.9%.

11. 3. The cured product according to claim 1, wherein the amount of acidic functional groups contained in said resin B, the neutralization point of which has a pH in the range of 7.0 to 12.0, is 0.0010 to 0.3000 mmol / g.

12. The cured product according to claim 1 or 2, wherein the amine value of the resin B is 0.001 to 0.300 mmol / g.

13. The cured product according to claim 1 or 2, wherein the imidization rate of the resin B is 3 to 40%.

14. The cured product according to claim 1 or 2, wherein the resin B contains a structure represented by the following formula (1), and the molar amount of the structure represented by formula (1) relative to the total solid content of the resin composition is 0.01 to 1.0 mmol / g: 【Chemistry 9】 In formula (1), R １ and R ２ each independently represents a saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 10 carbon atoms; X １ represents an oxygen atom or a sulfur atom, L １ is -C(=O)- or -S(=O) ２ represents - and * １ and * ２ each independently represents a bonding site to another structure, R １ , R ２ , * １ and * ２ At least two of the structures bonded to may be bonded to form a ring structure.

15. A laminate comprising two or more layers each comprising the cured product according to claim 1 or 2, and a metal layer between any two adjacent layers each comprising the cured product.

16. A semiconductor device comprising the cured product according to claim 1 or 2.

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