Photosensitive resin composition, cured product, layered product, method for producing cured product, method for producing layered product, method for producing semiconductor device, semiconductor device, and resin

Abstract

Provided are: a photosensitive resin composition which contains a polyimide that is a resin having a structure represented by formula (A-1), a polymerizable compound and a photopolymerization initiator, where the molar quantity of the structure represented by formula (A-1) in 1 g of the resin is 0.2-3.0 mmol / g; a cured product obtained by curing said composition; a layered product containing the cured product; a method for producing the cured product; a method for producing a layered product; a method for producing a semiconductor device, which includes the method for producing the cured product; and a semiconductor device that contains the cured product. In formula (A-1), LA1 denotes an ester group or an amido group, Cy denotes a vinylphenyl group, and ＊ denotes the site of a bond to another structure.

Description

Photosensitive resin composition, cured product, laminate, method for manufacturing cured product, method for manufacturing laminate, method for manufacturing semiconductor device, semiconductor device, and resin

[0001] The present invention relates to a photosensitive 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 resin.

[0002] Resin materials produced from photosensitive resin compositions containing resins are now being utilized in a variety of 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, heterocycle-containing polymers such as polyimides are used in the form of photosensitive resin compositions containing the heterocycle-containing polymer or a precursor thereof. Such photosensitive resin compositions are applied to a substrate, for example, by coating to form a photosensitive film, and then, as necessary, exposed to light, developed, heated, etc., to form a cured product on the substrate. Since photosensitive resin compositions can be applied by known coating methods, for example, they have excellent manufacturing adaptability, such as a high degree of design freedom in the shape, size, application position, etc., of the applied photosensitive resin composition. In addition to the high performance of heterocycle-containing polymers such as polyimides, from the viewpoint of such excellent manufacturing adaptability, the industrial application development of the above-mentioned photosensitive resin compositions is increasingly expected.

[0004] For example, Patent Document 1 describes a negative photosensitive resin composition containing (A) a polyimide, (B) a crosslinking agent containing a polyfunctional (meth)acrylate, and (C) a photopolymerization initiator, in which the polyimide (A) contains a structural unit with a specific structure.

[0005] International Publication No. 2022 / 270541

[0006] In recent years, in the field of semiconductor devices and the like, progress has been made in miniaturization, high frequency, high integration, etc. of devices. Accordingly, photosensitive resin compositions used, for example, for forming rewiring layers and the like are required to have excellent resolution in order to form fine patterns, and also excellent elongation at break in order to prevent damage to components due to thermal shock, etc., even in the case of fine patterns.

[0007] The present invention aims to provide a photosensitive resin composition that can give a cured product that has excellent resolution and elongation at break, a cured product obtained by curing the photosensitive 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 a semiconductor device that includes the method for producing the cured product, and a semiconductor device that includes the cured product. Another object of the present invention is to provide a novel resin.

[0008] Representative embodiments of the present invention are shown below: <1> A photosensitive resin composition comprising: a polyimide resin having a structure represented by the following formula (A-1), a polymerizable compound, and a photopolymerization initiator, wherein the molar amount of the structure represented by formula (A-1) per 1 g of the resin is 0.2 to 3.0 mmol / g. In formula (A-1), L Ａ１ represents an ester group or an amide group, Cy represents a vinylphenyl group, and * represents a bonding site to another structure. <2> The photosensitive resin composition according to <1>, wherein the resin contains a repeating unit represented by the following formula (1-1): In formula (1-1), X １ represents an organic group having 4 or more carbon atoms, and Y １ represents an organic group having 4 or more carbon atoms, and R １ each independently represents a structure represented by the above formula (A-1), m and n represent an integer of 0 to 4, and either m or n represents an integer of 1 or more. １ and Y １ each of which includes a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulas (V-1) to (V-5): 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. <4> The photosensitive resin composition according to any one of <1> to <3>, wherein the ratio of the molar amount of the structure represented by formula (A-1) to the amount of imide structures in the resin is 1 to 100%. <5> A photosensitive resin composition comprising: a resin that is a polyimide precursor or a polybenzoxazole precursor and has a structure represented by formula (A-1): In formula (A-1), L Ａ１ represents an ester group or an amide group, Cy represents a vinylphenyl group, and * represents a bonding site to another structure. <6> The photosensitive resin composition according to <5>, wherein the resin contains a repeating unit represented by the following formula (2-1): In formula (2-1), X ２ represents an organic group having 4 or more carbon atoms, and Y ２ represents an organic group having 4 or more carbon atoms, V １ and V ２ each independently represents a monovalent organic group; R ３ each independently represents a structure represented by the above formula (A-1), m and n represent an integer of 0 to 4, and either m or n represents an integer of 1 or more. １ and Y １ each of which includes a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulas (V-1) to (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 Ｘ３may be bonded to form a ring structure. <8> The photosensitive resin composition according to any one of <1> to <7>, in which the resin has a polymerizable group value of 0.2 to 5.0 mmol / g. <9> The photosensitive resin composition according to any one of <1> to <8>, in which the resins are: Resin P-1 having an amino group which may be protected; and Resin P-2 having Structure A in which two groups selected from the group consisting of carboxylate groups and carboxy groups which may be protected are linked by a linking group having a linking chain length of 2 to 4. <10> The photosensitive resin composition according to any one of <1> to <8>, in which the resin P-1 has, as the amino group which may be protected, a group represented by the following formula (R Ｔ The photosensitive resin composition according to <9>, wherein the photosensitive resin composition has a group represented by the formula (I). Formula (R Ｔ ) Medium, T １ <11> The photosensitive resin composition according to <9>, wherein the resin P-2 contains, as the structure A, a group represented by any one of the following formulas (S-1) to (S-4): In formulas (S-1) to (S-4), R Ｓ１ -OH, -O － Or -O-R Ｓ２ represents R Ｓ２ represents a protecting group, Cy represents an aliphatic ring structure, L １represents a single bond or an aliphatic group having a linking chain length of 1 or 2, n represents an integer of 1 or 2, and * represents a bonding site with another structure. <12> The photosensitive resin composition according to any one of <1> to <11>, wherein, when a 10 μm-thick cured film is formed, the cured film has a transmittance of 10% or more at a wavelength of 365 nm. <13> The photosensitive resin composition according to any one of <1> to <12>, wherein the polymerizable compound has a melting point of 25°C or lower. <14> The photosensitive resin composition according to any one of <1> to <13>, further comprising a solvent having a boiling point of 50°C to 300°C at 1 atmosphere. <15> The photosensitive resin composition according to any one of <1> to <14>, comprising an azole compound and a silane coupling agent. <16> The photosensitive resin composition according to any one of <1> to <15>, further comprising a solvent having a boiling point of 100°C to 260°C at 1 atmosphere. <17> The photosensitive resin composition according to <16>, wherein the content of the solvent having a boiling point of 100 to 260°C is 40% by mass or more relative to the total mass of the composition. <18> The photosensitive resin composition according to <16>, comprising two or more solvents having a boiling point of 100 to 260°C. <19> The photosensitive resin composition according to any one of <1> to <18>, which is used for forming an interlayer insulating film for a redistribution layer. <20> A cured product obtained by curing the resin composition according to any one of <1> to <19>. <21> A laminate comprising two or more layers made of the cured product according to <20>, and a metal layer between any two adjacent layers made of the cured products. <22> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of <1> to <19> onto a substrate to form a film. <23> A method for producing a cured product according to <22>, 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. <24> A method for producing the cured product according to <22> or <23>, comprising a heating step of heating the film at 50 to 450°C. <25> A method for producing a laminate, comprising the method for producing a cured product according to any one of <22> to <24>. <26> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of <22> to <24>. <27> A semiconductor device, comprising the cured product according to <20>.<28> A polyimide resin, having a structure represented by the following formula (A-1), containing a repeating unit represented by the following formula (1-1), wherein the molar amount of the structure represented by formula (A-1) per 1 g of the resin is 0.2 to 3.0 mmol / g: In formula (A-1), L Ａ１ represents an ester group or an amide group, Cy represents a vinylphenyl group, and * represents a bonding site with another structure. In formula (1-1), X １ represents an organic group having 4 or more carbon atoms, and Y １ represents an organic group having 4 or more carbon atoms, and R １ each independently represents a structure represented by the above formula (A-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more. １ and Y １ each of which includes a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulas (V-1) to (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 <30> The resin according to <28>, wherein the molar amount of the structure represented by formula (A-1) relative to the amount of the imide structure is 1 to 100%.

[0009] According to the present invention, there are provided a photosensitive resin composition that can give a cured product that has excellent resolution and elongation at break, a cured product obtained by curing the photosensitive resin composition, a laminate containing 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 containing the cured product. The present invention also provides a novel resin.

[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. Furthermore, 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] (Photosensitive Resin Composition) A photosensitive resin composition according to a first aspect of the present invention (hereinafter also simply referred to as the "first resin composition") is a polyimide resin having a structure represented by formula (A-1), a polymerizable compound, and a photopolymerization initiator, and the molar amount of the structure represented by formula (A-1) in 1 g of the resin is 0.2 to 3.0 mmol / g. A photosensitive resin composition according to a second aspect of the present invention (hereinafter also simply referred to as the "second resin composition") is a polyimide precursor or a polybenzoxazole precursor, and is a polyimide precursor or a polybenzoxazole precursor, and the molar amount of the structure represented by formula (A-1) in 1 g of the resin is 0.2 to 3.0 mmol / g. Hereinafter, the first resin composition and the second resin composition will be collectively referred to as the "resin composition". Hereinafter, a polyimide resin having a structure represented by formula (A-1) will be referred to as a "first specific resin," and a polyimide precursor or polybenzoxazole precursor having a structure represented by formula (A-1) will be referred to as a "second specific resin," and these will be collectively 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. In particular, use of the resin composition of the present invention to form an interlayer insulating film for a redistribution layer is also a preferred embodiment of the present invention. The resin composition of the present invention is also preferably used to form a photosensitive film that is subjected to negative development. 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 provides a cured product with excellent resolution and elongation at break. The mechanism by which this effect is achieved is unclear, but is presumed to be as follows. When the resin contains 0.2 mmol / g or more of the structure represented by Formula (A-1), 0.2 mmol / g or more of vinylphenyl groups are introduced into the resin. Therefore, crosslinking between resins or between the resin and a polymerizable compound occurs during exposure and heating, which is thought to improve resolution. Furthermore, the structure represented by Formula (A-1) contains a highly oriented structure, such as an aromatic ester structure or an aromatic amide structure. This facilitates orientation of the resin in the cured product, which is thought to improve elongation at break. In addition to this crosslinking, a crosslinked structure formed by a vinylphenyl group is less susceptible to depolymerization than, for example, a crosslinked structure formed by a (meth)acryloxy group, and therefore, it is thought that film loss after development (removal of part of the pattern obtained after development by the developer) can be suppressed. Furthermore, while attempts have been made to reduce the thermal expansion coefficient of the cured product by, for example, introducing a rigid structure, such as a mesogen structure, into the main chain, the introduction of such a rigid structure may result in a decrease in elongation at break. However, according to the cured product obtained from the photosensitive resin composition of the present invention, even if the above-mentioned rigid structure is introduced, since the structure represented by the above-mentioned formula (A-1) is contained, the above-mentioned resins can be oriented to each other, thereby improving the breaking elongation, and therefore it is possible to obtain a cured product having a sufficient breaking elongation while reducing the thermal expansion coefficient.

[0014] However, Patent Document 1 does not describe a resin composition containing a resin that falls under the category of the specific resin.

[0015] The components contained in the resin composition of the present invention will be described in detail below.

[0016] <Specific Resin> [First Specific Resin] The first resin composition is a polyimide and contains a resin (first specific resin) having a structure represented by the following formula (A-1): The second resin composition may contain the first specific resin. In formula (A-1), L Ａ１represents an ester group or an amide group, Cy represents a vinylphenyl group, and * represents a bonding site with another structure.

[0017] As used herein, polyimide refers to a resin having a repeating unit containing an imide group in the molecular chain, and is 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. As used herein, the term "main chain" refers to the relatively longest bonding chain in the resin molecule, and the term "side chain" refers to any other bonding chain. 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 two carbon atoms and all of the nitrogen atoms in the imide as ring members. The imide ring structure is preferably a five-membered ring. The first specific resin contains a five-membered imide ring structure in a repeating unit represented by formula (2-1). The polyimide may be a so-called polyamideimide, which has an amide group in the molecular chain in addition to an imide group. In this specification, the 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 carbon atom, and more preferably a bonding site to a hydrogen atom.

[0018] In the present invention, the polyimide precursor refers to a resin that undergoes a change in chemical structure in response to an external stimulus to become a polyimide, and is preferably a resin that undergoes a change in chemical structure in response to heat to become a polyimide, and more preferably a resin that undergoes a ring-closing reaction in response to heat to form a ring structure to become a polyimide. The preferred embodiments of the polyimide that are formed are as described above.

[0019] In the present invention, the term "polybenzoxazole precursor" refers to a resin that undergoes a change in chemical structure in response to an external stimulus to become polybenzoxazole; a resin that undergoes a change in chemical structure in response to heat to become polybenzoxazole is preferred, and a resin that undergoes a ring-closing reaction in response to heat to form a ring structure to become polybenzoxazole is more preferred. In the present invention, the term "polybenzoxazole" refers to a resin having a repeating unit containing a benzoxazole structure in the molecular chain. Furthermore, when the polybenzoxazole is a linear resin, the polybenzoxazole is preferably a resin having a repeating unit containing a benzoxazole structure in the main chain. In the present invention, the term "benzoxazole structure" refers to a structure represented by the following formula (PBO-1): In formula (PBO-1), * represents a bonding site to another structure.

[0020] [Formula (A-1)] In formula (A-1), L Ａ１ represents an ester group or an amide group, and from the viewpoints of resolution and elongation at break, an ester group is preferred. In formula (A-1), Cy represents a vinylphenyl group, and a 4-vinylphenyl group is preferred. In formula (A-1), * is preferably a bonding site to an aromatic ring structure.

[0021] In this specification, the term "ester group" refers to a structure represented by *-C(=O)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. Ａ１ When L is an ester group, its orientation is not particularly limited, but it is preferably the orientation in which Cy in formula (A-1) is bonded to the carbon atom in the ester group. Ａ１ When is an amide group, its orientation is not particularly limited, but it is preferably the orientation in which Cy in formula (A-1) is bonded to the carbon atom in the amide group.

[0022] The molar amount of the structure represented by formula (A-1) in 1 g of the first specific resin is 0.2 to 3.0 mmol / g, preferably 0.3 to 3.0 mmol / g, and more preferably 0.5 to 2.5 mmol / g. The molar amount of the resin in the composition can be calculated by the following method. 1 g of the composition is added to 50 g of methanol or water to cause crystallization, and the first specific resin is precipitated and filtered. The residue is recovered and dissolved in 3.0 g of THF (tetrahydrofuran), and this is added to 50 g of methanol or water to cause crystallization, filtered, and dried at 40°C for 20 hours. 0.1 g of the first specific resin dried above is dissolved in 0.9 g of deuterated dimethyl sulfoxide, and then １ The amount of vinylphenyl groups is calculated by measuring with H-NMR. １ The number of H-NMR measurements was 640. Benzenesulfonylanilide was used as the reference substance. １ The polymerizable group value of Resin A can be calculated from the ratio of the integrated intensity of the peak at around 4.9 to 7.0 ppm derived from the vinylphenyl group in the H-NMR chart to the integrated intensity of the peak derived from the reference material, the amount of the reference material, and the amount of Resin A. 1.00 g of Resin A and 0.0233 g (0.1 mmol) of benzenesulfonyl anilide were dissolved in 9.0 g of deuterated DMSO. １ H-NMR (integrated 640 times) is performed. The integral value of the peak near 10.3 ppm, which is the NH peak of benzenesulfonyl anilide, is set to 0.1, and the integrated value of one of the vinylphenyl-derived peaks of 4.9 to 5.5 ppm, 5.5 to 6.2 ppm, or 6.5 to 7.0 ppm is determined. The unit of the integrated value is mmol / g, and this value is the amount of vinylphenyl. The same method can be used for the composition.

[0023] The molar amount of the structure represented by formula (A-1) relative to the total solid content of the composition is preferably 0.05 to 3.0 mmol / g, more preferably 0.1 to 3.0 mmol / g, and even more preferably 0.1 to 2.5 mmol / g. The molar amount relative to the total solid content of the composition can be calculated by the following method. 0.1 g of the composition and 0.9 g of deuterated DMSO are weighed and dissolved in a sample bottle. １The amount of vinylphenyl groups is calculated by measuring with H-NMR. １ The number of H-NMR integrations is 640. For such a composition, the molar amount of the structure represented by formula (A-1) can be determined using a reference substance in the same manner as above.

[0024] [Repeating Unit Represented by Formula (1-1)] The first specific resin preferably contains a repeating unit represented by formula (1-1). In formula (1-1), X １ represents an organic group having 4 or more carbon atoms, and Y １ represents an organic group having 4 or more carbon atoms, and R １ each independently represents a structure represented by the above formula (A-1), m and n represent an integer of 0 to 4, and either m or n represents an integer of 1 or more.

[0025] -X １ -X １ The number of carbon atoms in X is 4 or more, preferably 4 to 50, and more preferably 4 to 40. １ preferably represents an organic group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulas (V-1) to (V-10). By using an organic group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-10), the chemical resistance and flatness of the cured product are improved. Furthermore, by using an organic group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-5), effects such as suppression of development residue generation, lowering the dielectric constant of the cured product, and reducing the thermal expansion coefficient are also obtained. Furthermore, particularly X １ is an organic group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-4) or formula (V-5), a cured product with excellent resolution can be obtained. １ is an organic group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-1) or formula (V-2), a cured product having excellent elongation at break can be obtained. 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. Ｘ５ are each independently a hydrogen atom, an alkyl group, or a halogenated alkyl group.

[0026] 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.

[0027] 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 site with the four carbonyl groups to which n1 is bonded, and n1 represents an integer of 0 to 5, and is also preferably an integer of 1 to 5. In addition, the hydrogen atom in the following structure is １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[0028] 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), X １ is preferably a group represented by the following formula (V-2-1) or formula (V-2-2), and from the viewpoint of lowering the amine value in the resin, it is preferably a group represented by formula (V-2-2). In this specification, a bond crossing a side of a ring structure means that it substitutes one of the hydrogen atoms in the ring structure. In the following formula, L Ｘ１ represents a single bond or —O—, and * represents X in formula (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 are R １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[0029] 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 are R １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[0030] 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-4), X １ is preferably a group represented by the following formula (V-4-1): In the following formula (V-4-1), * represents X in formula (1-1). １represents bonding sites with the four carbonyl groups to which n1 is bonded, and n2 represents an integer of 0 to 5. In addition, the hydrogen atom in formula (V-4-1) is １ or may be further substituted with a known substituent such as a hydrocarbon group. Known substituents include an alkyl group, a halogenated alkyl group, a halogen atom, etc. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-4-1) is substituted.

[0031] 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 The hydrogen atoms in formula (V-5-1) represent the bonding sites with the four carbonyl groups to which R in formula (1-1) is bonded. １ or may be further substituted with a known substituent such as a hydrocarbon group. Known substituents include an alkyl group, a halogenated alkyl group, a halogen atom, etc. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-5-1) is substituted.

[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-6), X １ is preferably a group represented by the following formula (V-6-1): 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. １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[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-7), X １ is preferably a group represented by the following formula (V-7-1): In the following formula, * represents X in formula (1-1). １represents the bonding site with the four carbonyl groups to which R is bonded. １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[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-8), X １ is preferably a group represented by the following formula (V-8-1): 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. Ｘ５ The definition and preferred embodiments of are as described above. In addition, the hydrogen atom in the following structure is R １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[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-9), X １ is preferably a group represented by the following formula (V-9-1): 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. １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[0036] 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-10), X １ is preferably a group represented by the following formula (V-10-1): 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. １ The alkyl group may be further substituted with a known substituent such as a hydrocarbon group.

[0037] Other, X １may 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.

[0038] Also, X １ It is preferable that X does not contain an imide bond in the structure. １ In the present invention, the urethane bond is *—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.

[0039] Also, X １ is a structure represented by the following formula (X-2), or X in the structure represented by (X-2): ２ or a hydrogen atom of a group represented by ３ is a hydrogen atom of a group represented by R １ It may also have a structure substituted with a group represented by the following formula: In formula (X-2), X ２ each independently represents a trivalent linking group; L ３represents a divalent linking group, and * represents a bonding site to another structure.

[0040] In formula (X-2), X ２ is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, or a group in which two or more of these are linked by a single bond or a linking group, and is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group. Examples of the linking group include -O-, -S-, -C(=O)-, -S(=O) ２ Preferred are -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferred are -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Furthermore, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms or may have all of the hydrogen atoms substituted with halogen atoms, but it is preferable that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0041] Also, X ２is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The halogenation is preferably chlorination. In the present invention, a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Two of the three carboxy groups in the tricarboxylic acid compound may be converted to acid anhydrides. Examples of tricarboxylic acid compounds that may be halogenated include branched aliphatic, cyclic aliphatic, and aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

[0042] X ２ It is preferable that X does not contain an imide structure in its structure. ２ It is preferable that X does not contain a urethane bond, a urea bond, or an amide bond in the structure. ２ It is preferable that X does not contain an ester bond in the structure. ２ It is preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that the copolymer does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0043] Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group, and more preferably a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group.

[0044] Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are bonded with a single bond, —O—, —CH ２ -, -C(CH ３ ) ２ -, -C(CF３ ) ２ -, -SO ２ These compounds may be compounds in which two carboxy groups are anhydride (e.g., trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).

[0045] In formula (X-2), L ３ is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, or a group in which two or more of these are linked by a single bond or a linking group, and is preferably a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group, and more preferably an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group. Examples of the linking group include -O-, -S-, -C(=O)-, -S(=O) ２Preferred are -, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these, and more preferred are -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Furthermore, examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. The halogenated alkylene group may contain hydrogen atoms or may have all of the hydrogen atoms substituted with halogen atoms, but it is preferable that all of the hydrogen atoms be substituted with halogen atoms. Examples of preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group. The arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.

[0046] Also, X １ is a structure represented by the following formula (X-3), or X in the structure represented by (X-3): ２ or a hydrogen atom of a group represented by ３ is a hydrogen atom of a group represented by R １ It may also have a structure substituted with a group represented by the following formula: In formula (X-3), X ２ each independently represents a trivalent linking group; L ３ represents a divalent linking group, and * represents a bonding site with another structure. ２ and L ３ A preferred embodiment of the formula (X-2) is ２ and L ３ This is the same as the preferred embodiment of the above.

[0047] -Y １ - Y １The number of carbon atoms in Y is 4 or more, preferably 4 to 50, and more preferably 4 to 40. １ may be a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the above formulas (V-1) to (V-10). By using an organic group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1) to (V-10), the chemical resistance and flatness of the cured product are improved.

[0048] Y 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), Y １ is preferably a group represented by the following formula (V-1-2): In the following formula, * represents Y in formula (1-1). １ represents the bonding site with the two nitrogen atoms to which n is bonded, and n1 represents an integer of 1 to 5. In addition, the hydrogen atoms in the following structures are bonded to the R １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[0049] Y 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), １ is preferably a group represented by the following formula (V-2-3) or formula (V-2-4), and from the viewpoint of reducing the dielectric constant of the cured product, it is preferably a group represented by formula (V-2-4). Ｘ１ represents a single bond or —O—, and * represents Y in formula (1-1). １ represents the bonding site with the two nitrogen atoms to which R is bonded. Ｘ１ The preferred embodiments of are as described above. In addition, the hydrogen atoms in these structures are R １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[0050] Y 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), １is preferably a group represented by the following formula (V-3-3) or formula (V-3-4), and from the viewpoint of reducing the dielectric constant of the cured product, it is preferably a group represented by formula (V-3-3). In the following formulas, * represents Y in formula (1-1). １ represents the bonding site with the two nitrogen atoms to which R is bonded. １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[0051] Y 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), １ is preferably a group represented by the following formula (V-4-2) or (V-4-3): １ represents the bonding site with the two nitrogen atoms to which n is bonded, and n1 represents an integer of 0 to 5. An embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. Furthermore, the hydrogen atoms in the following structures are bonded to R １ or may be further substituted with a known substituent such as a hydrocarbon group, etc. Known substituents include an alkyl group, a halogenated alkyl group, a halogen atom, etc.

[0052] 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-5-2): In the following formula, * represents Y in formula (1-1). １ represents the bonding site with the two nitrogen atoms to which R in formula (1-1) is bonded. １ or may be further substituted with a known substituent such as a hydrocarbon group. Known substituents include an alkyl group, a halogenated alkyl group, a halogen atom, etc. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-5-1) is substituted.

[0053] Y １is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-6), １ is preferably a group represented by the following formula (V-6-2): In the following formula, * represents Y in formula (1-1). １ represents the bonding site with the two nitrogen atoms to which R is bonded. １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[0054] Y １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-7), １ is preferably a group represented by the following formula (V-7-2): In the following formula, * represents Y in formula (1-1). １ represents the bonding site with the two nitrogen atoms to which R is bonded. １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[0055] Y １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-8), １ is preferably a group represented by the following formula (V-8-2): In the following formula, * represents Y in formula (1-1). １ represents the bonding site with the two nitrogen atoms to which R is bonded. １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[0056] Y １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-9), １ is preferably a group represented by the following formula (V-9-2): In the following formula, * represents Y in formula (1-1). １ represents the bonding site with the two nitrogen atoms to which R is bonded. １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[0057] Y １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-10), １ is preferably a group represented by the following formula (V-10-2): In the following formula, * represents Y in formula (1-1). １ represents the bonding site with the two nitrogen atoms to which R is bonded. １ , or may be further substituted with a known substituent such as a hydrocarbon group.

[0058] Others, Y １ may be a group described in paragraphs 0042 to 0053 of JP-A No. 2023-003421. １ It is preferable that Y does not contain an imide bond in the structure. １ It is preferable that Y does not contain a urethane bond, a urea bond, or an amide bond in the structure. １ It is preferable that Y does not contain an ester bond in the structure. 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.

[0059] Among these, X in formula (1-1) １ and Y １ is preferably an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-5). Preferred aspects of these groups are as described above.

[0060] -n and m- In formula (1-1), m is preferably an integer of 0 to 2, and more preferably 0 or 1. An embodiment in which m is 0 is also one of the preferred embodiments of the present invention. In formula (1-1), n ​​is preferably 1 or 2, and more preferably 1.

[0061] [Repeating unit represented by formula (4)] The first specific resin may contain a repeating unit represented by formula (4). A repeating unit corresponding to the repeating unit represented by formula (1-1) does not correspond to the repeating unit represented by formula (4). In formula (4), R １３１ represents a divalent organic group, and R １３２ represents a tetravalent organic group.

[0062] R １３１ represents a divalent organic group. １３１ Examples of R include the groups described in paragraphs 0042 to 0053 of JP-A No. 2023-003421. These descriptions are incorporated herein by reference. １３１ is Y in the above formula (1-1). １ In another preferred embodiment of the present invention, the group is one of the preferred embodiments of the present invention.

[0063] R １３２ represents a tetravalent organic group. １３２ Examples of R include the compounds described in paragraphs 0055 to 0057 of JP-A No. 2023-003421. These descriptions are incorporated herein by reference. １３２ is X in the above formula (1-1). １ In another preferred embodiment of the present invention, the group is one of the preferred embodiments of the present invention.

[0064] The content of the repeating unit represented by formula (1-1) relative to the total mass of the first specific resin is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, and particularly preferably 40% by mass or more. The upper limit of this content is not particularly limited and may be 100% by mass. Furthermore, the total content of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (4) relative to the total mass of the first specific resin 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. The upper limit of this content is not particularly limited and may be 100% by mass. Furthermore, when the first specific resin contains a repeating unit represented by formula (1-1), it may contain two or more repeating units represented by formula (1-1) with different structures. In this case, it is preferable that the total amount is within the above range. When the first specific resin contains a repeating unit represented by formula (4), it may contain two or more repeating units represented by formula (4) with different structures. In this case, the total amount is preferably within the above range.

[0065] The weight-average molecular weight (Mw) of the first specific resin is preferably 3,000 to 100,000. The lower limit of the Mw is preferably 5,000 or more, more preferably 6,000 or more, and even more preferably 8,000 or more. The upper limit of the Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. The number-average molecular weight (Mn) of the first specific resin is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and even more preferably 5,000 to 20,000. The molecular weight dispersity of the first 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 is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, even more preferably 4.5 or less, and particularly preferably 3.0 or less. In this specification, the molecular weight dispersity is a value calculated by weight average molecular weight / number average molecular weight. When the resin composition contains multiple types of resins as the first specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one 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 types of resins as one resin are each within the above ranges.

[0066] The imidization rate (also referred to as "ring closure rate") of the first specific resin is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. The upper limit of the imidization rate is not particularly limited, and it may be 100% or less. The content of imide groups in the first specific resin is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less. The lower limit of the content is not particularly limited, but can be, for example, 0.5 mmol / g or more. In this specification, the imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the resin is measured, and the absorption peak at 1377 cm, which is derived from the imide group, is detected. －１Next, the resin is heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum is measured again to determine the peak intensity P1 around 1377cm. －１ The peak intensity P2 around the peak intensity P1 is then measured. Using the measured peak intensities P1 and P2, the imidization rate of the resin can be calculated based on the following formula: Imidization rate (%) = (peak intensity P1 / peak intensity P2) x 100

[0067] The molar ratio of the structure represented by formula (A-1) to the amount of imide structures in the resin is preferably 1 to 100%, more preferably 10 to 85%, and even more preferably 10 to 50%. -1 The peak intensity (ethylenically unsaturated bond) near 1380 cm -1 It can be calculated as the molar amount of the structure represented by formula (A-1) relative to the amount of imide structures obtained by dividing by the nearby peak intensity (imide group).

[0068] [Second Specific Resin] The second resin composition contains a resin (second specific resin) that is a polyimide precursor or a polybenzoxazole precursor and has a structure represented by formula (A-1). The first resin composition may contain a second specific resin. Preferred aspects of the structure represented by formula (A-1) in the second specific resin, the molar amount of the structure in the resin, and the molar amount of the structure relative to the total solid content of the resin are the same as those preferred aspects of the first specific resin described above.

[0069] The second specific resin preferably contains a repeating unit represented by formula (2-1). In formula (2-1), X ２ represents an organic group having 4 or more carbon atoms, and Y ２ represents an organic group having 4 or more carbon atoms, V １ and V ２ each independently represents a monovalent organic group; R ３ each independently represents a structure represented by the above formula (A-1), m and n represent an integer of 0 to 4, and either m or n represents an integer of 1 or more.

[0070] In formula (2-1), X ２ , Y ２ and R ３ A preferred embodiment of the formula (1-1) is X １ , Y １ and R １ This is the same as the preferred embodiment of the above.

[0071] In formula (2-1), V １ and V ２ Preferably, at least one of V contains a polymerizable group. １ and V ２ An embodiment in which both of the above groups contain a polymerizable group is also one of the preferred embodiments of the present invention. １ and V ２ Examples of the polymerizable group in include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, etc., with the group having an ethylenically unsaturated bond being preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, a (meth)acrylamide group, etc. Among these, a (meth)acryloyl group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, with a (meth)acryloyl group being more preferred from the viewpoint of reactivity. Furthermore, a vinylphenyl group or a maleimide group is preferred from the viewpoint of reducing the dielectric loss tangent, etc.

[0072] V １ or V ２ As the group containing a polymerizable group in the formula (III), a group represented by the following formula (III) is preferred.

[0073]

[0074] 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. ２０１Examples 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.

[0075] V １ and V２ When is an organic group that does not contain a polymerizable group, it is preferably a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.

[0076] V １ and V ２ is a hydrogen atom, the second 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.

[0077] In formula (2-1), m is preferably an integer of 0 to 2, and more preferably 0 or 1. An embodiment in which m is 0 is also one of the preferred embodiments of the present invention. In formula (2-1), n ​​is preferably 1 or 2, and more preferably 1.

[0078] The second specific resin may contain a repeating unit represented by formula (2). A repeating unit that falls under the repeating unit represented by formula (2-1) does not fall under the repeating unit represented by formula (2). In formula (2), A １ and A ２ are each independently an oxygen atom or —NR ｚ represents -, and R １１１ represents a divalent organic group, and R １１５ represents a tetravalent organic group, R １１３ and R １１４ each independently represents a hydrogen atom or a monovalent organic group; R ｚ represents a hydrogen atom or a monovalent organic group.

[0079] A in formula (2) １ and A ２ are each independently an oxygen atom or —NR ｚ -, and an oxygen atom is preferred. ｚ represents a hydrogen atom or a monovalent organic group, and preferably a hydrogen atom. １１１ and R １１５ A preferred embodiment of the formula (4) is R １３１ and R １３２The preferred embodiments of R in formula (2) are the same as those of １１３ and R １１４ A preferred embodiment of is V in the above formula (2-1). １ and V ２ This is the same as the preferred embodiment of the above.

[0080] The content of the repeating unit represented by formula (2-1) relative to the total mass of the second specific resin is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, and particularly preferably 40% by mass or more. The upper limit of this content is not particularly limited and may be 100% by mass. Furthermore, the total content of the repeating unit represented by formula (2-2) and the repeating unit represented by formula (2) relative to the total mass of the second specific resin 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. The upper limit of this content is not particularly limited and may be 100% by mass. Furthermore, when the second specific resin contains a repeating unit represented by formula (2-1), it may contain two or more repeating units represented by formula (2-1) with different structures. In this case, it is preferable that the total amount is within the above range. When the second specific resin contains a repeating unit represented by formula (2), it may contain two or more repeating units represented by formula (2) with different structures. In this case, the total amount is preferably within the above range.

[0081] The weight-average molecular weight (Mw) of the second specific resin is preferably 3,000 to 100,000. The lower limit of the Mw is preferably 5,000 or more, more preferably 6,000 or more, and even more preferably 8,000 or more. The upper limit of the Mw is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. The number-average molecular weight (Mn) of the second specific resin is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, and even more preferably 5,000 to 20,000. The molecular weight dispersity of the second 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 is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, even more preferably 4.5 or less, and particularly preferably 3.0 or less. When the resin composition contains multiple types of resins as the second specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one 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 types of resins as one resin are each within the above ranges.

[0082] The imidization rate (also referred to as "ring closure rate") of the second specific resin is preferably less than 70%, more preferably 50% or less, and even more preferably 30% or less, from the viewpoints of the film strength, insulating properties, etc. of the resulting organic film. The lower limit of the imidization rate is not particularly limited, and may be 0% or more.

[0083] [Repeating Unit Represented by Formula (3)] The second specific resin is also preferably a resin having a repeating unit represented by the following formula (3). In formula (3), Y ３ represents a divalent organic group, and X ３ represents a tetravalent organic group, and V ３ and V ４ each independently represents a hydrogen atom or a monovalent organic group; R ４each independently represents a structure represented by the above formula (A-1), m and n represent an integer of 0 to 4, and either m or n represents an integer of 1 or more.

[0084] In formula (3), V ３ and V ４ are R in formula (2), respectively. １１３ In other words, it is preferable that at least one of Y is a polymerizable group. ３ A preferred embodiment of the formula (3) is R １２１ In a preferred embodiment of the present invention, n hydrogen atoms are R ４ In formula (3), X is the same as the structure substituted by ３ A preferred embodiment of the formula (3) is R １２２ In a preferred embodiment of the present invention, n hydrogen atoms are R ４ The structure is similar to that substituted by

[0085] In formula (3), m is preferably an integer of 0 to 2, and more preferably 0 or 1. An embodiment in which m is 0 is also one of the preferred embodiments of the present invention. In formula (3), n is preferably 1 or 2, and more preferably 1.

[0086] When the second specific resin is a polybenzoxazole precursor, the weight-average molecular weight (Mw) is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By adjusting the weight-average molecular weight to 5,000 or more, the fold resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties, the weight-average molecular weight is particularly preferably 20,000 or more. When two or more polybenzoxazole precursors are contained, it is preferable that the weight-average molecular weight of at least one polybenzoxazole precursor be within the above range. When the second specific resin is a polybenzoxazole precursor, the number-average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. When the second specific resin is a polybenzoxazole precursor, the molecular weight dispersity is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly specified, but is, for example, preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less. When the resin composition contains multiple polybenzoxazole precursors as the second specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one polybenzoxazole precursor 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 polybenzoxazole precursors as a single resin are each within the above ranges.

[0087] When the second specific resin is a polybenzoxazole precursor, the polybenzoxazole precursor preferably has an oxazolization rate of 15% or less, more preferably 10% or less. The lower limit is not particularly limited, and may be 0%. The oxazolization rate is measured, for example, by the following method. The infrared absorption spectrum of the polybenzoxazole is measured, and the absorption peak at 1650 cm, which is due to the amide structure of the precursor, is detected. －１ Next, the peak intensity Q1 around 1490 cm－１ The polybenzoxazole was heat-treated at 350°C for 1 hour, and then the infrared absorption spectrum was measured again. －１ The peak intensity Q2 around 1490 cm －１ The absorption intensity of the aromatic ring observed near the peak intensity Q1 is normalized. Using the normalized values ​​of the peak intensities Q1 and Q2 thus obtained, the oxazolization rate of polybenzoxazole can be calculated based on the following formula: Oxazolization rate (%) = (normalized value of peak intensity Q1 / normalized value of peak intensity Q2) × 100

[0088] The polybenzoxazole precursor is R １２１ ~R １２４ may contain repeating units of the above formula (3) in which the combination of R １２１ ~R １２４ The polybenzoxazole precursor may contain two or more repeating units of the formula (3) in which the combination of the following is different in part or in whole. In addition, the polybenzoxazole precursor may contain other types of repeating units in addition to the repeating unit of the formula (3).

[0089] [Polymerizable Group Value] The molar content (polymerizable group value) of the polymerizable group contained in 1 g of the specific resin is preferably 0.2 to 5.0 mmol / g, more preferably 0.3 to 4.5 mmol / g, and even more preferably 0.5 to 4.0 mmol / g. The molar content (radical polymerizable group value) of the radical polymerizable group contained in 1 g of the specific resin is preferably 0.2 to 5.0 mmol / g, more preferably 0.3 to 4.5 mmol / g, and even more preferably 0.5 to 4.0 mmol / g. The molar content (ethylenically unsaturated group value) of the ethylenically unsaturated group contained in 1 g of the specific resin is preferably 0.2 to 5.0 mmol / g, more preferably 0.3 to 4.5 mmol / g, and even more preferably 0.5 to 4.0 mmol / g.

[0090] In one preferred embodiment, the resin composition of the present invention comprises, as specific resins, a resin P-1 having an amino group which may be protected, and a resin P-2 having a structure A in which two groups selected from the group consisting of a carboxylate group and a carboxy group which may be protected are linked by a linking group having a linking chain length of 2 to 4. Herein, the resin P-1 may be a resin corresponding to the first specific resin or a resin corresponding to the second specific resin. Furthermore, the resin P-2 may be a resin corresponding to the first specific resin or a resin corresponding to the second specific resin. Hereinafter, the amino group and the protected amino group present in the resin P-1 will be collectively referred to as a specific substituent Sub-1. Hereinafter, a group containing a structure A in which two groups selected from the group consisting of a carboxylate group and a carboxy group which may be protected are linked by a linking group having a linking chain length of 2 to 4, present in the resin P-2, will be referred to as a specific substituent Sub-2.

[0091] Resin P-1 contains a compound represented by the following formula (R Ｔ ) is preferably a group represented by the formula (I). Formula (R Ｔ ) Medium, T １ represents a monovalent organic group. Ｔ ) Medium, T １ is preferably an alkyl group or an alkyl group substituted with a ring structure, more preferably a tertiary alkyl group or a methyl group substituted with a ring structure, and even more preferably a t-butyl group or a 9-fluorenylmethyl group.

[0092] The specific substituent Sub-1 may be present at a side chain terminal of the resin P-1, but is preferably present at a main chain terminal. The content of the specific substituent Sub-1 in the resin P-1 is not particularly limited, but is preferably 0.01 to 2 mmol / g, more preferably 0.05 to 1 mmol / g, and even more preferably 0.15 to 0.75 mmol / g. The number of specific substituents Sub-1 in the resin P-1 per molecule is preferably 2 to 10, more preferably 2 to 4, and even more preferably 2.

[0093] Resin P-2 preferably contains, as specific substituent Sub-2, a group represented by any one of formulas (S-1) to (S-4) below. In formulas (S-1) to (S-4), R Ｓ１ -OH, -O － Or -O-R Ｓ２ represents R Ｓ２ represents a protecting group, Cy represents an aliphatic ring structure, L １ represents a single bond or an aliphatic group with a linking chain length of 1 or 2, n represents an integer of 1 or 2, and * represents a bonding site with another structure. Ｓ１ is -OH or -O － is preferred. Ｓ１ Ga-O － In this case, the counter cation is not particularly limited, but may be a proton, Na ＋ , K. ＋ Examples of the metal cations include metal cations such as ammonium cations and iminium cations. Ｓ１ Ga-O-R Ｓ２ When R represents Ｓ２ is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a t-butyl group. Cy is preferably a cycloalkane structure, more preferably a cyclohexane ring structure. n is preferably 1. L １ is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond.

[0094] Furthermore, resin P-2 preferably contains, as specific substituent Sub-2, a group represented by either formula (CA-1) or formula (CA-2) below. In formula (CA-1), R Ｃ１ are each independently —OH, —O － Or -O-R Ｃ represents R Ｃ represents an organic group, R Ｃ２ represents a substituent, a represents an integer of 0 to 3, * represents a bonding site with another structure, b represents 1 or 2, and the sum of a and b is 4 or less. Ｃ１ are each independently —OH, —O － Or -O-RＣ represents R Ｃ represents an organic group, R Ｃ２ represents a substituent, a represents an integer of 0 to 9, * represents a bonding site to another structure, b represents 1 or 2, and the sum of a and b is 10 or less.

[0095] In formula (CA-1), R Ｃ１ is -OH or -O － It is preferable that R Ｃ１ Ga-O － In this case, the counter cation is not particularly limited, but may be a proton, Na ＋ , K. ＋ Examples of the metal cations include metal cations such as ammonium cations and iminium cations. Ｃ１ Ga-O-R Ｃ R when Ｃ is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a t-butyl group. Ｃ２ is preferably an alkyl group or an aryl group, and more preferably an alkyl group having 1 to 4 carbon atoms. In formula (CA-1), a is preferably 0 or 1. In formula (CA-1), b is preferably 1.

[0096] In formula (CA-2), R Ｃ１ , R Ｃ２ Preferred embodiments of a and b are R Ｃ１ , R Ｃ２ The preferred embodiments are the same as those of a, b and c.

[0097] [Method for Producing Specific Resin] The specific resin can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine at low temperature; by reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid, followed by esterification using a condensing agent or alkylating agent; by obtaining an ester compound (e.g., a diester) from a tetracarboxylic dianhydride with an alcohol, followed by reaction with a diamine in the presence of a condensing agent; or by obtaining an ester compound (e.g., a diester) from a tetracarboxylic dianhydride with an alcohol, followed by acid halogenation of the remaining dicarboxylic acid with a halogenating agent, followed by reaction with a diamine. Among the above-mentioned production methods, a more preferred method involves obtaining an ester compound (e.g., a diester) from a tetracarboxylic dianhydride with an alcohol, followed by acid halogenation of the remaining dicarboxylic acid with a halogenating agent, followed by reaction with a diamine. The specific resin can be obtained by using, as the tetracarboxylic dianhydride or its ester compound, at least one compound selected from the group consisting of a carboxylic dianhydride having a structure represented by Formula (A-1) and an ester compound of a carboxylic dianhydride having a structure represented by Formula (A-1). Furthermore, a specific resin can be obtained by using a compound having a structure represented by formula (A-1) as the diamine. Furthermore, by using a compound containing a polymerizable group as the tetracarboxylic dianhydride or diamine, a polymerizable group can be introduced into the resin. Furthermore, a polymerizable group can also be introduced into the resin by using a compound containing a reactive group such as a hydroxy group as the tetracarboxylic dianhydride or diamine, introducing the reactive group into the resin, and then reacting the resin with a compound having a polymerizable group and a group that forms a covalent bond with the reactive group, such as a carboxy group or an isocyanate group. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, etc. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphorus oxychloride, etc. Furthermore, when a polyimide is desired as the specific resin, it can be synthesized by using a method in which the resin obtained by the above method is completely imidized using a known imidization reaction method, a method in which the imidization reaction is terminated midway and partial imide groups are introduced, or a method in which partial imide groups are introduced by blending a completely imidized polymer with its polyimide precursor. Other known polyimide synthesis methods can also be applied. In the method for producing the specific resin, it is preferable to use an organic solvent during the reaction. One or more organic solvents may be used. The organic solvent can be appropriately selected depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing the specific resin, it is preferable to add a basic compound during the reaction. One type of basic compound may be used, or two or more types may be used. The basic compound can be appropriately selected depending on the raw materials, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0098] -End-capping agent- In order to further improve storage stability during the production method of the specific resin, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the specific resin. When capping the carboxylic acid anhydride or acid anhydride derivative remaining at the resin terminal, examples of the end-capping agent include monoalcohols, phenols, thiols, thiophenols, and monoamines. In terms of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecynol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.Preferred examples of the monoamine compound include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of suitable end-capping agents include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple end-capping agents may be reacted to introduce multiple different end groups. Furthermore, when capping the amino groups at the resin ends, they can be capped with a compound having a functional group capable of reacting with the amino group. Preferred examples of the capping agent for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, etc., and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides. Preferred carboxylic acid anhydride compounds include acetic anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, benzoic acid anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride.Preferred examples of carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.

[0099] -Solid Precipitation- The method for producing the specific resin may include a step of precipitating a solid. Specifically, after filtering out water-absorbing by-products of the dehydration condensation agent coexisting in the reaction solution as needed, the resulting polymer component is added to a poor solvent such as water, a lower aliphatic alcohol, or a mixture thereof to precipitate the polymer component as a solid, which is then dried to obtain the specific resin. To improve the degree of purification, the specific resin may be repeatedly subjected to operations such as redissolving, reprecipitation, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

[0100] [Specific Examples] Specific examples of the specific resin include SP-1 to SP-17 and SA-1 to SA-8 in the examples described below, but the present invention is not limited to these.

[0101] [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, even more preferably 50% by mass or more, and most preferably 60% by mass or more, based on the total solid content of the resin composition. Also, 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.

[0102] <Other Resins> The resin composition of the present invention may contain other resins (hereinafter simply referred to as "other resins") different from the specific resin described above. Examples of other resins include resins different from the specific resin, such as polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, polyamideimides, 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. Examples of other polyimide precursors, other polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, and polyamideimides include the compounds described in paragraphs 0017 to 0138 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0103] When the resin composition of the present invention contains another resin, the content of the other resin 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. The content of the other resin in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. 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.

[0104] <Compound Having an Optionally Protected Amino Group (Compound A)> The resin composition of the present invention preferably contains a compound having an optionally protected amino group (also referred to as "Compound A"). Compounds that fall under the above-mentioned Resin P-1 are not considered to fall under Compound A. For example, when the resin composition contains the above-mentioned Resin P-2 and Compound A, the reaction between Resin P-2 and Compound A can increase the molecular weight of the resin during heating, etc., which may improve elongation at break, chemical resistance, etc. Furthermore, because the final elongation at break and other properties can be improved in this way, the molecular weight of the Resin P-2 added initially can be lower than conventional. This can also improve resolution.

[0105] The molecular weight of compound A is preferably 100 to 1,000, and more preferably 150 to 500.

[0106] The number of optionally protected amino groups in Compound A is preferably 2 or more, more preferably 2 to 4, and even more preferably 2. The optionally protected amino groups in Compound A are represented by the above formula (R Ｔ ) is preferably a group represented by the formula (I).

[0107] The content of compound A is preferably 0.1 to 10 mass %, more preferably 0.5 to 5 mass %, based on the total solid content of the resin composition.

[0108] <Compound Having Structure A (Compound B)> The resin composition of the present invention preferably contains a compound having Structure A (also referred to as "Compound A"), which is a structure in which two groups selected from the group consisting of a carboxylate group and an optionally protected carboxy group are linked by a linking group having a linking chain length of 2 to 4. Compounds corresponding to the above-mentioned Resin P-2 are not considered to be Compound B. For example, when the resin composition contains the above-mentioned Resin P-1 and Compound B, the reaction between Resin P-1 and Compound B can increase the molecular weight of the resin during heating, etc., potentially improving properties such as elongation at break and chemical resistance. Furthermore, because the final properties such as elongation at break can be improved in this way, the molecular weight of the resin P-1 added initially can be lower than conventional. This can also improve resolution.

[0109] The molecular weight of compound B is preferably 100 to 1,000, and more preferably 150 to 500.

[0110] The number of Structure A in Compound B is preferably 2 or more, more preferably 2 to 4, and even more preferably 2. The group containing Structure A in Compound B is preferably a group represented by any one of Formulas (S-1) to (S-4) above, and more preferably a group represented by any one of Formulas (CA-1) or (CA-2) above.

[0111] The content of compound B is preferably 0.1 to 10 mass %, more preferably 0.5 to 5 mass %, based on the total solid content of the resin composition.

[0112] <Polymerizable Compound> The resin composition of the present invention contains a polymerizable compound.

[0113] The melting point of the polymerizable compound is preferably 25° C. or lower. By setting the melting point to 25° C. or lower, the coating film becomes more fluid when dried and heated, and the flatness of the cured product can be improved.

[0114] In particular, from the viewpoint of reducing the dielectric constant of the cured product, it is preferable that the polymerizable compound contains a compound having a ClogP value of 3.0 or more, and it is more preferable that the polymerizable compound contains a compound having a ClogP value of 3.0 or more and having an aromatic ring structure or an aliphatic ring structure having 6 or more carbon atoms.

[0115] The ClogP value is a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water. Known methods and software can be used to calculate the ClogP value, but unless otherwise specified, the present invention uses the ClogP program incorporated into the PC Models system from Daylight Chemical Information Systems.

[0116] The ClogP value is preferably 4.0 or more, and more preferably 6.0 or more. The upper limit of the ClogP value is not particularly limited, but is preferably 15.0 or less.

[0117] The aromatic ring structure may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but is preferably an aromatic hydrocarbon ring, and more preferably contains a benzene ring. From the viewpoint of reducing the dielectric constant of the cured product, it is preferably a fused ring such as a fluorene ring. As the aliphatic ring structure having 6 or more carbon atoms, an aliphatic ring structure having 6 to 30 carbon atoms is preferred, and an aliphatic ring structure having 6 to 20 carbon atoms is more preferred. As the aliphatic ring structure having 6 or more carbon atoms, a monocyclic ring such as a cyclohexane ring, a dicyclopentane ring, a tricyclo[5.2.1.0] ring, ２，６] A polycyclic ring such as a decane ring is preferred.

[0118] A polymerizable compound having a ClogP value of 3.0 or more (particularly, a compound having a ClogP value of 3.0 or more and having an aromatic ring structure or an aliphatic ring structure having 6 or more carbon atoms) is preferably a compound containing a group having an ethylenically unsaturated bond, more preferably a compound containing two or more groups having an ethylenically unsaturated bond. Also, a compound containing two groups having an ethylenically unsaturated bond is preferable. Furthermore, a polymerizable compound having a ClogP value of 3.0 or more (particularly, a compound having a ClogP value of 3.0 or more and having an aromatic ring structure or an aliphatic ring structure having 6 or more carbon atoms) is preferably a compound corresponding to the radical crosslinking agent described below.

[0119] Specific examples of polymerizable compounds having a ClogP value of 3.0 or more include, but are not limited to, the following compounds:

[0120] Examples of the polymerizable compound include a polymerizable compound having a radical polymerizable group (radical crosslinking agent) and other crosslinking agents.

[0121] [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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0127] 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.

[0128] 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).

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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. Furthermore, as the radical crosslinking agent, the above-mentioned crosslinking agent U or a radical crosslinking agent having an isocyanuric ring structure is preferred, and a radical crosslinking agent having a urea bond or an isocyanuric ring structure is more preferred. By including crosslinking agent U in the resin composition, chemical resistance, resolution, etc. may be improved. The mechanism by which the above effect is achieved is unclear; however, it is thought that, for example, upon curing by heating, a portion of crosslinking agent U is thermally decomposed to generate amines, etc., which then promote the cyclization of a precursor of a cyclized resin, such as a polyimide precursor. Crosslinking agent U may have only one urea bond or urethane bond, or may have one or more urea bonds and one or more urethane bonds, or may have no urethane bonds but two or more urea bonds, or may have no urea bonds but two or more urethane bonds. The total number of urea bonds and urethane bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When crosslinking agent U has no urethane bonds, the number of urea bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When crosslinking agent U has no urea bonds, the number of urethane bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0133] The radical polymerizable group in the crosslinking agent U is not particularly limited, but examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. A (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred. When the crosslinking agent U has two or more radical polymerizable groups, the structures of the respective radical polymerizable groups may be the same or different. The number of radical polymerizable groups in the crosslinking agent U may be only one or may be two or more, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4. The radical polymerizable group value (mass of the compound per mole of radical polymerizable group) in the crosslinking agent U is preferably 150 to 400 g / mol. From the viewpoint of chemical resistance of the cured product, the lower limit of the radical polymerizable group value is more preferably 200 g / mol or more, even more preferably 210 g / mol or more, even more preferably 220 g / mol or more, even more preferably 230 g / mol or more, still more preferably 240 g / mol or more, and particularly preferably 250 g / mol or more. From the viewpoint of developability, the upper limit of the radical polymerizable group value is more preferably 350 g / mol or less, even more preferably 330 g / mol or less, and particularly preferably 300 g / mol or less. In particular, the polymerizable group value of crosslinking agent U is preferably 210 to 400 g / mol, and more preferably 220 to 400 g / mol.

[0134] The crosslinking agent U preferably has a structure represented by the following formula (U-1): In formula (U-1), R Ｕ１ represents a hydrogen atom or a monovalent organic group, and A represents —O— or —NR Ｎ - and R Ｎ is a hydrogen atom or a monovalent organic group, Z Ｕ１ is an m-valent organic group, and Z Ｕ２ is an (n+1)-valent organic group, X is a radical polymerizable group, n is an integer of 1 or more, and m is an integer of 1 or more.

[0135] R Ｕ１ R is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom. Ｎ is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom. Ｕ１ represents a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ - is more preferred. The hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination of these. R Ｎ represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group. Ｕ２ represents a hydrocarbon group, -O-, -C(=O)-, -S-, -S(=O) ２ -, -NR Ｎ - or a group in which two or more of these are bonded is preferred, and a hydrocarbon group, or a hydrocarbon group and -O-, -C(=O)-, -S-, -S(=O) ２ - and -NR Ｎ A group bonded to at least one group selected from the group consisting of - is more preferred. Ｕ１Examples of the groups include those listed in 1. and preferred embodiments are also the same. X is not particularly limited, but examples include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group, with a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group being preferred, and a (meth)acryloxy group being more preferred. n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2, and particularly preferably 1. m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.

[0136] It is also preferable that the crosslinking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group. From the viewpoint of the chemical resistance of the resulting cured film, the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but an alcoholic hydroxy group is preferred. From the viewpoint of the chemical resistance of the resulting cured film, the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, even more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. The alkyleneoxy group may be contained in the crosslinking agent U as a polyalkyleneoxy group. In this case, the number of repeating alkyleneoxy groups is preferably 2 to 10, more preferably 2 to 6. The amide group is a -C(=O)-NR Ｎ - refers to a bond represented by R Ｎ When the crosslinking agent U has an amide group, the crosslinking agent U may be, for example, R—C(═O)—NR Ｎ - a group represented by *, or *-C(=O)-NR ＮIt can be contained as a group represented by -R. R represents a hydrogen atom or a monovalent substituent, and is preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group. Crosslinking agent U may have two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (however, when a polyalkyleneoxy group is formed, a polyalkyleneoxy group), an amide group, and a cyano group in the molecule, but an embodiment in which only one structure is present in the molecule is also preferred. The hydroxy group, alkyleneoxy group, amide group, and cyano group may be present at any position in crosslinking agent U, but from the viewpoint of chemical resistance, it is also preferred that at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group is linked to at least one radically polymerizable group contained in crosslinking agent U via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-1"). In particular, when crosslinking agent U contains only one radically polymerizable group, it is preferred that the radically polymerizable group contained in crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2"). When crosslinking agent U contains an alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2, the structure bonded to the side of the alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. As the hydrocarbon group, a hydrocarbon group having 20 or fewer carbon atoms is preferred, a hydrocarbon group having 18 or fewer carbon atoms is more preferred, and a hydrocarbon group having 16 or fewer carbon atoms is even more preferred. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof. Preferred embodiments of the radical polymerizable group are the same as those of the radical polymerizable group in the crosslinking agent U.When crosslinking agent U contains an amide group and has the linking group L2-1 or L2-2, the structure bonded to the side of the amide group opposite the linking group L2-1 or L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof. The hydrocarbon group is preferably a hydrocarbon group having 20 or fewer carbon atoms, more preferably a hydrocarbon group having 18 or fewer carbon atoms, and even more preferably a hydrocarbon group having 16 or fewer carbon atoms. Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof. Preferred aspects of the radically polymerizable group are the same as those of the radically polymerizable group in crosslinking agent U described above. In the above aspect, the carbon atom side of the amide group may be bonded to the linking group L2-1 or L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or L2-2. Among these, from the viewpoints of adhesion to the substrate, chemical resistance, and suppression of Cu voids, it is preferable that crosslinking agent U have a hydroxy group.

[0137] From the viewpoint of compatibility with the specific resin, etc., the crosslinking agent U preferably contains an aromatic group. The aromatic group is preferably directly bonded to a urea bond or urethane bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure. The aromatic heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocycle in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be condensed with other rings, for example, indole or benzimidazole. The heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The aromatic group is preferably contained in a linking group that links two or more radical polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radical polymerizable group contained in the crosslinking agent U.

[0138] The number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10. When crosslinking agent U contains a total of two or more urea bonds or urethane bonds, when it contains two or more radical polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radical polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group may be within the above range. In this specification, the "number of atoms (linking chain length) between the urea bond or urethane bond and the polymerizable group" refers to the atomic chain on the path connecting the two atoms or atomic groups to be linked that connects these objects via the shortest distance (minimum number of atoms). For example, in the structure represented by the following formula, the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.

[0139] [Axis of symmetry] It is also preferable that the crosslinking agent U is a compound having a structure that does not have an axis of symmetry. The fact that the crosslinking agent U does not have an axis of symmetry means that the crosslinking agent U is a bilaterally asymmetric compound that does not have an axis that would produce a molecule identical to the original molecule by rotating the entire compound. Furthermore, when the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that the fact that the crosslinking agent U does not have an axis of symmetry suppresses aggregation of the crosslinking agent U molecules in the composition film.

[0140] [Molecular Weight] The molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.

[0141] The method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a radical polymerizable compound and a compound having an isocyanate group with a compound having at least one of a hydroxy group and an amino group.

[0142] Specific examples of the crosslinking agent U are shown below, but the crosslinking agent U is not limited to these.

[0143] As the radical crosslinking agent having an isocyanuric ring structure, a compound having two or three radically polymerizable groups is preferred, and a compound having three radically polymerizable groups is more preferred. Furthermore, examples of the radical crosslinking agent having an isocyanuric ring structure include tris(2-acryloyloxyethyl) isocyanurate, tris(2-methacryloyloxyethyl) isocyanurate, EO (ethylene oxide)-modified isocyanuric acid diacrylate, EO-modified isocyanuric acid triacrylate, and compounds having the following structure, but are not limited to these. In the following structure, n each independently represents an integer of 1 to 20, and R represents a divalent linking group.

[0144] 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-pentyl glycol di ... Tandiol diacrylate, 1,6-hexanediol 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, 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 polyethylene glycol chain formula weight of approximately 200. 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.

[0145] 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.

[0146] 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.

[0147] [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 the photoacid generator or photobase generator described above. 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 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.

[0148] [Polymerization initiator] The resin composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] 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).

[0154] 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).

[0155] 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.

[0156] 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.

[0157] 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.

[0158] 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.

[0159]

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] [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.

[0165] 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.

[0166] [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.

[0167] 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.

[0168] 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.

[0169] The polymerization initiator may be a photoacid generator. The photoacid generator is preferably a photoacid generator that generates radicals. Specifically, it is preferably a compound that absorbs light, decomposes to generate radicals, and abstracts hydrogen from the solvent or the photoacid generator itself to generate an acid.

[0170] Examples of the photoacid generator include quinone diazide compounds, oxime sulfonate compounds, organic halide compounds, organic borate compounds, disulfone compounds, and onium salts, and onium salts are preferred. Examples of the onium salts include diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts.

[0171] Furthermore, the onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may or may not be bonded via a covalent bond. That is, the onium salt may be an intramolecular salt having a cation moiety and an anion moiety in the same molecular structure, or an intermolecular salt in which a cation molecule and an anion molecule, which are separate molecules, are ionically bonded, but an intermolecular salt is preferred. Furthermore, in the composition of the present invention, the cation moiety or the cation molecule and the anion moiety or the anion molecule may be bonded via an ionic bond or may be dissociated.

[0172] [Sulfonium Salt] In the present invention, the sulfonium salt means a salt of a sulfonium cation and an anion.

[0173] -Sulfonium Cation- As the sulfonium cation, a tertiary sulfonium cation is preferable, and a triaryl sulfonium cation is more preferable. Furthermore, as the sulfonium cation, a cation represented by the following formula (103) is preferable.

[0174] In formula (103), R ８ ~R １０ R each independently represents a hydrocarbon group. ８ ~R １０ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an aryl group having 6 to 12 carbon atoms, and even more preferably a phenyl group. ８ ~R １０may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among these, it is preferable that the substituent is an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. R ８ ~R １０ may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

[0175] -Anion- The anion is not particularly limited and may be selected in consideration of the acid to be generated. ６ F ５ ) ４ － , B.F. ４ － Boron-based anions such as (Rf) ｎ PF ６－ｎ － 、 PF ３ (C ２ F ５ ) ３－ , P.F. ６ － phosphorus-based anions such as SbF ６ － and other anions such as carboxylate anions and sulfonate anions.

[0176] [Iodonium Salt] In the present invention, the iodonium salt refers to a salt of an iodonium cation and an anion. Examples of the anion include the same anions as those in the sulfonium salt described above, and preferred embodiments are also the same.

[0177] -Iodonium Cation- As the iodonium cation, a diaryliodonium cation is preferred. Furthermore, as the iodonium cation, a cation represented by the following formula (104) is preferred.

[0178] In formula (104), R １１ and R １２ R each independently represents a hydrocarbon group. １１ and R １２ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an aryl group having 6 to 12 carbon atoms, and even more preferably a phenyl group. １１ and R １２ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among these, it is preferable that the substituent is an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. R １１ and R １２ may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

[0179] [Phosphonium Salt] In the present invention, the phosphonium salt refers to a salt of a phosphonium cation and an anion. Examples of the anion include the same anions as those in the sulfonium salt described above, and preferred embodiments are also the same.

[0180] -Phosphonium Cation- The phosphonium cation is preferably a quaternary phosphonium cation, such as a tetraalkylphosphonium cation, a triarylmonoalkylphosphonium cation, etc. Furthermore, the phosphonium cation is preferably a cation represented by the following formula (105):

[0181] In formula (105), R １３ ~R １６ R each independently represents a hydrogen atom or a hydrocarbon group. １３ ~R １６are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an aryl group having 6 to 12 carbon atoms, and even more preferably a phenyl group. １３ ~R １６ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. Among these, it is preferable that the substituent is an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. R １３ ~R １６ may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

[0182] The content of the photoacid generator is preferably 0.1 to 20% by mass, more preferably 0.5 to 18% by mass, even more preferably 0.5 to 10% by mass, even more preferably 0.5 to 3% by mass, and even more preferably 0.5 to 1.2% by mass, based on the total solid content of the resin composition. The photoacid generator may be used alone or in combination with multiple types. In the case of a combination of multiple types, it is preferable that the total amount thereof is within the above range. It is also preferable to use it in combination with a sensitizer to impart photosensitivity to a desired light source.

[0183] 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 the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.

[0184] 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.

[0185] 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 %.

[0186] [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.

[0187] 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.

[0188] 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%. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, it is preferable that the total amount is in the above range.

[0189] 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. In particular, when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in excellent 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, acyloxyimino compounds, etc. Specific examples of non-ionic base generators include compounds represented by formula (B1), formula (B2), or formula (B3).

[0190] In formula (B1) and formula (B2), Rb １ , Rb ２ and Rb ３ each independently represents an organic group not having a tertiary amine structure, a halogen atom, or a hydrogen atom, provided that Rb １ and Rb ２ cannot be hydrogen atoms at the same time. １ , Rb ２ and Rb ３None of the above has a carboxy group. In this specification, the term "tertiary amine structure" refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to carbon atoms of a hydrocarbon group. Therefore, if the carbon atom bonded to the trivalent nitrogen atom is a carbon atom constituting a carbonyl group, i.e., if it forms an amide group together with the nitrogen atom, it is not a tertiary amine structure.

[0191] In formula (B1) and formula (B2), Rb １ , Rb ２ and Rb ３ Preferably, at least one of these contains a cyclic structure, and more preferably, at least two contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a fused ring, and a monocyclic ring or a fused ring in which two monocyclic rings are fused is preferred. The monocyclic ring is preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.

[0192] More specifically, Rb １ and Rb ２ is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). These groups may have a substituent. Rb １ and Rb ２ may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring. １ and Rb ２is preferably a linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, more preferably a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms) which may have a substituent, and even more preferably a cyclohexyl group which may have a substituent.

[0193] Rb ３ Examples of the alkyl group include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, and even more preferably having 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably having 8 to 20 carbon atoms, and even more preferably having 8 to 16 carbon atoms), an alkoxyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), and an arylalkyloxy group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms). Among these, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably having 3 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferred. ３ may further have a substituent.

[0194] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or (B1-2):

[0195] In the formula, Rb １１ and Rb １２ , and Rb ３１ and Rb ３２ respectively represent Rb in formula (B1). １ and Rb ２ is the same as Rb １３is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), which may have a substituent. １３ is preferably an arylalkyl group.

[0196] Rb ３３ and Rb ３４ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 8 carbon atoms, and still more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 8 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and still more preferably having 7 to 11 carbon atoms), and a hydrogen atom is preferred.

[0197] Rb ３５ represents an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), with an aryl group being preferred.

[0198] The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a).

[0199] Rb １１ and Rb １２ represents Rb in formula (B1-1). １１ and Rb １２ Rb １５ and Rb １６is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and even more preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and even more preferably having 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 11 carbon atoms), and preferably a hydrogen atom or a methyl group. １７ represents an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 10 carbon atoms, and even more preferably having 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably having 7 to 19 carbon atoms, and even more preferably having 7 to 12 carbon atoms), and among these, an aryl group is preferred.

[0200]

[0201] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a linking chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the linking chain is 3 or more. Ｎ１ and R Ｎ２ each independently represents a monovalent organic group.

[0202] In this specification, the term "linking chain" refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked, which links these atoms or groups of atoms in the shortest possible manner (with the smallest number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as the saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as the "linking chain length" or "length of the linking chain") is 4.

[0203] The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the connecting chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly progressing the intramolecular cyclization reaction, the upper limit of the connecting chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the connecting chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of WO 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of WO 2018 / 038002.

[0204] The base generator also preferably contains a compound represented by the following formula (N1).

[0205] In formula (N1), R Ｎ１ and R Ｎ２ each independently represents a monovalent organic group, R Ｃ１ represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

[0206] L is a divalent linking group, and is preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms present in the atomic sequence that forms the shortest path between the two carbonyl groups in the formula.

[0207] In formula (N1), R Ｎ１ and R Ｎ２R each independently represents a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably having 2 to 18 carbon atoms, and even more preferably having 3 to 12 carbon atoms), and is preferably a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms). Specific examples include an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and even more preferably having 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and even more preferably having 6 to 10 carbon atoms), and an aliphatic hydrocarbon group is preferred. Ｎ１ and R Ｎ２ When an aliphatic hydrocarbon group is used as the base, the basicity of the generated base is high, and this is preferable. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have an oxygen atom in the aliphatic hydrocarbon chain, in the aromatic ring, or in the substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.

[0208] R Ｎ１ and R Ｎ２Examples of the aliphatic hydrocarbon group constituting the alkyl group include linear or branched chain alkyl groups, cyclic alkyl groups, groups containing a combination of a linear alkyl group and a cyclic alkyl group, and alkyl groups having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms. Examples of the linear or branched chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, and isohexyl groups. The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. The group containing a combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms. Examples of the group containing a combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group. The alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched. In particular, from the viewpoint of increasing the boiling point of the decomposition product base described below, R Ｎ１ and R Ｎ２ is preferably an alkyl group having 5 to 12 carbon atoms. However, in a formulation where importance is placed on adhesion when laminating with a metal (e.g., copper) layer, a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferred.

[0209] R Ｎ１ and R Ｎ２ may be linked to each other to form a cyclic structure. The cyclic structure may have an oxygen atom or the like in the chain. Ｎ１ and R Ｎ２The cyclic structure formed by may be a monocyclic ring or a fused ring, but is preferably a monocyclic ring. The cyclic structure formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), for example, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, etc., and preferred examples include a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.

[0210] R Ｃ１ represents a hydrogen atom or a protecting group, preferably a hydrogen atom. The protecting group is preferably a protecting group that decomposes under the action of an acid or a base, and preferably a protecting group that decomposes with an acid. Specific examples of the protecting group include linear or cyclic alkyl groups and linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group. Examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, and preferred are a methyloxymethyl (MOM) group and an ethyloxyethyl (EE) group. Examples of cyclic alkyl groups having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl (THP) group.

[0211] In formula (N1), the divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The hydrocarbon group may have a substituent and may have atoms other than carbon atoms in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group that may have an oxygen atom in the chain, more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a group containing a combination of a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group that may have an oxygen atom in the chain. These groups may not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group containing a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (for example, an arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10 carbon atoms.

[0212] Specific examples of the linking group L include linear or branched chain alkylene groups, cyclic alkylene groups, groups containing a combination of linear alkylene groups and cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylene groups, and arylene alkylene groups. The linear or branched chain alkylene groups preferably have 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The cyclic alkylene groups preferably have 3 to 12 carbon atoms, more preferably 3 to 6. The groups containing a combination of linear alkylene groups and cyclic alkylene groups preferably have 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkylene groups having an oxygen atom in the chain may be linear or cyclic, linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0213] The linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. The linear or branched chain alkenylene group preferably has 1 to 10 C═C bonds, more preferably 1 to 6, and even more preferably 1 to 3. The cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The cyclic alkenylene group preferably has 1 to 6 C═C bonds, more preferably 1 to 4, and even more preferably 1 to 2. The arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among these, a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferred, and a 1,2-ethylene group, a propanediyl group (particularly a 1,3-propanediyl group), a cyclohexanediyl group (particularly a 1,2-cyclohexanediyl group), a vinylene group (particularly a cis-vinylene group), a phenylene group (1,2-phenylene group), a phenylenemethylene group (particularly a 1,2-phenylenemethylene group), and an ethyleneoxyethylene group (particularly a 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.

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

[0215]

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

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

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

[0219] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0220] 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.

[0221] 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.

[0222] 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.

[0223] <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.

[0224] 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.

[0225] 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.

[0226] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0227] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0228] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0229] 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.

[0230] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0231] 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.

[0232] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0233] 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.

[0234] Furthermore, the resin composition of the present invention preferably contains a solvent having a boiling point of 50°C to 300°C at 1 atmosphere, and more preferably contains a solvent having a boiling point of 100 to 260°C. In the present invention, the boiling point of the solvent is the boiling point at 1 atmosphere. According to such an embodiment, it is believed that a cured product having excellent solvent removability and excellent resolution can be obtained. The boiling point is preferably 150°C or higher, preferably 180°C or higher, and more preferably 200°C or higher. The upper limit of the boiling point is preferably 250°C or lower, more preferably 240°C or lower, and even more preferably 230°C or lower. Furthermore, the resin composition of the present invention preferably contains two or more solvents having a boiling point of 100 to 260°C, more preferably two or more solvents having a boiling point of 150 to 250°C, and even more preferably two or more solvents having a boiling point of 180 to 230°C. The content of the solvent having a boiling point of 100 to 260°C is preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more, based on the total mass of the composition. When two or more solvents having a boiling point of 100 to 260°C are contained, the total amount thereof is preferably within the above range.

[0235] 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.

[0236] <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 metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0237] [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.).

[0238]

[0239] 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.).

[0240] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0241] 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.

[0242] 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.

[0243] <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.

[0244] 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.

[0245] Among these, the resin composition of the present invention preferably contains an azole compound. The azole compound is a compound containing an azole structure, and the azole structure refers to a five-membered ring structure containing a nitrogen atom as a ring member, and preferably a five-membered ring structure containing two or more nitrogen atoms as ring members. Specific examples of the azole structure include an imidazole structure, a triazole structure, and a tetrazole structure. These structures may form a polycycle by condensation with another ring structure, such as benzimidazole or benzotriazole. Furthermore, as a compound having an azole structure, a compound in which a group represented by the following formula (R-1) or the following formula (R-2) is directly bonded to the azole structure is also preferred. In formula (R-1), R １ represents a monovalent organic group, and * represents a bonding site with the azole structure. ２ represents a hydrogen atom or a monovalent organic group, R ３ represents a monovalent organic group, and * represents a bonding site with the azole structure. １ is a hydrocarbon group, or a hydrocarbon group and —O—, —C(═O)—, —S—, —S(═O) ２ - and -NR Ｎ - is preferably a group represented by a bond to at least one group selected from the group consisting of R Ｎ is as described above. The hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof. １ The total number of carbon atoms in R is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20. １ The bonding site with the carbonyl group in formula (R-1) is a hydrocarbon group or -NR Ｎ In formula (R-1), * represents a bonding site to the azole structure, and is preferably a bonding site to a carbon atom that is a ring member of the azole structure. ２ is preferably a hydrogen atom. ２ is a monovalent organic group, R ２ represents a hydrocarbon group, or a hydrocarbon group and —O—, —C(═O)—, —S—, —S(═O) ２- and -NR Ｎ - is preferably a group represented by a bond to at least one group selected from the group consisting of R Ｎ is as described above. The hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof. ２ When R is a monovalent organic group, the total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20. ２ is a monovalent organic group, R ２ The bonding site to the nitrogen atom in formula (R-2) in formula (R-2) is preferably a hydrocarbon group or —C(═O)—. ３ is a hydrocarbon group, or a hydrocarbon group and —O—, —C(═O)—, —S—, —S(═O) ２ - and -NR Ｎ - is preferably a group represented by a bond to at least one group selected from the group consisting of R Ｎ represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom. The hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof. ３ When R is a monovalent organic group, the total number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and even more preferably 3 to 20. ３ In formula (R-2), the bonding site to the nitrogen atom is preferably a hydrocarbon group or -C(=O)-. In formula (R-2), * represents the bonding site to the azole structure, and is preferably the bonding site to a carbon atom that is a ring member of the azole structure.

[0246] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0247] 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.

[0248] Specific examples of the migration inhibitor include the following compounds.

[0249]

[0250] 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.

[0251] 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.

[0252] <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.

[0253] In particular, from the viewpoint of improving adhesion to a substrate, the resin composition of the present invention preferably further contains the above-mentioned azole compound and the above-mentioned silane coupling agent. By containing these compounds, adhesion to a substrate is likely to be maintained, especially even after the cured product is exposed to high-temperature and high-humidity conditions.

[0254] <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.

[0255] 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.

[0256] 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.

[0257] 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.

[0258] <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.

[0259] [Surfactant] Various surfactants can be used as the surfactant, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0260] By including a surfactant in the photosensitive resin composition of the present invention, the liquid properties (particularly fluidity) of the coating liquid composition when prepared can be further improved, and the uniformity of the coating thickness and the liquid saving can be further improved. That is, when a film is formed using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. Therefore, it is possible to more suitably form a uniform film with little thickness unevenness.

[0261] Examples of fluorine-based surfactants include the compounds described in paragraph 0328 of WO 2021 / 112189, the contents of which are incorporated herein by reference. As the fluorine-based surfactant, fluorine-containing polymer compounds containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups, propyleneoxy groups) can also be preferably used, and examples thereof include the following compounds.

[0262] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As the fluorosurfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference. Commercially available products include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0263] The fluorine content in the fluorine-containing surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-containing surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

[0264] Examples of silicone surfactants, hydrocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329 to 0334 of WO 2021 / 112189, the contents of which are incorporated herein by reference.

[0265] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition.

[0266] [Inorganic Particles] Specific examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0267] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle size of the inorganic particles is the primary particle size and also the volume average particle size. The volume average particle size can be measured, for example, by dynamic light scattering using a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction / scattering method.

[0268] [Organotitanium Compound] When the resin composition contains an organotitanium compound, a resin layer having excellent chemical resistance can be formed even when cured at low temperatures.

[0269] Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown below in I) to VII): I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability to the resin composition and a good curing pattern. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate). II) Tetraalkoxytitanium compounds: for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis{2,2-(allyloxymethyl)butoxide}], etc. III) Titanocene compounds: for example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxytitanium compounds: for example, titanium tris(dioctylphosphate)isopropoxide, titanium tris(dodecylbenzenesulfonate)isopropoxide, etc. V) Titanium oxide compounds: for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanate coupling agents: for example, isopropyl tridodecylbenzenesulfonyl titanate, etc.

[0270] Among these, from the viewpoint of better chemical resistance, the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. In particular, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0271] It is also preferable to contain a compound represented by the following formula (T-1) as the organotitanium compound or in place of the organotitanium compound. In formula (T-1), M is titanium, zirconium, or hafnium, l1 is an integer of 0 to 2, l2 is 0 or 1, l1 + l2 × 2 is an integer of 0 to 2, m is an integer of 0 to 4, n is an integer of 0 to 2, l1 + l2 + m + n × 2 = 4, and R １１ are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group; R １２ is a substituted or unsubstituted hydrocarbon group, R ２ are each independently a group containing a structure represented by the following formula (T-2), and R ３ are each independently a group containing a structure represented by the following formula (T-2), Ａ are each independently an oxygen atom or a sulfur atom. In formula (T-2), X １ ~X ３ each independently represents -C(-*)= or -N=, * represents a bonding site to another structure, and # represents a bonding site to a metal atom.

[0272] In formula (T-1), from the viewpoint of storage stability of the composition, M is preferably titanium. In formula (T-1), an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention. In formula (T-1), m is preferably 2 or 4, and more preferably 2. In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1. Here, it is also preferable that in formula (T-1), l1 and l2 are 0, and m is 0, 2, or 4.

[0273] In formula (T-1), from the viewpoint of the stability of the specific metal complex, R １１ is preferably a substituted or unsubstituted cyclopentadienyl ligand. １１ The cyclopentadienyl group, alkoxy group and phenoxy group in the formula (I) may be substituted, but an embodiment in which they are unsubstituted is also one of the preferred embodiments of the present invention.

[0274] In formula (T-1), R １２ is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. １２ The hydrocarbon group in may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group. R １２ The substituent in R is preferably a monovalent substituent, such as a halogen atom. １２ When R is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. １２ is preferably an unsubstituted phenylene group. １２ The phenylene group in is preferably a 1,2-phenylene group.

[0275] In formula (T-1), m is 2 or more, and R ２ If two or more are included,２ In formula (T-1), n ​​is 2 or more, and R ３ If two or more are included, ３ The structures may be the same or different.

[0276] In formula (T-2), X １ ~X ３ each independently represents -C(-*)= or -N=, and it is preferable that at least one represents -C(-*)=, and it is more preferable that at least two represent -C(-*)=.

[0277] Specific examples of the compound represented by formula (T-1) include, but are not limited to, the compound I-3 in the examples.

[0278] When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 part by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is improved.

[0279] When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 part by mass or more, the heat resistance and chemical resistance of the obtained cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is superior.

[0280] Other additives include compounds described in paragraphs 0249 to 0282 and 0316 to 0358 of WO 2022 / 145355, the disclosures of which are incorporated herein by reference.

[0281] <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.

[0282] When a cured product having a film thickness of 10 μm is formed using the resin composition of the present invention, the transmittance of the cured product at a wavelength of 365 nm is preferably 10% or more, more preferably 20% or more, and even more preferably 25% or more. The upper limit of the transmittance is not particularly limited and may be 100%. For example, the cured product can be obtained by applying the resin composition of the present invention to a silicon wafer, drying it at 100° C. for 5 minutes, and then applying a 500 mJ / cm ２ After exposing the entire surface to i-rays at an exposure energy of 1000 kJ / min, the temperature is increased at a rate of 10° C. / min in a nitrogen atmosphere, and the film is heated at 230° C. for 180 minutes.

[0283] <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.

[0284] 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.

[0285] 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.

[0286] 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.

[0287] 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.

[0288] <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

[0289] <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.

[0290] <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.

[0291] Filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the resin composition of the present invention. 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. The filter may be pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. An example of a connection mode is a mode in which an HDPE filter with a pore size of 1 μm is connected in series as the first stage and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtering under pressure, the pressure to be applied is preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less. In addition to filtering using a filter, a process of removing impurities using an adsorbent may be performed. Filter filtration and a process of removing impurities using an adsorbent may be combined. Known adsorbents can be used as the adsorbent. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtering using a filter, the resin composition filled in a bottle may be subjected to a degassing process by placing it under reduced pressure.

[0292] (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.

[0293] <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.

[0294] [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.

[0295] 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.

[0296] 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.

[0297] <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.

[0298] <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.

[0299] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0300] 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.

[0301] <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.

[0302] <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.

[0303] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0304] When the developer is an alkaline aqueous solution, examples of the basic compound that can be contained in the alkaline aqueous solution include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferred are TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine, and more preferred is TMAH. The content of the basic compound in the developer is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.3 to 3% by mass, based on the total mass of the developer.

[0305] 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.

[0306] 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.

[0307] 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.

[0308] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0309] [Method of Supplying Developer] The method of supplying the developer is not particularly limited as long as it can form the desired pattern, and includes a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to the film formed on the substrate using a nozzle, and a method of continuously supplying the developer. The type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoints of the permeability of the developer, the removability of non-image areas, and production efficiency, a method of supplying the developer using a straight nozzle or a method of continuously supplying the developer using a spray nozzle is preferred, and from the viewpoint of the permeability of the developer to the image areas, a method of supplying using a spray nozzle is more preferred. In addition, a process may be adopted in which the developer is continuously supplied using a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again using a straight nozzle, and the substrate is spun to remove the developer from the substrate, or this process may be repeated multiple times. Methods of supplying the developer in the development process include a process in which the developer is continuously supplied to the substrate, a process in which the developer is kept substantially stationary on the substrate, a process in which the developer is vibrated on the substrate using ultrasound or the like, and a combination thereof.

[0310] The development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

[0311] 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.

[0312] [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.

[0313] 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.

[0314] 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.

[0315] 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.

[0316] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0317] [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.

[0318] 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.

[0319] <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, a resin such as a polyimide precursor is cyclized to form a resin such as a 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.

[0320] When the resin composition contains a resin corresponding to a polyimide precursor, the heating step is preferably a step of promoting a cyclization reaction of the polyimide precursor in the pattern by the action of a base or the like generated from the base generator upon heating.

[0321] 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.

[0322] 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.

[0323] 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.

[0324] 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.

[0325] 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.

[0326] 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.

[0327] <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 polyimide precursor or the like progresses due to exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group progresses due to 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.

[0328] <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).

[0329] 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.

[0330] 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.

[0331] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0332] <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).

[0333] 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.

[0334] (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.

[0335] 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.

[0336] 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.

[0337] <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.

[0338] 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.

[0339] 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.

[0340] 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.

[0341] (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.

[0342] (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.

[0343] (Resin) The resin of the present invention is a polyimide containing a repeating unit represented by the above formula (1-1). A preferred embodiment of the resin of the present invention is the same as the preferred embodiment of the first specific resin described above, except that it is essential that the resin contains a repeating unit represented by formula (1-1).

[0344] In particular, in the resin of the present invention, X in formula (1-1) １ and Y １ Each of these preferably contains a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-5).

[0345] The molar ratio of the structure represented by formula (A-1) to the amount of imide structures is preferably 1 to 100%, more preferably 10 to 85%, and even more preferably 10 to 50%.

[0346] 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.

[0347] <Synthesis of Raw Material Styrene Compound> In a flask equipped with a stirrer, a condenser, and a thermometer, 24.0 g (100 mmol) of a 50 wt % p-hydroxystyrene propylene glycol monomethyl ether acetate solution, 10.9 g (100 mmol) of 4-chloro-1-butanol, 16.6 g (120 mmol) of potassium carbonate, 1.99 g (12 mmol) of potassium iodide, 40 g of N-methylpyrrolidone, and 0.01 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were mixed and reacted at 90°C for 15 hours. The reaction solution was filtered to remove salts. Subsequently, the filtrate was dissolved in 500 mL of ethyl acetate and washed twice each with 200 mL of water, 100 mL of 0.5 N hydrochloric acid, 200 mL of saturated sodium bicarbonate water, and 200 mL of saturated saline, in that order. The mixture was dried over magnesium sulfate, and the solvent was removed using an evaporator to obtain 16.3 g of a-1. The fact that it is a-1 means that １ This was confirmed by H-NMR spectrum.

[0348] <Synthesis of Dinitro Compound A-1> In a flask equipped with a stirrer, a condenser, and a thermometer, 23.06 g (100 mmol) of 3,5-dinitrobenzyl chloride, 0.005 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 9.50 g (120 mmol) of dehydrated pyridine were dissolved in 80 g of dehydrated tetrahydrofuran, and the solution was cooled to a temperature range of 0 to 10° C. Subsequently, 11.92 g (100 mmol) of 4-aminostyrene was dissolved in 40 g of dehydrated tetrahydrofuran and added dropwise over 1 hour at a temperature range of 0 to 10° C. After stirring for 1 hour, the temperature was raised to 20 to 25° C. and the solution was further stirred for 2 hours. The reaction solution was added to 1 L of water to cause crystallization, filtered, reslurried twice with 500 mL of 0.1 N (mol / L) hydrochloric acid, washed with 500 mL of water, and dried at 40°C for 24 hours to obtain 30.0 g of dinitro compound A-1 having a vinylphenyl group. １ This was confirmed by H-NMR spectrum. １ H-NMR (BRUKER, AVANCE NEO 400): δ (ppm, DMSO-d6) 5.22-5.26 (d, 1H), 5.79-5.83 (d, 1H), 6.70-6.77 (q, 1H), 7.52-7.54 (d, 2H), 7.79-7.81 (d, 2H), 9.01-9.02 (t, 1H), 9.17-9.18 (d, 2H), 10.91 (s, 1H)

[0349] Synthesis of dinitro compounds A-2 to A-9: A-2 to A-9 were synthesized in the same manner as in the synthesis of dinitro compound A-1. The structures of A-2 to A-9 are shown below.

[0350] <Synthesis of diamine compound AA-1> 5.75 g (95.8 mmol) of acetic acid, 11.3 g (210 mmol) of ammonium chloride, 0.01 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 240 mL of isopropyl alcohol, and 60 g of water were added to a flask equipped with a stirrer, a condenser, and a thermometer. Subsequently, 55.7 g (958 mmol) of reduced iron was added, and 30.0 g (95.8 mmol) of the A-1 synthesized above was added in small portions over 1 hour. After stirring for 30 minutes, the mixture was heated to 80°C and stirred for 4 hours. The mixture was then filtered using a funnel filled with Celite, and the filtrate was collected. Subsequently, the filtrate was transferred to a separatory funnel, diluted with 500 mL of ethyl acetate, washed three times with 300 mL of saturated sodium bicarbonate water, and once with 300 mL of saturated saline, dried over sodium sulfate, and then the solvent was removed using an evaporator. The precipitated solid was dried at 40°C for 24 hours to obtain 22 g of diamine compound AA-1 having a nitrophenyl group. １ This was confirmed by H-NMR spectrum. １ H-NMR (BRUKER, AVANCE NEO 400): δ (ppm, DMSO-d6) 4.94 (s, 4H), 5.15-5.18 (d, 1H), 5.71-5.76 (d, 1H), 5.98-5.99 (t, 1H), 6.27-6.28 (d, 2H), 6.64-6.71 (q, 1H), 7.40-7.42 (d, 2H), 7.73-7.75 (d, 2H), 9.99 (s, 1H)

[0351] <Synthesis of diamine compounds AA-2 to AA-9> AA-2 to AA-9 were synthesized in the same manner as for the diamine compound AA-1, except that A-2 to A-9 were used instead of A-1. The structures of AA-2 to AA-9 are shown below.

[0352] Synthesis Example SP-1: Synthesis of Polyimide (SP-1) In a flask equipped with a stirrer, a condenser, and a thermometer, 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were dissolved in 120 g of N-methylpyrrolidone (NMP) while removing water. Subsequently, 9.34 g (25.36 mmol) of 4,4'-bis(3-aminophenoxy)biphenyl and 6.42 g (25.36 mmol) of AA-1 were dissolved in 100 g of NMP and added dropwise to the solution over 1 hour at a temperature of 10°C to 25°C. After stirring at 25°C for 2 hours, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the mixture was allowed to react at 80°C for 4 hours. After completion of the reaction, the mixture was cooled to 25°C and diluted with 200 g of tetrahydrofuran. Subsequently, the reaction solution was added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water, stirred for 15 minutes, and the resulting polyimide resin was filtered. Next, the resin was reslurried in 1 L of water, filtered, and then reslurried again in 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 10 hours. Subsequently, the dried resin was dissolved in 250 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added, and the mixture was stirred for 4 hours. The ion exchange resin was removed by filtration, and the resulting polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was collected by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin (SP-1). The resulting polyimide (SP-1) had a weight average molecular weight of 19,600, a number average molecular weight of 8,100, and an imidization rate of 92%. Polyimide (SP-1) is a resin having a repeating unit represented by the following formula (SP-1): １The molecular weight was determined from H-NMR spectra. In the following structure, the subscripts of the repeating units indicate the molar ratio of each repeating unit. The molar amount of the structure represented by formula (A-1) was 0.65 mmol / g. In the above and following synthesis examples, unless otherwise specified, the weight-average molecular weight and number-average molecular weight were measured by the following method. GPC measurements were performed using a high-speed GPC apparatus HLC-8420GPC (manufactured by Tosoh Corporation) with a TSK guard column, a Super AW-H (4.6 mm x 35 mm), and two TSKgel Super AWM-H (4.6 mm x 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.

[0353] [Method for measuring the molar amount of the structure represented by formula (A-1)] 0.1 g of resin was dissolved in 0.9 g of deuterated dimethyl sulfoxide, １ The vinylphenyl content was calculated by H-NMR. １ The number of H-NMR measurements was 640.

[0354] Synthesis Examples SP-2 to SP-15: Synthesis of Polyimides (SP-2 to SP-15) SP-2 to SP-15 were synthesized in the same manner as SP-1, except that the diamine and dianhydride were changed appropriately. Polyimides (SP-2) to (SP-15) are resins having repeating units represented by the following formulae SP-2 to SP-15, respectively. The structure of each repeating unit is: １ The molecular weights were determined from H-NMR spectra. In the structures below, the subscripts in parentheses indicate the molar ratio of each structure. The weight-average molecular weight, number-average molecular weight, and imidization ratio of these resins are shown in the table below.

[0355]

[0356] Synthesis Example SP-16: Synthesis of Polyimide (SP-16) 30.00 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 0.08 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were dissolved in 120 g of N-methylpyrrolidone (NMP) to obtain a solution. Subsequently, 12.17 g (47.84 mmol) of AA-2 (the above-synthesized product) was dissolved in 80 g of NMP and added dropwise to the above-mentioned solution at a temperature of 10 to 25°C over 1 hour. After stirring at 25°C for 60 minutes, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the mixture was reacted at 80°C for 4 hours. After completion of the reaction, the mixture was cooled to 25°C and diluted with 200 g of tetrahydrofuran. Subsequently, the reaction solution was added dropwise to 2.0 L of water, stirred for 15 minutes, and the polyimide resin was filtered. Next, the resin was reslurried in 1 L of water for 30 minutes, filtered, and then reslurried again in 1 L of methanol, filtered, and dried under reduced pressure at 40 ° C for 10 hours. Subsequently, the dried resin was dissolved in 250 g of tetrahydrofuran and 20 g of water, and 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added and stirred for 4 hours. The ion exchange resin was removed by filtration, and then the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was collected by filtration and dried under reduced pressure at 45 ° C for 1 day to obtain polyimide resin (SP-16). The resulting polyimide (SP-16) had a weight average molecular weight of 13,800, a number average molecular weight of 5,700, and an imidization rate of 99% or more. The molar amount of the structure represented by formula (A-1) was 1.22 mmol / g.

[0357] Synthesis Example SP-17: Synthesis of Polyimide (SP-17) 7.25 g (28.5 mmol) of AA-2 (the above synthesized product), 3.08 g (28.5 mmol) of 1,4-phenylenediamine, and 0.08 g of 2,2,6,6-tetramethylpiperidine-1-oxyl free radical were dissolved in 90 g of N-methylpyrrolidone (NMP) to obtain a solution. Subsequently, 24.62 g (47.31 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was dissolved in 120 g of NMP and added dropwise to the above solution over 1 hour at a temperature of 10 to 25°C. After stirring at 25°C for 60 minutes, 2.63 g (10 mmol) of di-tert-butyl dicarbonate was added dropwise and the mixture was stirred at 45°C for 3 hours. Subsequently, 18.2 g of pyridine and 14.7 g of acetic anhydride were added, and the mixture was reacted at 80°C for 4 hours. After completion of the reaction, the mixture was cooled to 25°C and diluted with 200 g of tetrahydrofuran. Subsequently, the reaction solution was added dropwise to a mixture of 1.5 L of methanol and 0.5 L of water, stirred for 15 minutes, and the polyimide resin was filtered. Next, the resin was reslurried in 1 L of water for 30 minutes, filtered, and then reslurried again in 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 10 hours. Subsequently, the dried resin was dissolved in 250 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added, and the mixture was stirred for 4 hours. The ion exchange resin was removed by filtration, and the polyimide resin was precipitated in 2 L of methanol and stirred for 15 minutes. The polyimide resin was collected by filtration and dried under reduced pressure at 45°C for 1 day to obtain polyimide resin (SP-17). The resulting polyimide (SP-17) had a weight-average molecular weight of 14,000, a number-average molecular weight of 5,700, an imidization rate of 99% or more, and a molar amount of the structure represented by formula (A-1) of 0.75 mmol / g.

[0358] <Synthesis of Additive: BA-1> In a recovery flask equipped with a thermometer and a calcium chloride tube, 5.00 g (19.2 mmol) of 4,4''-diamino-p-phenyl was dissolved in 40 g of dimethylformamide. Subsequently, 8.60 g (39.4 mmol) of t-butyl dicarbonate was added, and the mixture was stirred at 60°C for 3 hours. The reaction solution was added to 500 mL of acetone to cause crystallization, and the precipitate was filtered, collected, and dried at 40°C for 24 hours to obtain 5.9 g of the target product (BA-1). The structure of BA-1 is shown below. The following structure is １ This was confirmed by H-NMR spectrum.

[0359] <Synthesis of Additive: BC-1> 6.20 g (20 mmol) of 4,4'-oxydiphthalic anhydride, 4.93 g (41 mmol) of diethylene glycol monomethyl ether, and 44.5 g of tetrahydrofuran were weighed into a flask and stirred at 60°C for 12 hours. Subsequently, this reaction solution was transferred to an eggplant flask, and the solvent was removed using an evaporator, yielding 11 g of BC-1 (mixture of isomers). １ This was confirmed by H-NMR spectrum. BC-1 was a mixture of isomers with the following three structures.

[0360] Synthesis of Polyimide Precursor Synthesis Example SA-1 Synthesis of Polyimide Precursor (SA-1) In a flask equipped with a stirrer, condenser, and thermometer, 10.94 g (50 mmol) of pyromellitic anhydride, 13.7 g (102 mmol) of diethylene glycol monoethyl ether, 0.05 g of hydroquinone, 17.6 g (222 mmol) of pyridine, and 60 g of diglyme were mixed while removing water, and the mixture was stirred at 60° C. for 5 hours to synthesize a diester of pyromellitic anhydride and diethylene glycol monoethyl ether. Subsequently, the mixture was cooled to −5° C., and then 12.5 g (104 mmol) of thionyl chloride was added dropwise over 90 minutes. The mixture was stirred for 2 hours, and a white precipitate of pyridinium hydrochloride was obtained. Next, 17.98 g (41 mmol) of the diamine (AA-7) synthesized above dissolved in 80 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over 2 hours and stirred for an additional 4 hours at temperatures ranging from -5°C to 0°C. Subsequently, 10.0 g (217 mmol) of ethanol was added, and the mixture was stirred for 1 hour. The polyimide precursor was then precipitated in 3 L of water, and the water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was collected by filtration, stirred again in 4 L of water for 30 minutes, and filtered again. The resulting polyimide precursor was then dried under reduced pressure at 45°C for 24 hours. The polyimide precursor dried above was dissolved in 300 mL of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added. The mixture was stirred for 4 hours. The ion exchange resin was removed by filtration, and then the polyimide precursor was precipitated in 3 L of water. The water-polyimide precursor mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor was collected by filtration, stirred again in 4 L of water for 30 minutes, filtered again, and dried at 45°C for 24 hours to obtain polyimide precursor (SA-1). The resulting polyimide precursor (SA-1) had a weight-average molecular weight of 16,500, a number-average molecular weight of 7,200, and an imidization rate of 2%. The polyimide precursor (SA-1) is presumed to be a resin having a repeating unit represented by the following formula (SA-1). The molar amount of the structure represented by (A-1) was 1.12 mmol / g.

[0361] [Synthesis Examples SA-2 to SA-8: Synthesis of Polyimide Precursors (SA-2) to (SA-8)] Polyimide precursors (SA-2) to (SA-8) were synthesized in the same manner as in Synthesis Example SA-1, except that the raw materials were changed appropriately. Polyimide precursors (SA-2) to (SA-8) are resins having repeating units represented by the following formulae SA-2 to SA-8, respectively. The structure of each repeating unit is: １ The molecular weights were determined from H-NMR spectra. In the structures below, the subscripts in parentheses indicate the molar ratio of each structure. The weight-average molecular weight, number-average molecular weight, and imidization ratio of these resins are shown in the table below.

[0362]

[0363] <Synthesis of Comparative Compound CA-1> In a flask equipped with a stirrer, a condenser, and a thermometer, 41.4 g (114 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 57.29 g (125.0 mmol) of bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene were added while removing water, and 492.43 g of γ-butyrolactone was added, followed by stirring at a temperature of 60°C for 1.5 hours. Subsequently, 50 mL of toluene was added, and the temperature was raised to 180°C while flowing nitrogen at a flow rate of 200 mL / min, followed by stirring for 3 hours and cooling to room temperature. The obtained polymerization solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 3 / 1 to precipitate a white solid. The resulting white solid was collected and vacuum-dried at 120°C to obtain 90 g of polymer. Subsequently, 73.86 g of the polymer obtained above (150.0 mmol in terms of hydroxy groups), 21.17 g (150.0 mmol) of 2-isocyanatoethyl acrylate (hereinafter also referred to as AOI, manufactured by Showa Denko K.K.), and 828.26 g of γ-butyrolactone (GBL) were placed in a reaction vessel equipped with a stirrer and a cooling tube. Thereafter, the temperature was raised to 120°C with stirring, and the reaction was carried out for 6 hours. Subsequently, the resulting reaction solution was diluted with acetone to prepare a diluted solution, and then the diluted solution was added dropwise to a mixed solution of water / methanol = 2 / 1 to precipitate a white solid. The resulting white solid was collected and vacuum-dried at 40°C to obtain 85.8 g of CA-1. The weight average molecular weight (Mw) of CA-1 was 32,200, and the number average molecular weight (Mn) was 12,800. The structure of CA-1 was determined to be mainly composed of the structure represented by the following formula (CA-1): １ This was confirmed by H-NMR spectrum. １ The results of H-NMR measurement showed that the introduction rate of crosslinking groups was 50%.

[0364] <Synthesis of Comparative Compound CA-2> 77.5 g of 4,4'-oxydiphthalic dianhydride (ODPA) and 73.5 g of 4,4'-biphthalic dianhydride were placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. 79.1 g of pyridine was added with stirring at room temperature to obtain a reaction mixture. After the heat generated by the reaction ceased, the mixture was allowed to cool to room temperature and allowed to stand for an additional 16 hours. Next, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 96.0 g of 4,4'-diaminodiphenyl ether suspended in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and stirred for 1 hour. Then, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was collected by filtration to obtain a reaction solution. The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was collected by filtration and dissolved in 1.5 L of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 L of water to precipitate the polymer, and the resulting precipitate was collected by filtration and vacuum dried to obtain powdered polymer CA-2. The weight average molecular weight of CA-2 was 32,100 and the number average molecular weight was 12,500.

[0365] Examples and Comparative Examples In each example, the components listed in the table below were mixed to obtain a resin composition. In each comparative example, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content of each component listed in the table was the amount (parts by mass) listed in the "Amount Added" column of each column in the table. The obtained resin composition and comparative composition were pressure-filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm. In the table, the "Vinylphenyl Group Value in Composition" column lists the molar amount of vinylphenyl groups per 1 g of the total solids content of the composition. In the table, "-" indicates that the composition does not contain the corresponding component.

[0366]

[0367]

[0368] [Resins] SP-1 to SP-17: SP-1 to SP-17 synthesized above SA-1 to SA-8: SA-1 to SA-8 synthesized above CA-1 to CA-2: Synthetic products as above

[0369] [Polymerizable compounds (all trade names)] B-1: SR-209: SR-209 (manufactured by Sartomer Corporation, melting point: 25°C or less) B-2: ADPH: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., melting point: 25°C or less) B-3: tris(2-acryloyloxyethyl) isocyanurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0370] [Solvents] DMSO: dimethyl sulfoxide GBL: γ-butyrolactone NMP: N-methylpyrrolidone γ-valerolactone MDMPA: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd.) In the table, the descriptions "DMSO / GBL" and "DMSO / γ-valerolactone" indicate that DMSO and GBL were mixed in a mixing ratio (mass ratio) of DMSO:GBL = 20:80 and DMSO:γ-valerolactone = 20:80, respectively.

[0371] [Polymerization initiators (all trade names)] C-1: IRGACURE OXE 01 (manufactured by BASF Corporation) C-2: IRGACURE OXE 02 (manufactured by BASF Corporation) C-3: IRGACURE OXE 03 (manufactured by BASF Corporation) C-4: Irgcue 784 (manufactured by BASF Corporation) C-5: CPI-310B (manufactured by San-Apro Co., Ltd.) (sulfonium salt type photoacid generator) C-6: Benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0372] [Migration inhibitors] E-1 to E-7: Compounds having the following structure

[0373] [Metal adhesion improvers] F-1 to F-3: Compounds having the following structures F-4: X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.) (blocked isocyanate silane with protected isocyanate groups) F-5: KBM-51073 (manufactured by Shin-Etsu Chemical Co., Ltd.) (3-acryloxypropyltrimethoxysilane) F-6: X-12-1214A (manufactured by Shin-Etsu Chemical Co., Ltd.) (silane coupling agent containing a benzotriazole group)

[0374] [Polymerization inhibitors] G-1: 1,4-benzoquinone G-2: 4-methoxyphenol G-3: 1,4-dihydroxybenzene G-4: Compound having the following structure G-5: 2-nitroso-1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0375] [Metal complexes and other additives] I-1: TC-750 (manufactured by Matsumoto Fine Chemical) (titanium diisopropoxy bis(ethylacetoacetate)) I-2: TC-401 (manufactured by Matsumoto Fine Chemical) (titanium tetraacetylacetonate) I-3: Compound of the following structure BA-1: The above-mentioned synthetic product BC-1: The above-mentioned synthetic product

[0376] ・J-1: Nymeen (registered trademark) L-202 (manufactured by NOF Corporation) (polyether-based nonionic surfactant) ・J-2: Nonion E-212 (manufactured by NOF Corporation) (polyether-based nonionic surfactant) ・J-3: MEGAFACE EFS-801 (manufactured by Dainippon Ink Co., Ltd.) (PFAS-free nonionic surfactant) ・J-4: Shin-Etsu Silicone KF6028 (manufactured by Shin-Etsu Chemical Co., Ltd.) (PEG-9 polydimethylsiloxyethyl dimethicone)

[0377] <Evaluation> [Method for detecting vinylphenyl group value in composition] 0.1 g of the resin composition prepared in each Example and Comparative Example and 0.9 g of deuterated DMSO were weighed and dissolved in a sample bottle. １ The vinylphenyl content was calculated by H-NMR. １ The number of H-NMR measurements was 640. The measurement results are shown in the column "Vinylphenyl group value in composition" in the table.

[0378] [Evaluation of Resolution] Each of the resin compositions prepared in each Example and Comparative Example was applied in the form of a layer by spin coating onto the surface of a thin copper layer of a resin substrate having a thin copper layer formed on its surface, and dried at 100°C for 5 minutes to form a resin composition layer having a thickness of 5 μm after film formation. Then, a stepper (FPA-3000 i5 (manufactured by Canon Corporation)) was used to apply a 300 mJ / cm ２ The exposure was performed at a wavelength of 365 nm through a hole pattern mask in which a hole pattern with a diameter of 3 to 20 μm was formed in 1 μm increments. The film was then developed for 15 seconds using the developer listed in the "Developer" column of the table, rinsed with PGMEA for 30 seconds, and heated at a temperature increase rate of 10°C / min under a nitrogen atmosphere for the temperature and curing time listed in the "Curing Conditions" column of the table, resulting in a hole pattern with a diameter of 3 to 20 μm. The hole pattern thus formed was evaluated according to the following evaluation criteria. The evaluation results are listed in the "Resolution" column of the table. Images were analyzed using a scanning electron microscope (SEM), and a film residual rate of 1% or less at the bottom of the hole was deemed resolvable. The smaller the diameter of a hole pattern that can be formed, the better the resolution; for example, a rating of A or B is preferred. -Evaluation Criteria- A: Hole patterns with a diameter of up to 3 μm were resolvable. B: A hole pattern with a diameter of 5 μm was resolvable, but a hole pattern with a diameter of 3 μm was not resolvable. C: A hole pattern with a diameter of 7 μm was resolvable, but a hole pattern with a diameter of 5 μm was not resolvable. D: A hole pattern with a diameter of 10 μm was resolvable, but a hole pattern with a diameter of 7 μm was not resolvable. E: A hole pattern with a diameter of 10 μm was not resolvable.

[0379] [Evaluation of Film Remaining Rate After Development] Each of the resin compositions prepared in each Example and Comparative Example was applied in the form of a layer by spin coating to the surface of a thin copper layer of a resin substrate having a thin copper layer formed on the surface thereof, and dried at 100°C for 5 minutes to form a resin composition layer having a film thickness of 10 μm after film formation. The film thickness (film thickness A) before development was measured using a scanning electron microscope (SEM). Subsequently, the above-mentioned coating film was subjected to a spin coating of 300 mJ / cm using a stepper (FPA-3000 i5 (manufactured by Canon Corporation)) with NA = 0.50. ２The film was exposed at a wavelength of 365 nm through a hole pattern mask with a hole pattern of 15 μm diameter formed therein. The film was then developed for 15 seconds with the developer listed in the "Developer" column of the table, rinsed with PGMEA for 30 seconds, and the film thickness after development (film thickness B) was measured using a SEM (scanning electron microscope) and evaluated according to the following evaluation criteria. The evaluation results are listed in the "Residual Film After Development" column of the table. The residual film ratio after development was calculated as film thickness B / film thickness A x 100 (%). The higher the residual film ratio, the better the residual film after development. -Evaluation Criteria- A: The residual film ratio was 90% or more. B: The residual film ratio was 80% or more but less than 90%. C: The residual film ratio was 70% or more but less than 80%. D: The residual film ratio was less than 70%.

[0380] [Evaluation of Coefficient of Linear Thermal Expansion (CTE)] In each Example and Comparative Example, a resin composition or a comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to obtain a uniform resin composition layer with a thickness of approximately 15 µm on the silicon wafer. A stepper (Nikon NSR 2005 i9C) was used to apply 500 mJ / cm to the entire surface of the obtained resin composition layer. ２The resin composition layer (resin layer) after exposure was heated at a heating rate of 10°C / min under a nitrogen atmosphere until the temperature reached the temperature listed in the "Temperature" column under "Curing Conditions" in the table, followed by heating for the time listed in the "Time" column. The cured resin layer (cured film) was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and the cured film was peeled off from the silicon wafer. The peeled cured film was punched out using a punching machine to prepare test specimens with a width of 3 mm and a length of 30 mm. The elongation (displacement) of the test specimens (cured products) was measured while changing the temperature using a Discovery TMA thermomechanical analyzer / thermal expansion coefficient analyzer manufactured by TA Instruments Japan Co., Ltd. The heating and cooling conditions for evaluation were as follows (1) to (4): (1) The temperature was raised from room temperature to 130°C at a heating rate of 5°C / min. (2) The temperature was lowered from 130°C to 10°C at a rate of 5°C / min. (3) The temperature was raised from 10°C to 220°C at a rate of 5°C / min. (4) The sample was allowed to cool naturally to room temperature. The elongation (displacement) of the sample was measured during the temperature increase and decrease processes (1) to (4) above. The thermal expansion coefficient was calculated by dividing the elongation (displacement) of the sample at 25°C and 125°C in process (3) by the temperature. (For example, if the sample length at 25°C was 30 mm and the sample length at 125°C was 30.12 mm, the displacement was 0.4% = 4000 ppm, and the thermal expansion coefficient was calculated as 4000 / (125-25) = 40 ppm / K.) The obtained thermal expansion coefficients were evaluated according to the following evaluation criteria, and the evaluation results are listed in the "CTE" column in the table. (Evaluation Criteria) A: CTE was 40 ppm / K or less. B: CTE was greater than 40 ppm / K and equal to or less than 50 ppm / K. C: CTE was greater than 50 ppm / K and equal to or less than 60 ppm / K. D: CTE was greater than 60 ppm / K.

[0381] [Evaluation of Elongation at Break] In each Example and Comparative Example, a photosensitive resin composition or a comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to obtain a uniform resin composition layer with a thickness of approximately 15 µm on the silicon wafer. A stepper (Nikon NSR 2005 i9C) was used to apply 500 mJ / cm to the entire surface of the obtained resin composition layer. ２ The resin composition layer (resin layer) after the exposure was heated at a rate of 10°C / min under a nitrogen atmosphere until the temperature reached the temperature listed in the "Temperature" column under "Curing Conditions" in the table, followed by heating for the time listed in the "Time" column under "Curing Conditions." The cured resin layer (cured film) was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and the cured film was peeled off from the silicon wafer. The peeled cured film was punched out using a punching machine to prepare test specimens with a width of 3 mm and a length of 30 mm. The resulting test specimens were subjected to measurement of longitudinal elongation at break in accordance with JIS-K6251 using a tensile tester (Tensilon) at a crosshead speed of 300 mm / min under an environment of 25°C and 65% RH (relative humidity). Each measurement was performed five times, and the arithmetic mean value of the elongation at break (elongation at break) was used as an index value. The index values ​​were evaluated according to the following evaluation criteria, and the evaluation results are shown in the "Elongation at break" column in the table. The larger the index value, the better the film strength (elongation at break) of the resulting cured film. (Evaluation criteria) A: The index value was 60% or more. B: The index value was 50% or more and less than 60%. C: The index value was 40% or more and less than 50%. D: The index value was less than 40%.

[0382] Example 101 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 layer was then dried at 100°C for 4 minutes to form a 20 μm-thick resin composition layer, 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 exposure, the substrate was heated at 100°C for 4 minutes. After the heating, the substrate was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern. The substrate was then heated 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 3 hours to form an interlayer insulating film for a rewiring layer. This interlayer insulating film for a rewiring layer had excellent insulating properties. Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for rewiring layers, it was confirmed that they operated without any problems.

Claims

1. A photosensitive resin composition comprising: a polyimide resin having a structure represented by the following formula (A-1); a polymerizable compound; and a photopolymerization initiator, wherein the molar amount of the structure represented by formula (A-1) in 1 g of the resin is 0.2 to 3.0 mmol / g. In formula (A-1), L Ａ１ represents an ester group or an amide group, Cy represents a vinylphenyl group, and * represents a bonding site with another structure.

2. The photosensitive resin composition according to claim 1, wherein the resin contains a repeating unit represented by the following formula (1-1): In formula (1-1), X １ represents an organic group having 4 or more carbon atoms; Y １ represents an organic group having 4 or more carbon atoms; R １ each independently represents a structure represented by formula (A-1), m and n represent an integer of 0 to 4, and either m or n represents an integer of 1 or more.

3. X in formula (1-1) １ and Y １ Each of the structures represented by the following formulas (V-1) to (V-5) includes a structure in which two or more hydrogen atoms have been removed. In formula (V-2), R Ｘ１ Each of R independently represents 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 linked to form a ring structure.

4. The photosensitive resin composition according to claim 1, wherein the molar ratio of the structure represented by formula (A-1) to the amount of imide structures in the resin is 1 to 100%.

5. A photosensitive resin composition comprising: a polyimide precursor or a polybenzoxazole precursor, the resin having a structure represented by the following formula (A-1); a polymerizable compound; and a photopolymerization initiator, wherein the molar amount of the structure represented by formula (A-1) in 1 g of the resin is 0.2 to 3.0 mmol / g. In formula (A-1), L Ａ１ represents an ester group or an amide group, Cy represents a vinylphenyl group, and * represents a bonding site with another structure.

6. The photosensitive resin composition according to claim 5, wherein the resin contains a repeating unit represented by the following formula (2-1): In formula (2-1), X ２ represents an organic group having 4 or more carbon atoms; Y ２ represents an organic group having 4 or more carbon atoms; V １ and V ２ each independently represents a monovalent organic group; R ３ each independently represents a structure represented by formula (A-1), m and n represent an integer of 0 to 4, and either m or n represents an integer of 1 or more.

7. X in formula (1-1) １ and Y １ Each of the structures represented by the following formulas (V-1) to (V-5) includes a structure in which two or more hydrogen atoms have been removed. In formula (V-2), R Ｘ１ Each of R independently represents 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 linked to form a ring structure.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the resin has a polymerizable group value of 0.2 to 5.0 mmol / g.

9. A photosensitive resin composition according to any one of claims 1 to 7, comprising as the resins: Resin P-1 having an amino group which may be protected; and Resin P-2 having Structure A in which two groups selected from the group consisting of a carboxylate group and a carboxy group which may be protected are linked by a linking group having a linking chain length of 2 to 4.

10. The resin P-1 has the following formula (R Ｔ The photosensitive resin composition according to claim 9 , wherein the photosensitive resin composition has a group represented by the formula: Formula (R Ｔ ) Medium, T １ represents a monovalent organic group.

11. The photosensitive resin composition according to claim 9, wherein the resin P-2 contains, as the structure A, a group represented by any one of the following formulas (S-1) to (S-4). In formulas (S-1) to (S-4), R Ｓ１ -OH, -O － Or -O-R Ｓ２ represents R Ｓ２ represents a protecting group, Cy represents an aliphatic ring structure, L １ represents a single bond or an aliphatic group having a linking chain length of 1 or 2, n represents an integer of 1 or 2, and * represents a bonding site with another structure.

12. A photosensitive resin composition according to any one of claims 1 to 7, in which, when a film-like cured product having a thickness of 10 μm is formed, the transmittance of the cured product at a wavelength of 365 nm is 10% or more.

13. The photosensitive resin composition according to any one of claims 1 to 7, wherein the polymerizable compound has a melting point of 25°C or lower.

14. The photosensitive resin composition according to any one of claims 1 to 7, further comprising a solvent having a boiling point of 50°C to 300°C at 1 atmospheric pressure.

15. The photosensitive resin composition according to any one of claims 1 to 7, comprising an azole compound and a silane coupling agent.

16. The photosensitive resin composition according to any one of claims 1 to 7, which contains a solvent having a boiling point of 100 to 260°C at 1 atmospheric pressure.

17. The photosensitive resin composition according to claim 16, wherein the content of the solvent having a boiling point of 100 to 260° C. is 40 mass % or more based on the total mass of the composition.

18. The photosensitive resin composition according to claim 16, which contains two or more solvents having a boiling point of 100 to 260°C.

19. The photosensitive resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulating film for a rewiring layer.

20. A cured product obtained by curing the resin composition according to any one of claims 1 to 7.

21. A laminate comprising two or more layers of the cured product according to claim 20, and including a metal layer between any two of the layers of the cured product.

22. 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 7 onto a substrate to form a film.

23. The method for producing a cured product according to claim 22, 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.

24. A method for producing a cured product according to claim 22, comprising a heating step of heating the film at 50 to 450°C.

25. A method for producing a laminate, comprising the method for producing the cured product according to claim 22.

26. A method for producing a semiconductor device, comprising the method for producing the cured product according to claim 22.

27. A semiconductor device comprising the cured product according to claim 20.

28. A polyimide resin having a structure represented by the following formula (A-1) and including a repeating unit represented by the following formula (1-1), wherein the molar amount of the structure represented by formula (A-1) per 1 g of the resin is 0.2 to 3.0 mmol / g. In formula (A-1), L Ａ１ represents an ester group or an amide group, Cy represents a vinylphenyl group, and * represents a bonding site with another structure. In formula (1-1), X １ represents an organic group having 4 or more carbon atoms; Y １ represents an organic group having 4 or more carbon atoms; R １ each independently represents a structure represented by formula (A-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more.

29. X in formula (1-1) １ and Y １ Each of the structures represented by the following formulas (V-1) to (V-5) has two or more hydrogen atoms removed from it. In formula (V-2), R Ｘ１ Each of R independently represents 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 linked to form a ring structure.

30. The resin according to claim 28, wherein the ratio of the molar amount of the structure represented by formula (A-1) to the amount of the imide structure is 1 to 100%.

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