Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, semiconductor device, and method for producing polyamic acid ester

Abstract

Provided is a resin composition comprising a resin and a polymerization initiator, wherein the resin is a polyamic acid ester having an imidization rate of 3-45% and an absorbance of 0.62 or less at a wavelength of 365 nm in a 0.050 mass % solution. Also provided are a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, a semiconductor device, and a method for producing a polyamic acid ester.

Description

Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, semiconductor device, and method for producing polyamic acid ester

[0001] The present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, a semiconductor device, and a method for producing a polyamic acid ester.

[0002] Nowadays, resin materials produced from resin compositions containing resins are being utilized in various fields. For example, 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, encapsulants, or protective films for semiconductor devices used for packaging. They are also used as base films or coverlays for flexible substrates.

[0003] For example, in the above-mentioned applications, polyimide is used in the form of a resin composition containing a polyamic acid ester. Such a resin composition is applied to a substrate, for example, by coating or the like to form a photosensitive film, and then, as necessary, exposure, development, heating, or the like is performed to form a cured product on the substrate. Since the resin composition can be applied by known coating methods, for example, it can be said to have excellent manufacturing adaptability, such as a high degree of design freedom in the shape, size, application position, etc., when applying the resin composition to be applied. In addition to the high performance of heterocycle-containing polymers such as polyimides, from the perspective of such excellent manufacturing adaptability, the industrial application development of the above-mentioned resin composition is increasingly expected.

[0004] For example, Patent Document 1 describes a photosensitive resin composition containing a photosensitive polyimide precursor, which is obtained by sequentially going through the following steps (1) to (5): (1) spin-coating a resin composition onto a sputtered Cu wafer substrate; (2) heating the spin-coated wafer substrate on a hot plate at 110°C for 270 seconds to obtain a spin-coated film with a film thickness of 13 μm; (3) exposing a round-hole recessed pattern with a mask size of 8 μm by changing the focus in 2 μm increments from the film surface to the bottom of the film, using the surface of the spin-coated film as a reference; (4) developing the exposed wafer to form a relief pattern; and (5) heat-treating the developed wafer at 230°C for 2 hours in a nitrogen atmosphere. The focus margin of the round-hole recessed relief pattern obtained by the steps is 8 μm or more.

[0005] Japanese Patent Application Laid-Open No. 2019-197227

[0006] When a resin composition containing a polyimide or a precursor thereof is exposed to light and developed to produce a pattern of a cured product, there is a demand for obtaining a cured product with excellent resolution in line with the trend toward smaller devices and higher integration.

[0007] The present invention aims to provide a resin composition that can give a cured product with excellent resolution, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing the cured product, and a semiconductor device including the cured product. Another object of the present invention is to provide a method for producing a polyamic acid ester that, when used in a resin composition, can give a cured product with excellent resolution.

[0008] Representative embodiments of the present invention are shown below. <1> A resin composition comprising a resin and a polymerization initiator, wherein the resin is a polyamic acid ester having an imidization rate of 3 to 45% and an absorbance at 365 nm of a 0.050 mass% solution of the resin being 0.62 or less. <2> The resin composition according to <1>, wherein the resin has at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1-1), a repeating unit represented by the formula (1-2), a repeating unit represented by the formula (1-3), and a repeating unit represented by the formula (1-4). In formula (1-1), X １ is a tetravalent organic group, and Y １ is a divalent organic group. ２ is -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 Y ２ is a divalent organic group. ３ is -O- or -NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R ３ is a hydrogen atom or a monovalent organic group, and X ３ is a tetravalent organic group, and Y ３ is a divalent organic group. ４１ and A ４２ are each independently —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 Y ４ <3> The resin composition according to <2>, wherein the resin contains at least one repeating unit selected from the group consisting of the following repeating units A-1, A-2, A-3, and A-4: Repeating unit A-1: ​​A repeating unit represented by the above formula (1-1), wherein X １is any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (V-4). Repeating unit A-2: A repeating unit represented by the above formula (1-2), in which X ２ is any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (V-4). Repeating unit A-3: A repeating unit represented by the above formula (1-3), wherein X ３ is any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (V-4). Repeating unit A-4: A repeating unit represented by the above formula (1-4), in which X ４ A repeating unit having any of the structures represented by the following formulas (2a) to (2e), or a repeating unit having a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (V-4): In formulas (2a) to (2e), L １ and L ２ are each independently a divalent group that is not conjugated with the benzene ring to which they are bonded, or a single bond, and *1 to *4 respectively represent a bonding site with the carbonyl group described in formula (1-1), formula (1-2), formula (1-3) or formula (1-4), and hydrogen atoms in these structures may be substituted with a substituent. In formula (V-4), n1 represents an integer of 1 or more. <4> The resin composition according to <2> or <3>, wherein the resin contains at least one repeating unit selected from the group consisting of the following repeating unit B-1, repeating unit B-2, repeating unit B-3 and repeating unit B-4. Repeating unit B-1: A repeating unit represented by formula (1-1), wherein X １ Repeating unit B-2: a repeating unit represented by the above formula (1-2), wherein X ２Repeating unit B-3: a repeating unit represented by the above formula (1-3), wherein X ３ Repeating unit B-4: a repeating unit represented by the above formula (1-4), wherein X ４ a repeating unit 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), (V-2), (V-3) and (V-5): In formula (V-2), R Ｘ１ are each independently a hydrogen atom, an alkyl group, or a halogenated alkyl group. Ｘ２ and R Ｘ３ each independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ may bond to form a ring structure. <5> The resin is a repeating unit represented by the formula (1-2), ２ is a monovalent organic group having an ethylenically unsaturated bond, a repeating unit represented by the above formula (1-3), ３ is a monovalent organic group having an ethylenically unsaturated bond, and a repeating unit represented by the above formula (1-4), wherein R ４１ and R ４２ The resin composition according to any one of <2> to <4>, wherein the resin contains at least one repeating unit selected from the group consisting of repeating units in which at least one of the repeating units is a monovalent organic group having an ethylenically unsaturated bond. <6> The resin contains a repeating unit represented by formula (1-1) above, wherein Y １ a repeating unit having a structure represented by the following formula (C-1) to formula (C-3), a repeating unit having a structure represented by the above formula (1-2), ２ a repeating unit having a structure represented by the following formula (C-1) to formula (C-3), a repeating unit having a structure represented by the above formula (1-3), ３A repeating unit having a structure containing a structure represented by the following formula (C-1) to formula (C-3), and a repeating unit having the above formula (1-4), wherein Y ４ The resin composition according to any one of <2> to <5>, wherein the repeating unit is a repeating unit having a structure including a structure represented by the following formula (C-1) to formula (C-3): In formula (C-1), R １ each independently represents a hydrogen atom or a monovalent organic group, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 3, and * represents a bonding site with another structure. １ each independently represents a hydrogen atom or a monovalent organic group, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 3, R ２ Each independently represents an alkyl group or a fluoroalkyl group, and * represents a bonding site with another structure. １each independently represents a hydrogen atom or a monovalent organic group, n1 represents an integer of 0 to 3, and * represents a bonding site with another structure. <7> The resin composition according to any one of <1> to <6>, wherein the weight average molecular weight of the resin is 5,000 or more and less than 40,000. <8> The resin composition according to any one of <1> to <7>, wherein the imidization rate is 10% or more and 30% or less. <9> The resin composition according to any one of <1> to <8>, further comprising 8-azaadenine. <10> The resin composition according to any one of <1> to <9>, wherein the resin composition is a negative-type photosensitive resin composition. <11> The resin composition according to any one of <1> to <10>, wherein the resin composition is used for forming an interlayer insulating film for a redistribution layer. <12> A cured product obtained by curing the resin composition according to any one of <1> to <12>. <13> A laminate comprising two or more layers made of the cured product according to <12>, and comprising a metal layer between any two adjacent layers made of the cured product. <14> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of <1> to <12> onto a substrate to form a film. <15> A method for producing the cured product according to <14>, comprising an exposure step of selectively exposing the film to light, and a development step of developing the film with a developer to form a pattern. <16> A method for producing the cured product according to <14> or <15>, comprising a heating step of heating the film at 50 to 450°C. <17> A method for producing a laminate, comprising the method for producing a cured product according to any one of <14> to <16>. <18> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <14> to <16>. <19> A semiconductor device, comprising the cured product according to <12>. <20> A method for producing a polyamic acid ester, comprising a step of polycondensing a dicarboxylic acid and a diamine in the presence of a carbodiimide compound as a condensing agent and an active esterifying agent, wherein the method satisfies the following conditions (a) and (b): (a) an imidization rate of 3 to 45%; and (b) an absorbance at a wavelength of 365 nm of a 0.050% by mass solution is 0.62 or less. <21> The method for producing a polyamic acid ester according to <20>, wherein the active esterifying agent is 1-hydroxybenzotriazole or 1-hydroxy-7-azabenzotriazole.<22> The method for producing a polyamic acid ester according to <20> or <21>, comprising a step of treating the condensate obtained in the polycondensation step with an ion exchange resin.

[0009] According to the present invention, there are provided a resin composition which gives a cured product having excellent resolution, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing the cured product, and a semiconductor device including the cured product. Also, according to the present invention, there is provided a method for producing a polyamic acid ester which, when used in a resin composition, gives a cured product having excellent resolution.

[0010] The following describes the main embodiments of the present invention. However, the present invention is not limited to the explicitly described embodiments. 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 and upper limits, respectively. In this specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the process achieves its intended effect. In the description of a group (atomic group), a notation that does not specify whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams. As used herein, "(meth)acrylate" refers to either or both of "acrylate" and "methacrylate," "(meth)acrylic" refers to either or both of "acrylic" and "methacrylic," and "(meth)acryloyl" refers to either or both of "acryloyl" and "methacryloyl." In the structural formulae herein, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Furthermore, as used herein, the term "solid content concentration" refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. As used herein, 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, unless otherwise specified.In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and 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, when NMP is not suitable as the eluent, for example, due to low solubility, THF (tetrahydrofuran) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is assumed to be performed using a UV (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 another layer is 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." Alternatively, 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, the composition may contain two or more compounds corresponding to each component contained in the composition. 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. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0011] (Resin Composition) The resin composition of the present invention (hereinafter also simply referred to as "resin composition") comprises a resin and a polymerization initiator, wherein the resin is a polyamic acid ester having an imidization rate of 3 to 45% and an absorbance at 365 nm of 0.62 or less in a 0.050 mass% solution. Hereinafter, the polyamic acid ester having an imidization rate of 3 to 45% and an absorbance at 365 nm of 0.62 or less in a 0.050 mass% solution is also simply referred to as a "specific resin."

[0012] The resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent. The resin composition of the present invention can be used, for example, to form an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer. The resin composition of the present invention is also preferably used to form a photosensitive film that is subjected to negative development. Such a resin composition used to form a photosensitive film that is subjected to negative development is also referred to as a negative photosensitive resin composition. In the present invention, negative development refers to development in which unexposed areas are removed by development in exposure and development, and positive development refers to development in which exposed areas are removed by development. The exposure method, developer, and development method may, for example, be the exposure method described in the exposure step and the developer and development method described in the development step in the description of the method for producing a cured product described below.

[0013] The resin composition of the present invention can provide a cured product with excellent resolution. The mechanism by which the above-mentioned effects are obtained is unknown, but is presumed to be as follows.

[0014] Traditionally, carbodiimide compounds such as dicyclohexylcarbodiimide have been used as condensing agents in the synthesis of polyamic acid esters as polyimide precursors. The inventors have found that, in such synthesis methods, the acidity of the polymerization solution is reduced compared to polymerization conditions using an acid chloride as a reaction intermediate, which can lead to the imidization reaction of the resin during polymerization and the progression of a side reaction that produces an isoimide structure with high i-line absorbance. Furthermore, the inventors have found that the isoimide structure reduces the i-line transmittance of the resulting polyimide precursor, potentially resulting in a deterioration in resolution. Therefore, the inventors have found that resolution can be improved by using a resin composition containing a resin and a polymerization initiator, wherein the resin is a polyamic acid ester (specific resin) with an imidization rate of 3 to 45% and an absorbance at 365 nm of 0.62 or less in a 0.050% by mass solution. Furthermore, resins containing unstable isoimides are thought to undergo nucleophilic attack or other reactions in the composition, leading to deterioration and therefore poor storage stability. In the present invention, the absorbance is 0.62 or less, i.e., the content of isoimide structures is thought to be low, so the resin in the composition is thought to be less likely to deteriorate and the storage stability of the composition is thought to be excellent. In addition, the resin in the resin composition of the present invention has an imidization rate of 3 to 45%. This is thought to increase the imidization rate of the resin in the cured product after imidization compared to polyamic acids with an imidization rate of less than 3%. As a result, the cured product obtained from the resin composition of the present invention is thought to have excellent mechanical properties, such as elongation at break. Furthermore, the present inventors have discovered that a polyamic acid ester satisfying the following conditions (a) and (b) can be obtained by a method for producing a polyamic acid ester, which includes a step of polycondensing a dicarboxylic acid and a diamine compound in the presence of a condensing agent, a carbodiimide compound, and an active esterifying agent. (a) an imidization rate of 3 to 45%; (b) an absorbance at a wavelength of 365 nm of a 0.050% by mass solution of the polyamic acid ester is 0.62 or less. Furthermore, it was found that the absorbance can be further reduced by subjecting the polyamic acid ester obtained by the above process to an ion exchange treatment.In addition, we confirmed that applying these polyamic acid esters to negative-type photosensitive resin compositions exhibited superior resolution and insulation reliability compared to resins synthesized by conventional methods. Although the reasons for these effects are unclear, we believe that the reasons are due to (1) the addition of an active esterifying agent suppressing the isoimidization reaction at the carbodiimide active terminal of the dicarboxylic acid, and (2) the decomposition of the isoimide structure contained in the resin by the ion exchange treatment.

[0015] However, Patent Document 1 does not describe a resin composition containing a specific resin.

[0016] The components contained in the resin composition of the present invention will be described in detail below.

[0017] <Specific Resin> The resin composition of the present invention contains a polyamic acid ester (specific resin) having an imidization rate of 3 to 45% and an absorbance at 365 nm of a 0.050% by mass solution of 0.62 or less. The specific resin is preferably a polyimide precursor. A polyimide precursor refers to a resin whose chemical structure changes upon external stimulation to become a polyimide, preferably a resin whose chemical structure changes upon heating to become a polyimide, and more preferably a resin whose ring structure is formed by a ring closure reaction upon heating to become a polyimide. In the present invention, polyimide refers to a resin having a repeating unit containing an imide group in the molecular chain, and preferably a resin having a repeating unit containing an imide ring structure in the molecular chain. Furthermore, when the polyimide is a linear resin, the polyimide is preferably a resin having a repeating unit containing an imide group in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain. In this specification, the term "main chain" refers to the relatively longest connecting chain in the resin molecule, and the term "side chain" refers to other connecting chains. As used herein, the term "imide group" refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site to another structure, preferably a bonding site to a carbon atom, and more preferably a bonding site to a quaternary carbon atom. As used herein, the term "imide ring structure" refers to a ring structure containing all of the two carbon atoms and the nitrogen atom in the imide as ring members. The imide ring structure is preferably a five-membered ring. The polyimide may be a so-called polyamideimide, which has an amide group in the molecular chain in addition to the imide group. As used herein, the term "amide group" refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site to another structure, preferably a bonding site to a carbon atom, and more preferably a bonding site to a quaternary carbon atom. Furthermore, # represents a bonding site to another structure, preferably a bonding site to a hydrogen atom or a bonding site to a carbon atom, and more preferably a bonding site to a hydrogen atom.

[0018] [Imidization ratio] The imidization ratio of the specific resin is 3 to 45%. From the viewpoint of elongation at break, the imidization ratio is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more. From the viewpoint of resolution, the imidization ratio is preferably 40% or less, more preferably less than 40%, even more preferably 35% or less, even more preferably 30% or less, and particularly preferably 25% or less.

[0019] 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 such solvents include solvents contained in the resin composition, such as NMP. The viscosity may also be adjusted as appropriate within an adjustable range. The silicon wafer to which the resulting resin layer is applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer on the silicon wafer with a uniform thickness of approximately 15 μm after film formation. Here, if only a resin solution with a low viscosity is obtained and it is difficult to obtain a resin layer with a thickness of 15 μm, the film thickness may be adjusted as appropriate. For example, if the film thickness is 5 μm or greater, a similar imidization rate value can be obtained. The resin layer was measured by the ATR method using NicoletiS20 (manufactured by Thermofisher) in the measurement range of 4000 to 700 cm －１ , the measurement is performed 50 times. －１ Around (1350-1450 cm －１ (If there are multiple peaks, the peak with the greatest intensity) and 1500 cm －１ Around (1460-1550 cm －１The imidization index A of the resin is calculated by dividing the imidization index B by the peak height of the peak (or the peak with the greatest intensity if there are multiple peaks) in a nitrogen atmosphere. The imidization index B is calculated in the same manner for a film heated at a heating rate of 10°C / min under a nitrogen atmosphere and heated at 350°C for 1 hour. The imidization index A is then divided by the imidization index B to calculate the imidization rate of the resin. In measuring the imidization rate, the resin whose imidization rate is 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, resulting in a resin that is then 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 crystallization is then filtered and dried at 45°C for 20 hours to obtain a resin. Hereinafter, when measuring the physical properties of a specific resin, such as absorbance, acid value, and amine value, the resin can be obtained and measured by the same method.

[0020] [Absorbance] The specific resin has an absorbance of 0.62 or less at a wavelength of 365 nm in a 0.050% by mass solution. From the viewpoint of resolution, the absorbance is preferably 0.50 or less, more preferably 0.45 or less, and even more preferably 0.40 or less. The lower limit of the absorbance is not particularly limited, as long as it is 0.00 or more. The absorbance is measured as a solution of the specific resin in dimethyl sulfoxide (DMSO). However, if the specific resin is not soluble in DMSO at a dissolution amount of 0.050% by mass, N-methyl-2-pyrrolidone (NMP) may be used as a solvent. The absorbance is measured using a UV-1800 ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation) and a 1 cm cell. That is, the optical path length is 1 cm. The temperature during measurement is 23°C and the pressure is 1 atmosphere.

[0021] [Acid Value] From the viewpoint of storage stability and adhesion, the acid value of the specific resin is preferably 0.066 to 0.400 mmol / g, more preferably 0.069 to 0.356 mmol / g, and even more preferably 0.071 to 0.321 mmol / g. Furthermore, the acid value of the specific resin is preferably 3.70 to 22.5 mgKOH / g, more preferably 3.85 to 20.0 mgKOH / g, and even more preferably 4.00 to 18.0 mgKOH / g. The acid value is measured by a known method, for example, the method described in JIS K 0070:1992.

[0022] Furthermore, from the viewpoint of adhesion, the specific resin is preferably a polyamic acid ester having an acidic functional group content of less than 0.1 mgKOH / g at a pH below 8.0 and an acidic functional group content of 3.70 to 22.5 mgKOH / g at a pH of 8.0 or higher when titrated under the following conditions: Conditions: 0.300 g of resin is completely dissolved in 80 mL of NMP, followed by addition of 5 mL of water, and titration with a 0.01 mol / L NaOH aqueous solution. Complete dissolution can be confirmed by visual inspection to determine whether or not there is any residue. 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 complete dissolution occurs. The acidic functional group content of the above pH below 8.0 is preferably less than 0.01 mgKOH / g, more preferably less than 0.001 mgKOH / g. The acidic functional group content of the above pH at 8.0 or higher is preferably 3.70 to 22.5 mgKOH / g, more preferably 4.00 to 18.0 mgKOH / g.

[0023] [Amine Value] From the viewpoint of the storage stability of the composition, the amine value of the specific resin is preferably 0.100 mmol / g or less, more preferably 0.0001 to 0.090 mmol / g, and even more preferably 0.001 to 0.080 mmol / g. The lower limit of the amine value is not particularly limited and may be 0.00 mmol / g. The amine value is measured by dissolving 0.62 g of the resin in 50 mL of diglyme and then adding 10 mL of acetic acid to prepare a measurement solution. The solution is titrated with a 0.01 N (0.01 mol / L) solution of perchloric acid in acetic acid to detect the neutralization point.

[0024] The specific resin preferably has a polymerizable group, more preferably a radically polymerizable group. Furthermore, the resin composition of the present invention preferably satisfies at least one of the following conditions: (1) the specific resin has a polymerizable group; and (2) it further contains a polymerizable compound that does not fall under the category of the specific resin. When the specific resin has a radically polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator, more preferably contains both a radical polymerization initiator and a radical crosslinking agent. Furthermore, if necessary, a sensitizer may be included. From such a resin composition, for example, a negative-type photosensitive film is formed. Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film is formed.

[0025] The specific resin preferably has at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1-1), a repeating unit represented by the formula (1-2), a repeating unit represented by the formula (1-3), and a repeating unit represented by the formula (1-4). Among these, the specific resin preferably has at least a repeating unit represented by the formula (1-4), and more preferably has a repeating unit represented by the formula (1-4) and at least one repeating unit selected from the group consisting of a repeating unit represented by the formula (1-1), a repeating unit represented by the formula (1-2), and a repeating unit represented by the formula (1-3). In formula (1-1), X １ is a tetravalent organic group, and Y １ is a divalent organic group. ２ is -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 Y ２ is a divalent organic group. ３ is -O- or -NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R ３ is a hydrogen atom or a monovalent organic group, and X ３ is a tetravalent organic group, and Y ３ is a divalent organic group. ４１ and A ４２ are each independently —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 Y ４ is a divalent organic group.

[0026] [X １ ] In formula (1-1), X １ The number of carbon atoms in X is preferably 4 or more, more preferably 4 to 50, and even more preferably 6 to 40. １ is preferably any of the structures represented by the following formulas (2a) to (2e), or includes a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (V-4). In formulas (2a) to (2e), L １ and L ２are each independently a divalent group that is not conjugated with the benzene ring to which it is bonded, or a single bond, and *1 to *4 represent bonding sites with the carbonyl group shown in formula (1-1), formula (1-2), formula (1-3), or formula (1-4), respectively, and hydrogen atoms in these structures may be substituted with substituents. In formula (V-4), n1 represents an integer of 1 or more.

[0027] In formula (2c), L １ and L ２ are each independently —CH ２ - or -O- is preferred.

[0028] The hydrogen atoms in formulas (2a) to (2e) may be substituted with a substituent, and examples of the substituent include an alkyl group, a halogenated alkyl group, etc., and are preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group refers to a group in which at least one hydrogen atom of an alkyl group is substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F.

[0029] In formula (V-4), n1 is preferably an integer of 1 to 5, more preferably 1 or 2, and even more preferably 1. １ 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 ２ is preferably a group represented by the following formula (V-4-1): In the following formula, * represents X in formula (1-1). １ represents the bonding sites with the four carbonyl groups to which n is bonded. The definition and preferred embodiments of n1 are as described above. The hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups.

[0030] In addition, in formula (1-1), X １ It is also preferable that the compound represented by formula (V-1), (V-2), (V-3) or (V-5) below contains a structure in which two or more hydrogen atoms have been removed. In formula (V-2), R Ｘ１are each independently a hydrogen atom, an alkyl group, or a halogenated alkyl group. 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.

[0031] In formula (V-2), R Ｘ１ 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 a group in which at least one hydrogen atom of an alkyl group has been substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F. In formula (V-3), R Ｘ２ and R Ｘ３ are each preferably independently a hydrogen atom. Ｘ２ and R Ｘ３ When R Ｘ２ and R Ｘ３ The structure formed by bonding is a single bond, —O— or —C(R) ２ - is preferred, and -O- or -C(R) ２ R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom.

[0032] X １ 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 １ is preferably a group represented by the following formula (V-1-1): １ 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.

[0033] X １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-2), X１ is preferably a group represented by the following formula (V-2-1): 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, * represents X in formula (1-1). １ represents the bonding site with the four carbonyl groups to which R is bonded. 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.

[0034] X １ 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 １ 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 (1-1). １ represents the bonding site with the four carbonyl groups to which R is bonded. 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.

[0035] X １ 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 １ is preferably a group represented by the following formula (V-5-1): In the following formula, * represents X in formula (1-1). １ 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.

[0036] Other, X １ may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic acid dianhydride described in paragraphs 0055 to 0057 of JP-A No. 2023-003421.

[0037] Also, X１ It is preferable that X does not contain an imide bond in the structure. １ In the present invention, the urethane bond is preferably *—O—C(═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. Ｎ —C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ R each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. Ｎ The preferred embodiments of X are as described above. １ It is preferable that X does not contain an ester bond in its structure. In the present invention, the ester bond is a bond represented by *--O--C(=O)--*. Among these, X １ It is preferable that the copolymer does not contain an imide bond, a urethane bond, a urea bond, or an amide bond, and it is more preferable that the copolymer does not contain an imide bond, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0038] [Y １ ] In formula (1-1), Y １ The number of carbon atoms in Y is preferably 4 or more, more preferably 4 to 50, and even more preferably 6 to 40. １ is preferably a structure containing a structure represented by formula (C-1) to formula (C-3). In formula (C-1), R １ each independently represents a hydrogen atom or a monovalent organic group, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 3, and * represents a bonding site with another structure. １ each independently represents a hydrogen atom or a monovalent organic group, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 3, R ２Each independently represents an alkyl group or a fluoroalkyl group, and * represents a bonding site with another structure. １ each independently represents a hydrogen atom or a monovalent organic group, n1 represents an integer of 0 to 3, and * represents a bonding site to another structure.

[0039] In formula (C-1), R １ 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. The halogen atom in the halogenated alkyl group is preferably F or Cl, and more preferably F. In formula (C-1), n1 is preferably 0 or 1, and more preferably 1. In formula (C-1), n2 is preferably 0 or 1, and more preferably 1.

[0040] In formula (C-2), R １ Preferred embodiments of n1 and n2 are each R １ In formula (C-2), R ２ are each independently preferably an alkyl group having 1 to 4 carbon atoms or a fluoroalkyl group having 1 to 4 carbon atoms, more preferably a methyl group or a trifluoromethyl group.

[0041] In formula (C-3), R １ and n1 are each preferably represented by R １ and n1 are the same as the preferred embodiments.

[0042] In formulae (C-1) to (C-3), each * is preferably a bonding site to a nitrogen atom.

[0043] Also, Y １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (C-1), Y １is preferably a group represented by the following formula (C-1-2) or formula (C-1-3). In the following formulas, * represents a bonding site with the nitrogen atom, 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.

[0044] Also, Y １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (C-2), Y １ is preferably a group represented by the following formula (C-2-3) or formula (C-2-4), and from the viewpoint of reducing the dielectric constant of the cured product, it is preferably a group represented by formula (C-2-4). Ｘ１ represents a single bond or —O—, and * represents the bonding site with the nitrogen atom. ２ 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.

[0045] [X ２ , Y ２ X in formula (1-2) ２ and Y ２ A preferred embodiment of the formula is X １ and Y １ However, the preferred embodiments of X are the same as those of １ and Y １ In the explanation of the formula (1-1), the expression "formula (1-1)" should be read as "formula (1-2)".

[0046] [A ２ A in formula (1-2) ２ is —O— or —NR ｚ -, and -O- is preferred. ｚ represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.

[0047] [R ２ R in formula (1-2) ２represents 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. ２ It is preferable that the specific resin contains a polymerizable group. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, or the like, and a radically polymerizable group is preferable. 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 specific resin 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 (e.g., a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and a group represented by the following formula (III) is preferable.

[0048]

[0049] 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 with another structure. In formula (III), R ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group. ２０１ Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a dodecamethylene group; a 1,2-butanediyl group, a 1,3-butanediyl group; a —CH ２ CH(OH)CH ２ alkylene groups such as ethylene and propylene; ２ CH(OH)CH ２More preferred are alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups. In the present invention, a 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 a polyalkyleneoxy group contains multiple alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having an alternating pattern. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent if the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group. In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. The preferred embodiments of the number of repeating ethyleneoxy groups and the like in these groups are as described above.

[0050] In formula (1-2), R ２is a hydrogen atom, the specific resin 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.

[0051] In formula (1-2), R ２ However, it may also 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. However, 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.

[0052] [X ３ , Y ３ , A ３ , R ３ X in formula (1-3) ３ and Y ３ A preferred embodiment of the formula is X １ and Y １ However, the preferred embodiments of X are the same as those of １ and Y １ In the explanation of the formula (1-1), the description of "formula (1-1)" should be read as "formula (1-3)". ３ and R ３ A preferred embodiment of the formula (1-2) is ２ and R ２ However, the same as the preferred embodiment of A ２ and R ２ In the explanation of the formula (1-2), the expression "formula (1-2)" should be read as "formula (1-3)."

[0053] [X４ , Y ４ , A ４１ , A ４２ , R ４１ , R ４２ X in formula (1-4) ４ and Y ４ A preferred embodiment of the formula is X １ and Y １ However, the preferred embodiments of X are the same as those of １ and Y １ The description of "Formula (1-1)" in the explanation of (1) should be read as "Formula (1-4)". ４１ and A ４２ A preferred embodiment of each of the above is A in formula (1-2). ２ However, the same as the preferred embodiment of A ２ The description of "formula (1-2)" in the explanation of formula (1-4) should be read as "formula (1-4)". ４１ and R ４２ Preferred embodiments of the formula (1-2) are: ２ However, the preferred embodiments are the same as those of the above. ２ In the explanation of the formula (1-2), the expression "formula (1-2)" should be read as "formula (1-4)."

[0054] Here, in all of the repeating units represented by formula (1-2), the repeating units represented by formula (1-3), and the repeating units represented by formula (1-4) contained in the specific resin, R ２ and R ３ , R ４１ and R ４２ R relative to the total molar amount of ２ and R ３ , R ４１ and R ４２ The content of monovalent organic groups is preferably 50.0 to 100%, more preferably 85.0 to 100%, and even more preferably 92.0 to 100%.

[0055] Furthermore, the ratio of the molar content of amic acid ester structures to the total molar content of amic acid structures and amic acid ester structures in the specific resin (esterification rate) is preferably 90% or more, more preferably 95% or more, and even more preferably 97% or more. The upper limit of this ratio is not particularly limited, and it is sufficient if it is 100% or less. The esterification rate can be estimated from the acid value and structure of the resin.

[0056] The specific resin preferably contains at least one repeating unit selected from the group consisting of the following repeating units A-1, A-2, A-3, and A-4: Repeating unit A-1: ​​A repeating unit represented by the above formula (1-1), wherein X １ is any one of the structures represented by formula (2a) to formula (2e), or a repeating unit containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-4). Repeating unit A-2: A repeating unit represented by formula (1-2) above, wherein X ２ is any of the structures represented by formula (2a) to formula (2e), or a repeating unit containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-4). Repeating unit A-3: A repeating unit represented by formula (1-3) above, wherein X ３ is any of the structures represented by formula (2a) to formula (2e), or a repeating unit containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-4). Repeating unit A-4: A repeating unit represented by formula (1-4) above, wherein X ４ a repeating unit having any of the structures represented by formula (2a) to formula (2e), or a repeating unit containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-4). Among these, the specific resin preferably contains the repeating unit A-4, and more preferably contains the repeating unit A-4 and at least one repeating unit selected from the group consisting of the repeating unit A-1, the repeating unit A-2, and the repeating unit A-3.

[0057] The specific resin preferably contains at least one repeating unit selected from the group consisting of the following repeating units B-1, B-2, B-3, and B-4. In particular, the specific resin preferably contains at least one repeating unit selected from the group consisting of the repeating unit A-1, A-2, A-3, and A-4, and at least one repeating unit selected from the group consisting of the following repeating units B-1, B-2, B-3, and B-4. Of these, the specific resin preferably contains the repeating unit A-4 and the repeating unit B-4. Repeating unit B-1: A repeating unit represented by the above formula (1-1), wherein X １ Repeating unit B-2: a repeating unit represented by the above formula (1-2), wherein X ２ Repeating unit B-3: a repeating unit represented by the above formula (1-3), wherein X ３ Repeating unit B-4: a repeating unit represented by the above formula (1-4), wherein X ４ a repeating unit containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1), (V-2), (V-3) and (V-5):

[0058] The specific resin is a repeating unit represented by the above formula (1-2), R ２ is a monovalent organic group having an ethylenically unsaturated bond, a repeating unit represented by the above formula (1-3), ３ is a monovalent organic group having an ethylenically unsaturated bond, and a repeating unit represented by the above formula (1-4), wherein R ４１ and R ４２and R ４１ and R ４２ It is more preferable that at least one of the repeating units contains a monovalent organic group having an ethylenically unsaturated bond.

[0059] The specific resin is a repeating unit represented by the above formula (1-1), １ a repeating unit having a structure represented by formula (C-1) to formula (C-3), a repeating unit having a structure represented by formula (1-2), ２ a repeating unit having a structure represented by the following formula (C-1) to formula (C-3), a repeating unit having a structure represented by the above formula (1-3), ３ a repeating unit having a structure containing a structure represented by formula (C-1) to formula (C-3), and a repeating unit having a structure represented by formula (1-4), wherein Y ４ It is preferable that the repeating unit represented by formula (1-1) contains at least one repeating unit selected from the group consisting of repeating units having a structure containing a structure represented by formula (C-1) to formula (C-3). １ The repeating unit having a structure containing the structure represented by formula (C-1) to formula (C-3) is preferably a repeating unit corresponding to the repeating unit A-1 or repeating unit B-1 described above. ２ The repeating unit having a structure containing the structure represented by formula (C-1) to formula (C-3) is preferably a repeating unit corresponding to the repeating unit A-2 or repeating unit B-2 described above. ３ The repeating unit having a structure containing the structure represented by formula (C-1) to formula (C-3) is preferably a repeating unit corresponding to the repeating unit A-3 or repeating unit B-3 described above. ４The repeating unit having a structure containing the structure represented by formula (C-1) to formula (C-3) is preferably a repeating unit corresponding to the repeating unit A-4 or repeating unit B-4 described above.

[0060] In one embodiment of the specific resin of the present invention, the total content of repeating units represented by formula (1-1), formula (1-2), formula (1-3), or formula (1-4) 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%. The upper limit of the total content is not particularly limited, and all repeating units in the specific resin except for the terminal repeating units may be repeating units represented by formula (1-1), formula (1-2), formula (1-3), or formula (1-4).

[0061] In another embodiment of the specific resin of the present invention, the total content of repeating units represented by formula (1-4) is 50 mol% or more of all repeating units. The total content is more preferably 60 mol% or more, even more preferably 70 mol% or more, and particularly preferably 80 mol% or more. The upper limit of the total content is preferably 97 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less, and particularly preferably 85 mol% or less.

[0062] Furthermore, in the specific resin of the present invention, the total content of repeating units corresponding to repeating unit A-1, repeating unit A-2, repeating unit A-3, or repeating unit A-4 (also referred to as "repeating unit A") is preferably 20 mol% or more of all repeating units. The total content is more preferably 30 mol% or more, even more preferably 40 mol% or more, and particularly preferably 50 mol% or more. There is no particular upper limit to the total content, and all repeating units in the specific resin except for the terminal repeating units may be repeating units A.

[0063] Furthermore, in the specific resin of the present invention, the total content of repeating units corresponding to repeating unit B-1, repeating unit B-2, repeating unit B-3, or repeating unit B-4 (also referred to as "repeating unit B") is preferably 0 to 80 mol % of all repeating units, more preferably 5 to 70 mol %, even more preferably 10 to 60 mol %, and particularly preferably 15 to 50 mol %.

[0064] In addition, the total content of repeating units A and B in the specific resin of the present invention is preferably 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%. The upper limit of the total content is not particularly limited, and all repeating units in the specific resin except for the terminal repeating units may be repeating units A or B.

[0065] From the viewpoint of adhesiveness, it is also preferable that the specific resin is substantially free of fluorine atoms. Here, "substantially free" means that the amount of fluorine atoms relative to the total mass of the specific resin 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. The lower limit of the amount of fluorine atoms is not particularly limited, and may be 0% by mass.

[0066] The weight average molecular weight (Mw) of the specific resin is preferably 120,000 or less, more preferably 50,000 or less, and even more preferably less than 40,000. 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 the specific resin 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 specific resin is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the specific resin is not particularly specified, but is, for example, 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 specific resins as specific resins, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one specific resin 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 specific resins as one resin are each within the above ranges.

[0067] [Method for Producing Specific Resin] The method for producing the specific resin preferably includes a step of polycondensing a dicarboxylic acid and a diamine in the presence of a carbodiimide compound as a condensing agent and an active esterifying agent (polycondensation step).

[0068] -Dicarboxylic Acid- The dicarboxylic acid used in the polycondensation step can be obtained, for example, by esterifying a carboxylic acid dianhydride by a known method. For example, the method described in paragraphs 0049 to 0051 of WO 2023 / 162905 can be referenced.

[0069] Examples of the dicarboxylic acid include compounds represented by the following formula (DCa-1), and examples of the carboxylic acid dianhydride include compounds represented by the following formula (DCa-2). In formula (DCa-1), X １ is a tetravalent organic group, and R ４１ and R ４２ Each of X independently represents a monovalent organic group. １ In formula (DCa-1), X is a tetravalent organic group. １ A preferred embodiment of the formula (1-1) is X １ In formula (DCa-1), R ４１ and R ４２ A preferred embodiment of the formula (1-4) is R ４１ and R ４２ In formula (DCa-2), X １ A preferred embodiment of the formula (1-1) is X １ This is the same as the preferred embodiment of the above.

[0070] For example, by mixing a compound represented by formula (DCa-2) with an alcohol in the presence of a basic catalyst such as pyridine, an esterification reaction of the acid anhydride proceeds, thereby obtaining a compound represented by formula (DCa-1). The reaction conditions can be, for example, a temperature of 20 to 50°C and a reaction time of 4 to 10 hours. However, the reaction conditions can be set depending on the compound.

[0071] The esterification reaction is preferably carried out in a solvent. The solvent is preferably one that can dissolve the raw materials, the compound represented by formula (DCa-2) and the alcohol, as well as the product, the compound represented by formula (DCa-1). A more preferred solvent is one that can dissolve the polyamic acid ester, which is the polycondensate finally obtained in the polycondensation step. Examples of such reaction solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons. Among these, examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; examples of esters include methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate; examples of lactones include γ-butyrolactone; examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran; examples of halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, and o-dichlorobenzene; and examples of hydrocarbons include hexane, heptane, benzene, toluene, and xylene.

[0072] -Diamine- Examples of diamines include compounds represented by the following formula (DAm-1). In formula (DAm-1), Y １ represents a divalent organic group. １ A preferred embodiment of the formula (1-1) is Y １ This is the same as the preferred embodiment of the above.

[0073] -Carbodiimide Compound- As the carbodiimide compound, dialkylcarbodiimide is preferred, and dicyclohexylcarbodiimide or diisopropylcarbodiimide is more preferred. The amount of the carbodiimide compound used is not particularly limited and may be appropriately determined depending on the raw material, but is preferably 1.0 to 5.0 molar equivalents, more preferably 1.5 to 3.0 molar equivalents, relative to the molar amount of the dicarboxylic acid used as the raw material.

[0074] -Active esterifying agent- Examples of the active esterifying agent include 1-hydroxybenzotriazole or 1-hydroxy-7-azabenzotriazole, N-hydroxysuccinimide, ethyl cyanohydroxyiminoacetate (oxyma), etc., with 1-hydroxybenzotriazole or 1-hydroxy-7-azabenzotriazole being preferred. The amount of the active esterifying agent used is not particularly limited and may be appropriately determined depending on the raw materials, but is preferably 0.1 to 2.5 molar equivalents, and more preferably 0.2 to 2.2 molar equivalents, relative to the molar amount of the dicarboxylic acid used as the raw material.

[0075] -Polycondensation Method- For example, the above-mentioned dicarboxylic acid is mixed with the above-mentioned carbodiimide compound, preferably under ice cooling, to convert the dicarboxylic acid into a polyacid anhydride as an intermediate, and then the above-mentioned diamine dissolved in a solvent (preferably the solvent described in the above esterification reaction) is added dropwise to the polyacid anhydride to cause amide polycondensation between the two, thereby obtaining a polyamic acid ester.

[0076] After the polycondensation step is completed, precipitated by-products may be filtered off as needed, and then a suitable poor solvent (e.g., water, aliphatic lower alcohol, or a mixture thereof) may be added to the solution containing the polyamic acid ester to precipitate the polyamic acid ester. Further, redissolution and reprecipitation procedures may be repeated as needed to purify the polyamic acid ester, followed by vacuum drying to isolate the desired polyamic acid ester.

[0077] -Step of treating with ion exchange resin- Furthermore, the method for producing the specific resin preferably includes a step of treating the condensate obtained in the polycondensation step with an ion exchange resin. The ion exchange resin is preferably an amphoteric ion exchange resin or an anion exchange resin. The treatment with the ion exchange resin can be carried out, for example, by passing a solution of the condensate obtained in the polycondensation step (which may be purified, if necessary, by repeating the redissolution and reprecipitation procedures described above) through a column packed with the ion exchange resin swollen with a solvent (preferably the solvent described in the esterification reaction above).

[0078] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the specific resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0079] <Other Resins> The resin composition of the present invention may contain the above-described specific resin and another resin (hereinafter simply referred to as "other resin") different from the specific resin. Examples of other resins include polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamides not falling under the category of 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, which do not fall under the category of specific 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 below, a polymerizable compound having a high polymerizable group value and a weight average molecular weight of 20,000 or less (for example, a polymerizable group content of 1×10 per 1 g of resin) can be used. －３ By adding a (meth)acrylic resin (having a molecular weight of at least 100 mol / g) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0080] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. When the resin composition of the present invention 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, based on the total solid content of the resin composition. A preferred embodiment of the resin composition of the present invention may also be an embodiment in which the content of the other resin is low. In the above embodiment, the content of the other resin 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, as long as it is 0% by mass or more. The resin composition of the present invention 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.

[0081] <Polymerizable Compound> The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include a radical crosslinking agent and other crosslinking agents.

[0082] [Radical Crosslinking Agent] The resin composition of the present invention 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.

[0083] 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. The radical crosslinking agent may 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 obtained pattern (cured product), it is also preferable that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.

[0084] 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.

[0085] 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 group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. Specific examples can be found in paragraphs 0113 to 0122 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0086] 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.

[0087] Other preferred radical crosslinking agents than those mentioned above include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0088] 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.)), and structures in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue. Oligomers of these agents can also be used.

[0089] 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 ester include UAS-10 and 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).

[0090] 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 JP-A No. 01-105238, can also be used as radical crosslinking agents.

[0091] 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 obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group. Particularly preferred is a radical crosslinking agent obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of an aliphatic polyhydroxy compound to provide an acid group, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by Toagosei Co., Ltd.

[0092] 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. Furthermore, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.

[0093] As the radical crosslinking agent, 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") is also preferred. When the resin composition contains crosslinking agent U, chemical resistance, resolution, etc. may be improved. Examples of crosslinking agent U include the compounds described in paragraphs 0133 to 0143 of WO 2023 / 190064, the contents of which are incorporated herein by reference.

[0094] From the viewpoints of pattern resolution and film stretchability, the resin composition preferably uses a bifunctional methacrylate or acrylate. 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-hexyl ... Xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, EO-modified isocyanuric acid dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having a urethane bond 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 approximately 200 for the polyethylene glycol chain. From the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinking agent can preferably be used as the radical crosslinking agent in the resin composition of the present invention.Preferred examples of monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. Preferred monofunctional radical crosslinking agents include compounds having a boiling point of 100°C or higher under normal pressure in order to suppress volatilization before exposure. Other examples of bifunctional or higher radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0095] 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, based on 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.

[0096] 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.

[0097] [Other Crosslinking Agents] The resin composition of the present invention preferably contains another crosslinking agent different from the radical crosslinking agent described above. The other crosslinking agent refers to a crosslinking agent other than the radical crosslinking agent described above. It is preferably a compound having multiple groups in its molecule that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products upon exposure to light by a photoacid generator or a photobase generator. It is preferable that the compound have multiple groups in its molecule that promote the reaction of forming a covalent bond with other compounds in the composition or their reaction products under the action of an acid or base. The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator during the exposure step. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0098] [Polymerization initiator] The resin composition of the present invention contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0099] The photoradical polymerization initiator has a capacity of at least about 50 L·mol within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure the molar absorption coefficient using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g / L using ethyl acetate as a solvent.

[0100] Any known compound can be used as the photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, 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 of these compounds, please refer to 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 can be mentioned, the contents of which are incorporated herein by reference.

[0101] 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. As a commercially available product, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

[0102] 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.

[0103] Examples of α-hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).

[0104] Examples of α-aminoketone initiators that can be used include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF).

[0105] As the aminoacetophenone initiator, acylphosphine oxide initiator, and metallocene compound, for example, 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.

[0106] 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.

[0107] 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) described compounds, 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.

[0108] 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 the resin composition, it is particularly preferable to use an oxime compound as a photoradical polymerization initiator. The oxime compound as a photoradical polymerization initiator has a linking group of >C=N-O-C(=O)- in the molecule.

[0109]

[0110] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (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 ChemiX Co., Ltd.), and SpeedCure PDO (SARTOMER Also, an oxime compound having the following structure can be used.

[0111] Examples of photoradical polymerization initiators include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, and oxime compounds having a fluorine atom, as described in paragraphs 0169 to 0171 of WO 2021 / 112189. Also usable are oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxy group is bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of WO 2021 / 020359. The contents of these compounds are incorporated herein by reference.

[0112] 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.

[0113] When the resin composition contains a photopolymerization initiator, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. 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. Note that the photopolymerization initiator may also function as a thermal polymerization initiator, and therefore crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, hot plate, or the like.

[0114] [Sensitizer] The resin composition may contain a sensitizer. The sensitizer absorbs specific actinic radiation and becomes electronically excited. The electronically excited sensitizer comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and undergoes electron transfer, energy transfer, heat generation, and other actions. This causes the thermal radical polymerization initiator or the photoradical polymerization initiator to undergo a chemical change and decompose, generating a radical, acid, or base. Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds.Examples of the sensitizer 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-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, and Non, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (ethyl 7-(diethylamino)coumarin-3-carboxylate), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate Examples of sensitizing dyes include soamyl, 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, and 3',4'-dimethylacetanilide. Other sensitizing dyes may also be used. For details of sensitizing dyes, please refer to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein by reference.

[0115] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and still more preferably 0.5 to 10 mass %, based on the total solid content of the resin composition. The sensitizer may be used alone or in combination of two or more types.

[0116] [Chain Transfer Agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684. Examples of chain transfer agents include those having -S-S-, -SO ２ Examples of compounds that can be used include compounds having -S-, -N-O-, SH, PH, SiH, and GeH, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can donate hydrogen to low-activity radicals to generate radicals, or can be oxidized and then deprotonated to generate radicals. Thiol compounds are particularly preferred.

[0117] 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.

[0118] 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. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total content thereof is preferably within the above range.

[0119] In another preferred embodiment of the present invention, the resin composition of the present invention contains two or more polymerization initiators. Specifically, the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or contains the above-mentioned photoradical polymerization initiator and a photoacid generator.

[0120] By including a photopolymerization initiator and a thermal polymerization initiator described below, pattern formation by exposure becomes possible, and radical polymerization also proceeds more easily 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 included, the content of the thermal polymerization initiator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0121] Inclusion of a photoradical polymerization initiator and a photoacid generator may improve performance such as resolution. When a photopolymerization initiator and a photoacid generator are included, 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 %.

[0122] [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 a thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance.

[0123] Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein by reference.

[0124] When a thermal polymerization initiator is contained, 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%, 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 in the above range.

[0125] <Base Generator> The resin composition of the present invention 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. When the resin composition contains a thermal base generator, the cyclization reaction of the precursor can be promoted by heating, for example, 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 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.

[0126] Examples of the base generator include, but are not limited to, the following compounds:

[0127]

[0128] 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.

[0129] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0130] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0131] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0132] 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.

[0133] 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 diamine, 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 ter, 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, but are not limited to these.

[0134] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.

[0135] <Solvent> The resin composition of the present invention 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.

[0136] 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 (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters ...alkyloxypropionate, ethyl 3-alkyloxypropionate, 2-alkyloxypropionic acid alkyl esters (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 3- Preferred examples thereof include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), 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.

[0137] 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.

[0138] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0139] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0140] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0141] 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.

[0142] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0143] 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.

[0144] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0145] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more solvents, is preferred. 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-dimethylpropionamide and γ-butyrolactone, a combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or a combination of N-methyl-2-pyrrolidone and ethyl lactate. An embodiment in which toluene is further added to these combined solvents in an amount of approximately 1 to 10% by mass, based on the total mass of the solvent, is also a preferred embodiment of the present invention. In particular, from the viewpoint of the storage stability of the resin composition, an embodiment in which γ-valerolactone is included as a solvent is also a preferred embodiment 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 above content is not particularly limited and may be 100% by mass. The above content may be determined taking into consideration the solubility of components such as the specific resin contained in the resin composition, etc. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, the solvent preferably contains 60 to 90 mass% of γ-valerolactone and 10 to 40 mass% of dimethyl sulfoxide, more preferably 70 to 90 mass% of γ-valerolactone and 10 to 30 mass% of dimethyl sulfoxide, and even more preferably 75 to 85 mass% of γ-valerolactone and 15 to 25 mass% of dimethyl sulfoxide, relative to the total mass of the solvent.

[0146] From the viewpoint of coatability, the content of the solvent is preferably an amount such that the total solids concentration of the resin composition of the present invention is 5 to 80 mass%, more preferably an amount such that the total solids concentration is 5 to 75 mass%, even more preferably an amount such that the total solids concentration is 10 to 70 mass%, and even more preferably an amount such that the total solids concentration is 20 to 70 mass%. The solvent content 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 of the solvents is preferably within the above range.

[0147] <Metal Adhesion Improver> The resin composition of the present invention 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.

[0148] [Silane Coupling Agent] Examples of silane coupling agents include the compounds described in paragraph 0316 of WO 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573 A, 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 JP 2011-128358 A. It is also preferable to use the following compounds as the silane coupling agent. In the formula below, 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.).

[0149]

[0150] 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 silane coupling agents 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-isocyanatopropyltriethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride. These may be used alone or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups may also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing a repeating unit represented by the following formula (S-1): In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ represents a hydrogen atom, a hydroxy group or an alkoxy group, and n represents an integer of 0 to 2. 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 (for example, 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, preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same. Here, of 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. Such oligomer-type compounds can be commercially available products, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0151] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0152] Other metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935, the contents of which are incorporated herein by reference.

[0153] 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 the specific resin. By ensuring that the content is equal to or greater than the above 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 above 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.

[0154] <Compound X1> The resin composition of the present invention may contain compound X1. Compound X1 is a compound having at least one structure selected from the group consisting of a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure, and having a molecular weight of 1,000 or less. Here, the 1,3-dicarbonyl structure refers to a structure represented by formula (DC-1) below, and the β-hydroxycarbonyl structure refers to a structure represented by formula (HC-1) below.

[0155] In formula (DC-1) or formula (HC-1), * and # each represent a bonding site with another structure. Here, * is preferably a bonding site with a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. Also, # is preferably a bonding site with a hydrogen atom or a carbon atom. Here, the structure represented by (DC-1) above may be an enol type as shown in formula (DC-2) below. Also, the structure represented by (HC-1) above may be an enol type as shown in formula (HC-2) below. In formula (DC-2) or formula (HC-2), * and # each represent a bonding site to another structure. * is preferably a bonding site to a carbon atom, oxygen atom, nitrogen atom, or sulfur atom. Also, # is preferably a bonding site to a hydrogen atom or carbon atom.

[0156] It is preferable that compound X1 does not contain a metal atom in its structure. The metal atom here does not include metalloid atoms such as silica atoms. Furthermore, it is preferable that compound X1 is not coordinated to a metal atom in the resin composition.

[0157] [Molecular Weight] The molecular weight of compound X1 is 1,000 or less, preferably 100 to 500, more preferably 100 to 400, even more preferably 100 to 350, particularly preferably 100 to 300, and even more preferably 100 to 250.

[0158] [Specific Examples] Specific examples of compound X1 include, but are not limited to, compounds having the following structures.

[0159] [Content] The content of compound X1 relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 30% by mass. The lower limit is more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more. The upper limit is more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less. An embodiment in which the content is 1% by mass or less is also one of the preferred embodiments of the present invention. One type of compound X1 may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total amount thereof preferably falls within the above range.

[0160] <Migration Inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively inhibited.

[0161] The migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used. Among these, the resin composition of the present invention preferably contains 8-azaadenine.

[0162] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0163] Other migration inhibitors include the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, the compounds described in paragraph 0052 of JP-A-2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, and the compounds described in paragraph 0166 of WO 2015 / 199219. The contents of this specification are incorporated herein by reference.

[0164] Specific examples of the migration inhibitor include the following compounds.

[0165]

[0166] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the resin composition.

[0167] The migration inhibitor may be one kind or two or more kinds. When two or more kinds of migration inhibitors are used, the total amount thereof is preferably within the above range.

[0168] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

[0169] Specific examples of the polymerization inhibitor include the compounds described in paragraph 0310 of WO 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, and the like, the contents of which are incorporated herein by reference.

[0170] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass%, more preferably 0.02 to 15 mass%, and even more preferably 0.05 to 10 mass%, based on the total solid content of the resin composition.

[0171] The polymerization inhibitor may be one kind or two or more kinds. When two or more kinds of polymerization inhibitors are used, the total amount thereof is preferably within the above range.

[0172] [Urea Compounds, Carbodiimide Compounds, Isourea Compounds] From the viewpoint of elongation at break and adhesion to a metal or resin layer, the resin composition of the present invention may contain at least one compound selected from the group consisting of a compound having a urea bond (urea compound), a compound having a carbodiimide structure (carbodiimide compound), and a compound having an isourea bond (isourea compound) (hereinafter also referred to as "urea compound, etc."). Among these, it is preferable that the resin composition of the present invention further contains a compound having a urea bond. The urea compounds, etc. referred to here do not include the above-mentioned polymerizable compounds and compounds corresponding to silane coupling agents. Examples of urea compounds include the compounds described in paragraphs 0334 to 0339 of WO 2022 / 070730.

[0173] Specific examples of the urea compound include, but are not limited to, dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea.

[0174] The total content of the urea compounds and the like is preferably 0.1 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, per 100 parts by mass of the specific resin. The urea compounds and the like may be used alone or in combination of two or more types. When two or more types of bases are used in combination in the base-containing treatment liquid, it is preferable that the total content thereof be within the above range.

[0175] <Light absorber> The resin composition of the present invention preferably contains a compound (light absorber) whose absorbance at the exposure wavelength is reduced by 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 these compounds are incorporated herein by reference.

[0176] It is also preferable to include a compound having the following structure as the light absorber.

[0177] The content of the light absorber relative to the total solid content of the resin composition of the present invention 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%.

[0178] <Other Additives> The resin composition of the present invention may contain various additives, as needed, within the scope of obtaining the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.). By appropriately incorporating these components, it is possible to adjust properties such as film physical properties. For details of these components, please refer to, for example, the descriptions in paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812 ), and the descriptions in paragraphs 0101 to 0104 and 0107 to 0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are blended, the total content thereof is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0179] <Characteristics of Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, and 2,500 mm ２ / s~8,000mm ２ Within the above range, it is easy to obtain a highly uniform coating film. ２ If the thickness is more than 12,000 mm / s, it is easy to apply the coating to a thickness required for an insulating film for rewiring, for example. ２ If the viscosity is less than 1 / s, a coating film with excellent surface condition can be obtained.

[0180] <Restrictions on substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0181] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. 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.

[0182] Furthermore, examples of methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.

[0183] Considering the use of the resin composition of the present invention 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. In particular, 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-mentioned range. Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.

[0184] A conventionally known container can be used as a container for storing the resin composition of the present invention. For the purpose of preventing impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six resin layers, 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.

[0185] <Cured Product of Resin Composition> A cured product of the resin composition can be obtained by curing the resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the resin composition. The resin composition is preferably cured by heating, with a heating temperature of 120°C to 400°C being more preferred, 140°C to 380°C being even more preferred, and 170°C to 350°C being particularly preferred. The form of the cured product of the resin composition 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 shape of the cured product can be selected depending on the application, such as forming a protective film on a wall surface, forming via holes for electrical conductivity, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage of change in volume of the resin composition before and after curing, and can be calculated by the following formula: Shrinkage rate [%] = 100 - (volume after curing / volume before curing) x 100

[0186] <Characteristics of cured product of resin composition> The imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties. The elongation at break of the cured product of the resin composition 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 resin composition of the present invention is preferably 180°C or more, more preferably 210°C or more, and even more preferably 230°C or more.

[0187] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited, and can be 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.

[0188] For the purpose of removing foreign matter such as dust and fine particles from the resin composition of the present invention, filtration using a filter is preferably performed. 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.

[0189] (Method for producing a cured product) The method for producing a cured product of the present invention preferably includes a film-forming step in which a resin composition is applied to a substrate to form a film. The method for producing a cured product more preferably includes the film-forming step, an exposure step in which the film formed in the film-forming step is selectively exposed to light, and a development step in which the film exposed in the exposure step is developed using a developer to form a pattern. The method for producing a cured product particularly preferably includes the film-forming step, the exposure step, the development step, and at least one of a heating step in which the pattern obtained in the development step is heated and a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product also preferably includes the film-forming step and a step of heating the film. Details of each step are described below.

[0190] <Film Forming Step> The resin composition of the present invention can be used in a film forming step of applying the resin composition to 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 to a substrate to form a film.

[0191] [Substrate] 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 plasma display panel (PDP) electrode plates. Substrates are particularly preferably semiconductor production substrates, with silicon substrates, Cu substrates, and mold substrates being more preferred. These substrates may have a surface layer such as an adhesion layer or an oxide layer formed by hexamethyldisilazane (HMDS) or the like. The shape of the substrate is not particularly limited and may be circular or rectangular. The size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular. If it is rectangular, the length of the short side is preferably, for example, 100 to 1000 mm, more preferably 200 to 700 mm. As the substrate, for example, a plate-shaped, preferably a panel-shaped substrate (substrate) is used.

[0192] 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.

[0193] Coating is preferred as a means for applying the resin composition to a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and coating conditions depending on the application method, a film of the desired thickness can be obtained. In addition, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc. are preferred, and for rectangular substrates, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a method can be used in which a coating film formed by applying the coating composition to a temporary support in advance using the above-described application method is transferred onto the substrate. Regarding the transfer method, the preparation 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. A step of removing excess film from the edge of the substrate may also be performed. Examples of such a step include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may also be employed in which the substrate is coated with various solvents before applying the resin composition to the substrate, improving the wettability of the substrate and then applying the resin composition.

[0194] <Drying Step> 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 carried out 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.

[0195] <Exposure Step> The film may be subjected to an exposure step in which the film is selectively exposed to light. The method for producing a cured product may include an exposure step in which the film formed in the film formation step is selectively exposed to light. Selective exposure means that a portion of the film is exposed to light. Furthermore, selective exposure forms exposed regions (exposed portions) and unexposed regions (unexposed portions) in the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is 50 to 10,000 mJ / cm2 in terms of exposure energy at a wavelength of 365 nm. ２ is preferred, and 200 to 8,000 mJ / cm ２ is more preferred.

[0196] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0197] The exposure wavelengths, in relation to the light source, are: (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.); (2) metal halide lamp; (3) high-pressure mercury lamp, 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 laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F ２Examples of such light include excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and (7) YAG laser second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, 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 portion of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0198] <Post-Exposure Bake Step> The film may be subjected to a heating step (post-exposure bake step) after exposure. That is, the method for producing a cured product of the present invention may include a post-exposure bake step in which the film exposed in the exposure step is heated. The post-exposure bake step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure bake step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure bake step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature rise rate in the post-exposure bake step from the temperature at the start of heating 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 also be changed as appropriate during heating. The heating means in the post-exposure bake step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. may 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.

[0199] <Development step> The above-mentioned film after exposure may be subjected to a development step in which it is developed using 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 using a developer to form a pattern. By carrying out development, one of the exposed and unexposed parts of the film is removed to form a pattern. Here, development in which the unexposed parts of the film are removed in the development step is called negative development, and development in which the exposed parts of the film are removed in the development step is called positive development.

[0200] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0201] When the developer is an alkaline aqueous solution, examples of basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Examples of basic compounds 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.

[0202] 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.

[0203] 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.

[0204] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the content may be 100% by mass.

[0205] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0206] In the developing step, after the treatment with the developer, the pattern may be further washed (rinsed) with a rinse liquid. Alternatively, a method may be employed in which a rinse liquid is supplied before the developer in contact with the pattern is completely dried.

[0207] [Rinse Liquid] 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.

[0208] When the rinse solution 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 solution 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.

[0209] 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.

[0210] 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, and may also account for 100% by mass of the total mass of the rinse solution.

[0211] The rinse solution may contain at least one of a basic compound and a base generator. Although not particularly limited, when the developer contains an organic solvent, an embodiment in which the rinse solution contains the organic solvent and at least one of a basic compound and a base generator is also one of the preferred embodiments of the present invention. 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 when the developer contains an organic solvent, and the same applies to preferred embodiments. The basic compound and base generator contained in the rinse solution may be selected taking into consideration the solubility in the solvent in the rinse solution, etc.

[0212] When the rinse solution contains at least one of a basic compound and a base generator, the content of the basic compound or base generator is preferably 10% by mass or less, and 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 0.1% by mass or more, for example. 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 also preferably 70 to 100% by 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 type of at least one of the basic compound and the base generator, or may contain two or more types. When at least one of the basic compound and the base generator is two or more types, the total content thereof is preferably within the above-mentioned range.

[0213] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0214] [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, methods of supplying the rinse liquid using a shower nozzle, straight nozzle, spray nozzle, etc. are available, and a method of continuously supplying using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, a method of supplying using a spray nozzle is more preferred. The type of nozzle is not particularly limited, and examples include a straight nozzle, shower nozzle, spray nozzle, etc. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinse liquid to the exposed film using a straight nozzle, and more preferably a step of supplying the rinse liquid using 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.

[0215] 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.

[0216] 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.

[0217] <Heating Step> The pattern obtained by the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step 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 in which the pattern obtained by the development step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a development step, or a film obtained by a film formation step is heated. In the heating step, the specific resin is cyclized to form a resin such as polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in a crosslinking agent other than the specific resin 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, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0218] The heating step is preferably a step in which the cyclization reaction of the specific resin is promoted within the pattern by the action of the base generated from the base generator due to heating.

[0219] The heating step is preferably carried out at a temperature increase rate of 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature. The temperature increase rate is more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. By setting the temperature increase rate to 1°C / min or more, it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity, and by setting the temperature increase rate to 12°C / min or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to increase the temperature from the temperature at the start of heating to the maximum heating temperature at a temperature increase rate of 1 to 8°C / sec, more preferably 2 to 7°C / sec, and even more preferably 3 to 6°C / sec.

[0220] The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating up to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, the temperature is the temperature of the film (layer) after this drying, and it is preferable to raise the temperature from, for example, a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0221] The heating time (heating time at the maximum heating temperature) is preferably from 5 to 360 minutes, more preferably from 10 to 300 minutes, and even more preferably from 15 to 240 minutes.

[0222] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher. The upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and even more preferably 240° C. or lower.

[0223] Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C / min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C / min, and held at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film's properties. The pretreatment step may be performed for a short period of time, preferably from 10 seconds to 2 hours, more preferably from 15 seconds to 30 minutes. The pretreatment step may be performed in two or more steps. For example, a first pretreatment step may be performed in the range of 100 to 150°C, followed by a second pretreatment step in the range of 150 to 200°C. Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably from 1 to 5°C / min.

[0224] The heating step is preferably carried out in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by carrying out the heating step under reduced pressure, in order to prevent decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less. The heating means used in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0225] <Post-development exposure step> The pattern obtained in the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern obtained in the development step is exposed to light, instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed to light. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step. The post-development exposure step can promote, for example, a reaction in which cyclization of a specific resin progresses due to the exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group progresses due to the exposure of a photoacid generator. In the post-development exposure step, it is sufficient that at least a portion of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed. The exposure dose in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity. ２ is preferred, and 100 to 15,000 mJ / cm ２ The post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.

[0226] <Metal Layer Forming Step> The pattern obtained by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step) may be subjected to a metal layer forming step of forming a metal layer 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 by the developing step (preferably subjected to at least one of a heating step and a post-development exposure step).

[0227] 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.

[0228] 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 of these. 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.

[0229] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0230] <Applications> Fields to which the method for producing a cured product of the present invention or 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 described above. For these applications, reference can be made to, for example, Science & Technology Co., Ltd.'s "High Performance Polyimide and Application Technology" (April 2008), edited by Masaaki Kakimoto, CMC Technical Library "Fundamentals and Development of Polyimide Materials" (November 2011), and Japan Polyimide and Aromatic Polymer Research Association's "Latest Polyimide Fundamentals and Applications" (NTS, August 2010).

[0231] 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.

[0232] (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 each made of the cured product, and may be a laminate including three or more layers. At least one of the two or more layers each made of the cured product contained in the laminate 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.

[0233] 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.

[0234] The laminate of the present invention preferably includes two or more layers made of a cured product and a metal layer between any 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 a layer made of a cured product between multiple cured product production processes. A preferred embodiment of the metal layer-forming step is as described above. Examples of the laminate include a laminate having at least a layer structure in which three layers are stacked in this order: a layer made of a first cured product, a metal layer, and a layer made of a second cured product. It is preferred that both the layer made of the first cured product and the layer made of the second cured product are layers made of the cured product of the present invention. The resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention 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.

[0235] <Lamination Step> The method for producing a laminate of the present invention preferably includes a lamination step. The lamination step is a series of steps including performing at least one of (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, and (d) a heating step and a post-development exposure step again on the surface of the pattern (resin layer) or the metal layer in this order. However, at least one of (a) the film formation step and (d) the heating step and the post-development exposure step may be repeated. Furthermore, after at least one of (d) the heating step and the post-development exposure step, (e) a metal layer formation step may be included. It goes without saying that the lamination step may further include the above-mentioned drying step or the like as appropriate.

[0236] 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.

[0237] The lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times. For example, a structure having 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a structure having 2 to 9 resin layers is even more preferred. Each of the layers may be the same or different in composition, shape, film thickness, etc.

[0238] 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 of the present invention is further formed so as to cover the metal layer.Specific examples include an embodiment in which the steps of (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order, or an embodiment in which the steps of (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step are repeated in this order.By alternately performing the lamination step of laminating the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

[0239] (Surface Activation Treatment Step) The method for producing a laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer are surface-activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be surface-activated before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or may be performed 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 to be formed. In this way, by performing the surface activation treatment on the surface of the metal layer, adhesion with the resin composition layer (film) provided on the surface can be improved. The surface activation treatment is also preferably performed on 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, adhesion with the metal layer or resin layer provided on the surface that has been surface-activated can be improved. In particular, when negative development is performed, when the resin composition layer is cured, it is less susceptible to damage due to 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 International Publication No. 2021 / 112189. The contents of this specification are incorporated herein.

[0240] (Semiconductor device and manufacturing method thereof) The present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention. The present invention also discloses a manufacturing method for a semiconductor device comprising the manufacturing method for the cured product or the manufacturing method for the laminate of the present invention. Specific examples of semiconductor devices using the resin composition of the present invention to form an interlayer insulating film for a rewiring layer can be found in paragraphs 0213 to 0218 and FIG. 1 of JP 2016-027357 A, the contents of which are incorporated herein by reference.

[0241] (Method for Producing Polyamic Acid Ester) The method for producing a polyamic acid ester of the present invention includes a step of polycondensing a dicarboxylic acid and a diamine in the presence of a carbodiimide compound as a condensing agent and an active esterifying agent, and the resulting polyamic acid ester satisfies the following conditions (a) and (b): (a) an imidization rate of 3 to 45%; and (b) an absorbance at a wavelength of 365 nm of a 0.050 mass% solution is 0.62 or less. Preferred aspects of the method for producing a polyamic acid ester of the present invention are as described above for the method for producing the specific resin. Furthermore, preferred aspects of the resulting polyamic acid ester are the same as those of the specific resin.

[0242] 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.

[0243] <Method for Producing Specific Resins> [Synthesis Example 1: Synthesis of Resin 4] 0.015 g of hydroquinone, 5.11 g of 4,4'-oxydiphthalic dianhydride (ODPA), and 3.23 g of bisphthalic dianhydride (BPDA) were placed in a separable flask, and 7.20 g of 2-hydroxyethyl methacrylate (HEMA) and 24.82 g of γ-butyrolactone were added and stirred at room temperature (25°C). 4.47 g of pyridine was added while stirring, and the mixture was stirred for 16 hours to obtain a reaction mixture. Next, 1.86 g of 1-hydroxybenzotriazole (HOBt), equivalent to 0.5 molar equivalents of the anhydride, was added, and the mixture was completely dissolved by stirring at room temperature. The mixture was then cooled under ice cooling, and a solution of 11.33 g of dicyclohexylcarbodiimide (DCC) dissolved in 11.17 g of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a solution of 4.98 g of 4,4'-diaminodiphenyl ether (ODA) dissolved in 21.72 g of NMP was added dropwise over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 1.30 g of ethyl alcohol and 0.054 g of TEMPO were added, followed by stirring for 1 hour. Next, 24.83 g of γ-butyrolactone was added. The reaction mixture was refrigerated overnight, then warmed to room temperature, and the precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction mixture was added to 132.07 g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The resulting crude polymer was recovered by decantation and dissolved in 73.36 g of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 1540.05 g of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum dried at 45° C. to obtain 14.82 g of powdered Resin 4. The weight average molecular weight (Mw), imidization rate (%), absorbance at 365 nm, acid value (mmol / g), acid value (mgKOH / g), and amine value of Resin 4 are shown in the table below. １ It was confirmed by H-NMR that the structure of Resin 4 was a structure represented by the following formula (PA): In the following structure, the subscripts in parentheses represent the molar ratio of each repeating unit.

[0244] [Synthesis Example 2: Synthesis of Resin 1] Resin 1 was synthesized in the same manner as in Synthesis Example 1, except that the molar ratio of ODPA to BPDA used was changed to ODPA:BPDA = 50:50 so as not to change the total molar amount of ODPA and BPDA used in Synthesis Example 1. The structure of Resin 1 is shown below. １ The structure was confirmed by H-NMR. In the following structure, the subscripts in parentheses represent the molar ratio of each repeating unit.

[0245] [Synthesis Examples 3 to 21: Synthesis of Resins 2, 3, and 5 to 21] Resins 2, 3, and 5 to 21 were synthesized by using the molar ratio of ODPA to BPDA used as shown in the table, while changing the type and amount of active esterifying agent used as shown in the table below so as not to change the total molar amount of ODPA and BPDA used in Synthesis Example 1. Ion exchange treatment was performed as necessary. Resins 11 to 19 were prepared from the same raw materials with different imidization rates. Resins with desired imidization rates were prepared in Synthesis Example 1 by varying the storage temperature (4 to 45°C) and storage time (0 to 16 hours) after adding 24.83 g of γ-butyrolactone after polymerization. Regarding the active esterifying agent, HOAt is 1-hydroxy-7-azabenzotriazole. For the examples described as "amphoteric ion exchange resin" in the ion exchange treatment column, 4.0 g of the powdered resin obtained by vacuum drying was dissolved in 26.7 g of tetrahydrofuran, and then 2.0 g of water was added. 5.0 g of ion exchange resin UP6040 (manufactured by AmberTec) was added and stirred for 4 hours. The ion exchange resin was then removed by filtration, and the resulting polymer solution was added to 163.5 g of water to obtain a precipitate. The precipitate was collected by filtration and dried at 45 °C under reduced pressure for 24 hours to obtain a resin powder. For the examples described as "anion exchange resin" in the ion exchange treatment column, a resin powder was obtained in the same manner as when an amphoteric ion exchange resin was used, except that Amberlyst 15 (manufactured by Sigma-Aldrich) was used instead of the ion exchange resin UP6040. All of the above ion exchange resins were used after washing using the following procedure. 150 g of purchased ion exchange resin was suspended in 450 mL of water and stirred for 30 minutes. Water was removed by decantation, and then 450 mL of tetrahydrofuran was added and stirred for 30 minutes. The ion exchange resin was recovered by filtration, washed with 150 mL of tetrahydrofuran, and air-dried on a Nutsche for 30 minutes to prepare washed ion exchange resin. The structures of resins 2, 3, and 5 to 19 were those represented by the above formula (P-A). The structures of resins 20 to 21 were those represented by the following formula. The structure of each resin was １ The structure was confirmed by H-NMR. In the following structure, the subscripts in parentheses represent the molar ratio of each repeating unit.

[0246] Synthesis Examples 22 to 30: Synthesis of Resins 22 to 30 By adjusting the equivalent weight of the diamine in Synthesis Example 1, resins 22 to 30 with different Mw were synthesized.

[0247] [Synthesis Examples 31 to 39: Synthesis of Resins 31 to 39] Resins 31 to 39 were synthesized in the same manner as in Synthesis Example 1, except that the total molar amount of ODPA and BPDA used in Synthesis Example 1 was not changed, the molar ratios of pyromellitic dianhydride (PMDA), 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA), and BPDA were changed to those shown in the table, and further, the diamine ODA was changed to m-tolidine while maintaining the equivalent weight relative to the anhydride. The structures of Resins 31 to 39 were represented by the following formulas. The structure of each resin was １ The structure was confirmed by H-NMR. In the following structure, the subscripts in parentheses represent the molar ratio of each repeating unit.

[0248] [Synthesis Example C1: Synthesis of Resin C1] Resin C1 was synthesized in the same manner as in Synthesis Example 2, except that no active esterifying agent was used. The structure of Resin C1 was a structure represented by the above formula (P-A). The structure of the resin was １ This was confirmed by H-NMR.

[0249] [Measurement of weight-average molecular weight (Mw)] GPC measurement was performed for each resin 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.

[0250] [Measurement of imidization rate] Each resin was dissolved in NMP, diluted to a viscosity of 2000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. The silicon wafer to which the obtained resin layer was applied was dried on a hot plate at 110°C for 5 minutes, obtaining 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 Nicolet iS20 (manufactured by ThermoFisher) in the measurement range of 4000 to 700 cm. －１ The measurement was carried out 50 times. －１ Around (1350-1450 cm －１ (If there are multiple peaks, the peak with the greatest intensity) and 1500 cm －１ Around (1460-1550 cm －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.

[0251] [Measurement of absorbance at 365 nm] Each resin was dissolved in 0.050% by mass in DMSO, and the absorbance at a wavelength of 365 nm was measured using a 1 cm cell with a UV-1800 ultraviolet-visible spectrophotometer (Shimadzu Corporation). The temperature during measurement was 23°C and the pressure was 1 atmosphere.

[0252] [Acid Value Measurement] 0.300 g of each resin was dissolved in 80 mL of NMP, and 5 mL of water was added to prepare a measurement solution. The solution was titrated with 0.01 N (0.01 mol / L) aqueous sodium hydroxide (NaOH) solution to detect the neutralization point, thereby measuring the acid value of the resin. The acid value (mg KOH / g) was calculated by conversion from the measured acid value (mmol / g).

[0253] [Measurement of amine value (mmol / g)] 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.

[0254]

[0255]

[0256] Examples and Comparative Examples In each example, the components listed in the table below were mixed to obtain a resin composition. In the comparative examples, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content (amount) of each component listed in the table other than the solvent was the amount (parts by mass) listed in the "Parts by Mass" column of each column in the table. The solvent content (amount) was adjusted so that the solids concentration of the composition was the value (% by mass) of "Solids Concentration" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvent was the ratio listed in the "Ratio" column in the table. The obtained resin composition and comparative composition were pressure-filtered using a polytetrafluoroethylene filter with a pore width of 0.8 μm. In the tables, "-" indicates that the composition did not contain the corresponding component.

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265] Details of each component listed in the table are as follows:

[0266] [Resins] Resins 1 to 39, C1: Resins 1 to 39, C1 obtained in the above synthesis examples

[0267] [Monomers (polymerizable compounds)] M-1 to M-3: Compounds having the following structures DPHA: Dipentaerythritol hexaacrylate

[0268] [Photopolymerization initiators] I-1 to I-7: Compounds having the following structures

[0269] [Base Generator] F-1 to F-5: Compounds having the following structure

[0270] [Polymerization inhibitors] B-1 to B-10: Compounds having the following structures (however, B-5 ​​is a compound that also functions as a migration inhibitor)

[0271] [Silane Coupling Agents (Metal Adhesion Improvers)] C-1 to C-4: Compounds having the following structures.

[0272] [Migration inhibitors] D-1 to D-5: Compounds having the following structure

[0273] [Additives] E-1 to E-6, E-9 to E-15: Compounds having the following structures E-7: Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid E-8: The following synthetic products: F-554 (manufactured by DIC Corporation) BYK-333 (manufactured by BYK Japan KK)

[0274] <Additive: Synthesis of Diazonaphthoquinone Compound E-8> 29.72 g (70 mmol) of 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene)bisphenol (Tris-PA, manufactured by Honshu Chemical Industry Co., Ltd.) was added to a flask. Subsequently, 46.93 g (174.9 mmol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride and 17.9 g of triethylamine were dissolved in 300 g of acetone with stirring, and the solution was added dropwise to the flask using a dropping funnel over 30 minutes, followed by stirring for 30 minutes at an internal temperature of 30°C. Subsequently, hydrochloric acid was added dropwise, and the mixture was stirred for an additional 30 minutes. Next, a solution of 1,640 g of pure water and 30 g of hydrochloric acid was prepared in a beaker, and the filtrate obtained by filtering the hydrochloride salt from the reaction solution was added dropwise to the solution. The precipitate was filtered, washed with water, and vacuum-dried at 40°C for 50 hours to obtain diazonaphthoquinone compound E-8.

[0275] [Solvents] NMP: N-methyl-2-pyrrolidone EL: ethyl lactate DMSO: dimethyl sulfoxide GBL: γ-butyrolactone γ-valerolactone MDMPA: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd.) toluene: toluene CP: cyclopentanone CH: cyclohexanone

[0276] <Evaluation> [Evaluation of Resolution] The resin composition or comparative composition prepared in each Example and Comparative Example was applied in the form of a layer on a copper substrate by spin coating, respectively, to form a resin composition layer or comparative composition layer. The copper substrate on which the obtained resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes, to form a resin composition layer or comparative composition layer with a uniform thickness of 20 µm on the copper substrate. In examples marked "M" in the exposure conditions column, the resin composition layer or comparative composition layer on the copper substrate was exposed to 500 mJ / cm using a stepper as a light source and a photomask on which a 1:1 line and space pattern with 1 µm increments from 5 µm to 25 µm was formed. ２The resin composition layer was exposed to light having an exposure wavelength (nm) as shown in the "Exposure Wavelength (nm)" column of the table, at an exposure energy of 1000 kJ / s. In examples marked "D" in the "Exposure Conditions" column, a direct exposure device (Adtec DE-6UH III) was used as the light source, and laser direct imaging exposure was performed in a 1:1 line and space pattern ranging from 5 μm to 25 μm in 1 μm increments without using a photomask. The resulting layer was then developed with cyclopentanone for 60 seconds and rinsed with PGMEA to obtain a square resin layer measuring 100 μm on each side. In examples marked with a numerical value in the "Cure Temperature (°C)" column, the exposed resin composition layer was heated at a rate of 10°C / min under a nitrogen atmosphere using a hot plate. After reaching the temperature as shown in the "Cure Temperature (°C)" column of the table, the temperature was maintained for the "Cure Time (min)" period in the table to obtain a cured product. In examples where "IR" is entered in the "Cure temperature (°C)" column, the resin film obtained in each example was heated at a rate of 10°C / min under a nitrogen atmosphere using an infrared lamp heating device (RTP-6, manufactured by Advance Riko Co., Ltd.). After reaching 230°C, this temperature was maintained for the time indicated in the "Cure time (min)" column in the table, to obtain a cured product. The line pattern of the obtained cured product was observed using a scanning electron microscope (SEM) to determine the minimum line width. Evaluation was performed according to the following evaluation criteria, and the evaluation results are listed in the "Resolution" column in the table. The smaller the minimum line width formed, the better the resolution. Evaluation criteria: A: The minimum line width of the line and space pattern formed was less than 10 μm. B: The minimum line width of the line and space pattern formed was 10 μm or more and less than 15 μm. C: The minimum line width of the line and space pattern formed was 15 μm or more and less than 20 μm. D: The minimum line width of the line and space pattern formed was 20 μm or more, or no pattern was obtained.

[0277] [Evaluation of Storage Stability of Composition] The resin compositions or comparative compositions prepared in each Example or Comparative Example were allowed to stand at 38°C for 3 days under light-shielded conditions. After the standing period was completed, the viscosity was measured using a viscometer (Toki Sangyo RE-85L). The viscosity change rate after the standing period was calculated using the formula below, compared with the initial state (before the standing period), and evaluated according to the following evaluation criteria. The evaluation results are shown in the "Storage Stability of Composition" column in the table. The smaller the viscosity change rate, the more excellent the storage stability of the composition. Viscosity Change Rate (%) = |(Viscosity After the Standing Period - Viscosity Before the Standing Period)| / (Viscosity Before the Standing Period) x 100 - Evaluation Criteria - A: The absolute value of the viscosity change rate was 3% or less. B: The absolute value of the viscosity change rate was more than 3% but not more than 10%. C: The absolute value of the viscosity change rate exceeded 10%.

[0278] [Evaluation of Elongation at Break] In each Example and Comparative Example, a cured product was obtained in the same manner as in the "Evaluation of Resolution" above, except that the photomask or laser direct imaging exposure range was set so that the exposed area was a rectangular region 3 mm wide and 30 mm long. The cured resin composition layer (cured product) was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and the cured product was peeled off from the silicon wafer. The longitudinal elongation of the peeled cured product (a test piece having a sample width of 3 mm and a sample length of 30 mm) was measured using a tensile tester (Tensilon) at a crosshead speed of 300 mm / min, 25°C, and 65% RH (relative humidity) in accordance with JIS K 6251:2017. Each measurement was performed five times, and the arithmetic mean value of the elongation at break (elongation at break) of the test piece from the five measurements was used as an index value. Evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the "Elongation at Break" column in the table. The higher the index value, the better the film strength of the cured product. -Evaluation criteria- A: The index value was 65% or more. B: The index value was 55% or more and less than 65%. C: The index value was less than 55%.

[0279] From the above results, it can be seen that the resin composition of the present invention can produce a cured product with excellent resolution. The comparative composition of Comparative Example 1 does not contain the specific resin. It can be seen that the cured product formed from such a comparative composition has poor resolution.

[0280] Example 201 The resin composition used in Example 1 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. The resulting layer was dried at 100°C for 5 minutes to form a 20 μm-thick photosensitive film, which was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After the exposure, the film was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern. The temperature was then increased at a rate of 10°C / min in a nitrogen atmosphere until it reached 230°C, at which point it was maintained at 230°C for 180 minutes to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for a redistribution layer had excellent insulating properties. Furthermore, a semiconductor device was manufactured using this interlayer insulating film for a redistribution layer, and it was confirmed to operate without any problems.

Claims

1. A resin composition comprising a resin and a polymerization initiator, wherein the resin is a polyamic acid ester having an imidization rate of 3 to 45% and an absorbance at a wavelength of 365 nm of 0.62 or less in a 0.050% by mass solution.

2. The resin composition according to claim 1, wherein the resin has at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1-1), a repeating unit represented by the formula (1-2), a repeating unit represented by the formula (1-3), and a repeating unit represented by the formula (1-4). In formula (1-1), X １ is a tetravalent organic group, and Y １ is a divalent organic group. ２ is -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 Y ２ is a divalent organic group. ３ is -O- or -NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R ３ is a hydrogen atom or a monovalent organic group, and X ３ is a tetravalent organic group, and Y ３ is a divalent organic group. ４１ and A ４２ are each independently —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 Y ４ is a divalent organic group.

3. The resin composition according to claim 2, wherein the resin contains at least one repeating unit selected from the group consisting of the following repeating units A-1, A-2, A-3, and A-4: Repeating unit A-1: ​​A repeating unit represented by formula (1-1), wherein X １ is any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (V-4). Repeating unit A-2: A repeating unit represented by the above formula (1-2), wherein X ２ is any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (V-4). Repeating unit A-3: A repeating unit represented by the above formula (1-3), wherein X ３ is any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (V-4). Repeating unit A-4: A repeating unit represented by the above formula (1-4), wherein X ４ A repeating unit having any of the structures represented by the following formulas (2a) to (2e), or a repeating unit having a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (V-4): In formulas (2a) to (2e), L １ and L ２ are each independently a divalent group that is not conjugated with the benzene ring to which it is bonded, or a single bond, and *1 to *4 represent bonding sites with the carbonyl group shown in formula (1-1), formula (1-2), formula (1-3), or formula (1-4), respectively, and hydrogen atoms in these structures may be substituted with substituents. In formula (V-4), n1 represents an integer of 1 or more.

4. The resin composition according to claim 2, wherein the resin contains at least one repeating unit selected from the group consisting of the following repeating units B-1, B-2, B-3, and B-4: Repeating unit B-1: A repeating unit represented by formula (1-1), wherein X １ Repeating unit B-2: a repeating unit represented by formula (1-2), wherein X ２ Repeating unit B-3: a repeating unit represented by formula (1-3), wherein X ３ Repeating unit B-4: a repeating unit represented by formula (1-4), wherein X ４ a repeating unit 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), (V-2), (V-3) and (V-5): In formula (V-2), R Ｘ１ are each independently a hydrogen atom, an alkyl group, or a halogenated alkyl group. 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.

5. The resin is a repeating unit represented by the formula (1-2), R ２ is a monovalent organic group having an ethylenically unsaturated bond, a repeating unit represented by the formula (1-3), ３ is a monovalent organic group having an ethylenically unsaturated bond, and a repeating unit represented by the formula (1-4), wherein R ４１ and R ４２ The resin composition according to any one of claims 2 to 4, comprising at least one repeating unit selected from the group consisting of repeating units in which at least one of the repeating units is a monovalent organic group having an ethylenically unsaturated bond.

6. The resin is a repeating unit represented by the formula (1-1), and Y １ a repeating unit having a structure represented by the following formula (C-1) to formula (C-3), a repeating unit having a structure represented by the formula (1-2), ２ a repeating unit having a structure represented by the following formula (C-1) to formula (C-3), a repeating unit having a structure represented by the formula (1-3), ３ A repeating unit having a structure represented by the following formula (C-1) to formula (C-3), and a repeating unit having the structure represented by the formula (1-4), wherein Y ４ The resin composition according to any one of claims 2 to 4, comprising at least one repeating unit selected from the group consisting of repeating units having a structure including a structure represented by the following formulas (C-1) to (C-3): In formula (C-1), R １ each independently represents a hydrogen atom or a monovalent organic group, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 3, and * represents a bonding site to another structure. １ each independently represents a hydrogen atom or a monovalent organic group, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 3, R ２ Each independently represents an alkyl group or a fluoroalkyl group, and * represents a bonding site with another structure. １ each independently represents a hydrogen atom or a monovalent organic group, n1 represents an integer of 0 to 3, and * represents a bonding site to another structure.

7. The resin composition according to any one of claims 1 to 4, wherein the weight average molecular weight of the resin is 5,000 or more but less than 40,000.

8. The resin composition according to any one of claims 1 to 4, wherein the imidization rate is 10% or more and 30% or less.

9. The resin composition according to any one of claims 1 to 4, further comprising 8-azaadenine.

10. The resin composition according to any one of claims 1 to 4, wherein the resin composition is a negative photosensitive resin composition.

11. The resin composition according to any one of claims 1 to 4, which is used to form an interlayer insulating film for a rewiring layer.

12. A cured product obtained by curing the resin composition according to any one of claims 1 to 4.

13. A laminate comprising two or more layers of the cured product according to claim 12, and a metal layer between any of the layers of the cured product.

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

15. The method for producing a cured product according to claim 14, comprising an exposure step of selectively exposing the film to light and a development step of developing the film with a developer to form a pattern.

16. The method for producing a cured product according to claim 14, further comprising a heating step of heating the film at 50 to 450°C.

17. A method for producing a laminate, comprising the method for producing the cured product according to claim 14.

18. A method for manufacturing a semiconductor device, comprising the method for manufacturing the cured product according to claim 14.

19. A semiconductor device comprising the cured product of claim 12.

20. A method for producing a polyamic acid ester that satisfies the following conditions (a) and (b), comprising a step of polycondensing a dicarboxylic acid and a diamine in the presence of a carbodiimide compound as a condensing agent and an active esterifying agent. (a) an imidization rate of 3 to 45%; (b) an absorbance of a 0.050% by mass solution at a wavelength of 365 nm of 0.62 or less; 21. The method for producing a polyamic acid ester according to claim 20, wherein the active esterifying agent is 1-hydroxybenzotriazole or 1-hydroxy-7-azabenzotriazole.

22. A method for producing a polyamic acid ester according to claim 20 or 21, comprising a step of treating the condensate obtained in the polycondensation step with an ion exchange resin.

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