Resin composition, cured product, laminated body, method for producing cured product, method for producing laminated body, method for producing semiconductor device, and semiconductor device

Abstract

The present invention provides a resin composition comprising: a resin A that is a polyimide and that contains a structure represented by formula (A-1) in an amount of 0.20-5 mmol / g with respect to the mass of the resin A; a polymerization initiator; and a polymerizable compound. The present invention also provides a cured product obtained by curing the composition, a laminated body comprising the cured product, a method for producing the cured product, a method for producing the laminated body, a method for producing a semiconductor device which includes the method for producing the cured product, and a semiconductor device comprising the cured product. In formula (A-1), LA1 represents a single bond or an m+1-valent linking group, each RR1 independently represents a hydrogen atom or an organic group, two RR1 may be coupled to each other, m represents an integer of 1 or more, and * represents a site of bonding with another atom.

Description

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

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

[0002] In recent years, resin materials produced from resin compositions containing resins have been utilized in various fields. For example, the applications of the resin materials are not particularly limited, but examples include insulating films, sealing materials, and protective films for semiconductor devices used for packaging. They are also used as base films and coverlays for flexible substrates.

[0003] The resin composition can be applied by known coating methods, etc., and therefore can be said to have excellent adaptability in manufacturing, for example, a high degree of freedom in designing the shape, size, application position, etc. of the resin composition when applied. From the viewpoint of such excellent adaptability in manufacturing, industrial application development of the above-mentioned resin composition is expected to become increasingly widespread.

[0004] For example, Patent Document 1 describes a photosensitive resin composition containing a bismaleimide compound (I) having a cyclic imide bond, which is obtained by reacting a diamine (A) derived from a dimer acid, a tetracarboxylic dianhydride (C) having an alicyclic structure, and maleic anhydride, and a photopolymerization initiator (II), in which the photopolymerization initiator (II) is a compound having an oxime structure or a thioxanthone structure.

[0005] Japanese Patent Application Laid-Open No. 2022-115907

[0006] It is required to reduce the dielectric loss tangent of a cured product obtained by curing a resin composition from the viewpoint of suppressing transmission loss and the like.

[0007] An object of the present invention is to provide a resin composition that can give a cured product having a low dielectric loss tangent, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device that includes the method for producing the cured product, and a semiconductor device that includes the cured product.

[0008] Representative embodiments of the present invention are shown below. <1> A resin composition comprising: Resin A, which is a polyimide and contains a structure represented by the following formula (A-1) in an amount of 0.20 to 5 mmol / g relative to the mass of Resin A; a polymerization initiator; and a polymerizable compound. In formula (A-1), L Ａ１ represents a single bond or an (m+1)-valent linking group, R Ｒ１ each independently represents a hydrogen atom or an organic group, and two R Ｒ１ may be linked together, m represents an integer of 1 or more, and * represents a bonding site with another atom. <2> The resin composition according to <1>, wherein the structure represented by formula (A-1) is contained in a side chain of resin A. <3> The resin composition according to <1> or <2>, wherein resin A has a radical polymerizable group value of 0.20 to 5 mmol / g. <4> L in formula (A-1) Ａ１ <5> The resin composition according to any one of <1> to <4>, further comprising a resin A2 that is a polyimide precursor. <6> The resin composition according to any one of <1> to <3>, wherein the resin A comprises 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 following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more. In formula (R-1), L １ represents a 2+1-valent linking group, Z １ represents an aromatic group, a cyclic aliphatic group, or a linear or branched saturated aliphatic hydrocarbon group; R Ｒ１each independently represents a hydrogen atom or an organic group, and two R Ｒ１ may be linked, and a1 is 1 or more and Z １ a2 represents an integer of 1 or more, * represents X in formula (1-1). １ or Y １ <7> X in formula (1-1) represents a bonding site with １ and Y １ Each of the above formulas (V-1) to (V-4) includes a structure in which two or more hydrogen atoms have been removed from the structure represented by the following formula (V-1) to formula (V-4): In formula (V-2), R Ｘ１ are each independently a hydrogen atom, an alkyl group, or a halogenated alkyl group. Ｘ２ and R Ｘ３ each independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ may be bonded to form a ring structure. <8> The resin composition according to <6>, which contains a repeating unit represented by formula (1-1) and has at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms. <9> A resin composition comprising: a resin B containing 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 Y １ is bonded to a nitrogen atom outside the repeating unit without a linking group, and R １ each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more. In formula (R-1), L １ represents a 2+1-valent linking group, Z １ represents an aromatic group, a cyclic aliphatic group, or a linear or branched saturated aliphatic hydrocarbon group; R Ｒ１each independently represents a hydrogen atom or an organic group, and two R Ｒ１ may be linked, and a1 is 1 or more and Z １ a2 represents an integer of 1 or more, * represents X in formula (1-1). １ or Y １ represents the binding site with 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, and R ２ each independently represents a group represented by the following formula (R-2), and n represents an integer of 1 or more. ３ represents an organic group having 4 or more carbon atoms, and Y ３ represents an organic group having 4 or more carbon atoms, A ３ and A ４ are each independently an oxygen atom or —NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group, R ３ and R ４ each independently represents a hydrogen atom or a monovalent organic group; R ２ each independently represents a group represented by the following formula (R-2), and n represents an integer of 0 or more. In formula (R-2), L ２ represents a b2+1-valent linking group, Z ２ represents a b1+1 valent organic group, A ２ represents a methacryloxy group, an acryloxy group, a methacrylamide group, an acrylamide group, a vinyl group, a styryl group, an allyl group, or a vinyl ether group; b1 is 1 or more and Z ２ represents an integer equal to or less than the maximum number of substituents, b2 represents an integer of 1 or more, * represents Y in formula (2-1), ２ Or Y in formula (3-1) ３ <10> In formula (3-1), R ３ and R ４ is a group having an ethylenically unsaturated bond, and X ３ <11> The resin composition according to <9>, wherein X in formula (1-1) contains a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4). １ and Y１ Each of the following formulas (V-1) to (V-4) includes a structure in which two or more hydrogen atoms have been removed from the structure: 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 bond to form a ring structure. <12> The resin composition according to any one of <9> to <11>, wherein the resin B has at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted by a linear aliphatic hydrocarbon group having 4 or more carbon atoms. <13> The resin composition according to any one of <1> to <12>, wherein, when a film-like cured product having a film thickness of 10 μm is formed using the resin composition, the cured product has a light transmittance of 15% or more at a wavelength of 365 nm. <14> The resin composition according to any one of <1> to <13>, wherein the melting point of the polymerizable compound is 25° C. or lower. <15> The resin composition according to any one of <1> to <14>, wherein the ClogP of the polymerizable compound is 3 or higher. <16> The resin composition according to any one of <1> to <15>, wherein the resin composition contains an azole compound and a silane coupling agent. <17> The resin composition according to any one of <1> to <16>, which is used for forming an interlayer insulating film for a redistribution layer. <18> A cured product obtained by curing the resin composition according to any one of <1> to <17>. <19> A laminate comprising two or more layers made of the cured product according to <18>, and a metal layer between any two of the layers made of the cured products. <20> A method for producing a cured product, comprising a film formation step of applying the resin composition according to any one of <1> to <12> onto a substrate to form a film. <21> A method for producing the cured product according to <20>, 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. <22> A method for producing the cured product according to <20> or <21>, comprising a heating step of heating the film at 50 to 450°C. <23> A method for producing a laminate, comprising the method for producing the cured product according to <20>. <24> A method for producing a semiconductor device, comprising the method for producing the cured product according to <20>. <25> A semiconductor device comprising the cured product according to <18>.

[0009] According to the present invention, there are provided a resin composition that can give a cured product with a low dielectric tangent, a cured product obtained by curing the resin composition, a laminate that includes 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.

[0010] FIG. 1 is a schematic cross-sectional view of a state in which a cured product is formed on a silicon wafer on which copper wiring has been formed.

[0011] 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 THF (tetrahydrofuran) as the eluent. However, when THF is not suitable as the eluent, for example, due to low solubility, NMP (N-methyl-2-pyrrolidone) 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.

[0012] (Resin Composition) A resin composition according to a first aspect of the present invention (hereinafter also simply referred to as the "first resin composition") comprises a resin A which is a polyimide and contains a structure represented by formula (A-1) in an amount of 0.20 to 5 mmol / g relative to the mass of resin A, a polymerization initiator, and a polymerizable compound. A resin composition according to a second aspect of the present invention (hereinafter also simply referred to as the "second resin composition") comprises a resin B which contains a repeating unit represented by formula (1-1), a resin C which contains at least one of repeating units represented by formula (2-1) and formula (3-1), a polymerization initiator, and a polymerizable compound. Hereinafter, resin A and resin B will be collectively referred to as the "specific resin".

[0013] 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.

[0014] The resin composition of the present invention provides a cured product with a low dielectric loss tangent. The mechanism by which this effect is achieved is unknown, but is presumed to be as follows.

[0015] Resin A, which is a polyimide in a first embodiment of the resin composition of the present invention, contains a group represented by formula (A-1) containing a maleimide group in an amount of 0.20 to 5 mmol / g relative to the mass of Resin A. Resin A in the first embodiment of the resin composition of the present invention contains a repeating unit represented by formula (1-1). Conventionally, cured products with excellent physical properties, such as chemical resistance, have been obtained by using a resin composition containing a resin having a polymerizable group such as a (meth)acryloxy group, a polymerizable compound, and a polymerization initiator as a polyimide-containing resin composition. Here, for example, the carbonyl group moiety contained in the (meth)acryloxy group is freely rotatable, which may result in a high degree of freedom of structural movement in the resulting cured product, resulting in an increased dielectric loss tangent. In contrast, maleimide groups are thought to have a reduced dielectric loss tangent because the carbonyl group is fixed within the ring structure, making them less prone to free rotation and more likely to be fixed in structure. Furthermore, since maleimide groups react with various structures in the composition, such as through addition reactions with phenolic hydroxy groups, in addition to radical polymerization, it is believed that crosslinks are formed between the resin and various components or various sites in the resin in the resulting cured product. That is, it is believed that a strong crosslinked network is formed in the cured product. As a result, it is believed that effects such as improved curability and chemical resistance upon exposure of the resulting cured product can also be obtained. In addition, since polymerization in maleimide groups is less susceptible to depolymerization due to heat, etc., compared to polymerization in (meth)acrylates, it is believed that the chemical resistance and adhesion of the cured product are less likely to decrease, for example, when exposed to high temperature or high humidity conditions, or even after a long period of time has passed. Furthermore, when a film made of the resin composition of the present invention is exposed to light and developed to form a pattern, the presence of maleimide groups in the resin is believed to improve the removability of non-image areas with a developer containing an organic solvent, and also improve resolution.

[0016] However, Patent Document 1 does not describe a resin composition containing a specific resin.

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

[0018] <Specific Resin> [Resin A] The first resin composition of the present invention contains Resin A, which is a polyimide and contains a structure represented by the following formula (A-1) in an amount of 0.20 to 5 mmol / g relative to the mass of Resin A: In formula (A-1), L Ａ１ represents a single bond or an (m+1)-valent linking group, R Ｒ１ each independently represents a hydrogen atom or an organic group, and two R Ｒ１ may be linked, m represents an integer of 1 or more, and * represents a bonding site to another atom.

[0019] In the present invention, a resin having an imidization rate of less than 70% as measured by the following method is referred to as a polyimide precursor, and a resin containing an imide structure in a repeating unit and having an imidization rate of 70% or more is referred to as a polyimide. In the present invention, the imide structure 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. In the present invention, the polyimide 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 structure in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain. In the present invention, the term "main chain" refers to the relatively longest bonding chain in the resin molecule, and the term "side chain" refers to other bonding chains.

[0020] The imidization rate of a resin is measured by the following method: The infrared absorption spectrum of the resin is measured, and the absorption peak at 1377 cm －１ Next, the specific 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 specific resin can be calculated based on the following formula: Imidization rate (%) = (peak intensity P1 / peak intensity P2) x 100

[0021] From the viewpoints of the film strength, insulating properties, flatness, etc. of the resulting organic film, the imidization rate of the specific resin is preferably 75% or more, more preferably 80% or more, and even more preferably 90% or more. The upper limit of the imidization rate is not particularly limited, and it is sufficient as long as it is 100% or less. Furthermore, from the viewpoint of reducing the dielectric loss tangent, the content of the imide structure in the 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.

[0022] -Formula (A-1)- The structure represented by formula (A-1) is preferably contained in a side chain of resin A. In addition, * in formula (A-1) is preferably a bonding site with an atom contained in the main chain of resin A. In addition, R Ｒ１ At least one of the above may have a structure containing a main chain of a resin.

[0023] In formula (A-1), L Ａ１ preferably contains an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms. The aromatic group or the aliphatic saturated hydrocarbon group having 4 or more carbon atoms is preferably bonded to the maleimide group (i.e., the nitrogen atom in Formula A-1) by a single bond without a linking group. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably an aromatic hydrocarbon group having 6 carbon atoms. Examples of heteroatoms in the aromatic heterocyclic group include an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms in the aromatic heterocyclic group is preferably 1 or 2. Furthermore, the aromatic heterocyclic group is preferably a 5- or 6-membered ring containing the above heteroatom. Furthermore, the aromatic heterocyclic group may be condensed with another aromatic heterocyclic group or another aromatic hydrocarbon ring group. The aliphatic saturated hydrocarbon group having 4 or more carbon atoms may be linear, branched, cyclic, or a structure represented by a combination thereof. The aliphatic saturated hydrocarbon group having 4 or more carbon atoms preferably has 4 to 20 carbon atoms, and more preferably has 5 to 10 carbon atoms.

[0024] Also, L Ａ１ It is also preferable that the formula is the following formula (A-1-1) or formula (A-2-2). In formula (A-1-1), Z １ is -O- or -NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group, R Ａ１ represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms, m represents an integer of 1 or more, * has the same meaning as * in formula (A-1), and # represents the bonding site with the nitrogen atom in formula (A-1). ２ is -O- or -NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group; R represents a hydrogen atom or a monovalent organic group; Ａ２ represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms, m represents an integer of 1 or more, * has the same meaning as * in formula (A-1), and # represents the bonding site with the nitrogen atom in formula (A-1).

[0025] In formula (A-1-1), Z １ is preferably —O—. 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. Ａ１ represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms, and preferred embodiments of these groups are as described above. In formula (A-1-1), m has the same meaning as m in formula (A-1), and preferred embodiments are also the same.

[0026] In formula (A-1-2), Z ２ is preferably —O—. Ｎ In formula (A-1-2), R Ａ２ A preferred embodiment of the formula (A-1-1) is R Ａ１ In formula (A-1-2), m has the same meaning as m in formula (A-1), and preferred embodiments are also the same.

[0027] R Ａ１ and R Ａ２Preferred embodiments of the formula (A-1) are shown below, but the present invention is not limited to these. In the formulas below, n each independently represents an integer of 0 or more, * has the same meaning as * in formula (A-1), and # represents the bonding site with the nitrogen atom in formula (A-1). Here, n in the formulas below is preferably an integer of 0 to 20, and more preferably an integer of 0 to 6.

[0028] In formula (A-1), R Ｒ１ are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. Ｒ１ Examples of the ring structure formed by linking include a cyclohexene ring.

[0029] In formula (A-1), m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably an integer of 1 to 3, and particularly preferably 1 or 2. An embodiment in which m is 1 is also one of the preferred embodiments of the present invention.

[0030] Resin A contains the structure represented by formula (A-1) in an amount of 0.20 to 5 mmol / g, preferably 0.30 to 4 mmol / g, and more preferably 0.50 to 3 mmol / g, relative to the mass of Resin A. The content of the structure represented by formula (A-1) in Resin A is １ This can be confirmed by H-NMR. Specifically, the polymer is dissolved in deuterated DMSO, １ The radical polymerizable group value of resin A (the molar amount of radical polymerizable groups relative to the mass of resin A) is preferably 0.20 to 5 mmol / g, more preferably 0.30 to 4 mmol / g, and even more preferably 0.50 to 3 mmol / g. The radical polymerizable group value of resin A is １This can be confirmed by H-NMR. The ratio of the content of the structure represented by formula (A-1) in Resin A to the radical polymerizable group value in Resin A is preferably 50% or more, more preferably 70% or more, and even more preferably 90% or more. There is no particular upper limit to this ratio, as long as it is 100% or less.

[0031] Resin A preferably 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 Y １ is bonded to a nitrogen atom outside the repeating unit without a linking group, and R １ each independently represents a structure represented by the following formula (R-1), m represents an integer of 0 to 4, and n represents an integer of 1 or more. In formula (R-1), L １ represents a 2+1-valent linking group, Z １ represents an aromatic group, a cyclic aliphatic group, or a linear or branched saturated aliphatic hydrocarbon group; R Ｒ１ each independently represents a hydrogen atom or an organic group, and two R Ｒ１ may be linked, and a1 is 1 or more and Z １ a2 represents an integer of 1 or more, * represents X in formula (1-1). １ or Y １ represents the binding site with

[0032] -R １ -R １ each independently represents a structure represented by formula (R-1).

[0033] In formula (R-1), L １ is preferably a group represented by the following formula (L-1). In formula (L-1), Z Ｌ１ -O-, -NR Ｎ -, -C(=O)O- or -C(=O)NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group, and when a2 is 1, L Ｘrepresents a single bond or a hydrocarbon group, and when a2 is 2 or more, L Ｘ represents a hydrocarbon group, Z Ｌ２ is a single bond or —O—, —NR Ｎ -, -C(=O)O- or -C(=O)NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group, * represents X in formula (1-1). １ or Y １ represents a bonding site with Z in formula (R-1), １ represents the binding site with

[0034] In formula (L-1), Z Ｌ１ is preferably —O— or —C(═O)O—. Ｌ１ Ga-NR Ｎ - or -C(=O)NR Ｎ R when - Ｎ In formula (L-1), L ｘ is preferably an aromatic hydrocarbon group, an aliphatic saturated hydrocarbon group, or a group represented by a combination thereof. As the aromatic hydrocarbon group, a group in which two or more hydrogen atoms have been removed from a benzene ring is preferred. As the aliphatic saturated hydrocarbon group, an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms is preferred, and an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms is more preferred. In formula (L-1), Z Ｌ２ is preferably —O— or —C(═O)O—. Ｌ２ Ga-NR Ｎ --or --C(=O)NR Ｎ R when - Ｎ The preferred embodiments of a2 in formula (L-1) are the same as the preferred embodiments of a2 in formula (R-1).

[0035] In formula (R-1), Z １ is preferably an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms. Ａ１ The preferred embodiments of these groups are the same as those in the above.

[0036] In formula (R-1), R Ｒ１ A preferred embodiment of the formula (A-1) is R Ｒ１This is the same as the preferred embodiment of the above.

[0037] In formula (R-1), a1 is preferably an integer of 1 to 4, and more preferably an integer of 1 or 2. An embodiment in which a1 is 1 is also one of the preferred embodiments of the present invention. In formula (R-1), a2 represents an integer of 1 or more, and is preferably 1 or 2, and more preferably 1.

[0038] -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-4). 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-4), 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-4), effects such as suppression of development residues, lowering the dielectric constant of the cured product, and reducing the thermal expansion coefficient are also 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 be bonded to form a ring structure.

[0039] 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 Ｘ３are 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.

[0040] 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 bonding sites 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. Furthermore, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups.

[0041] 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 may be further substituted with known substituents such as hydrocarbon groups.

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

[0043] 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, * represents X in formula (1-1). １ represents the bonding sites with the four carbonyl groups to which n is bonded, and n1 represents an integer of 0 to 5. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. However, it is also preferred that none of the hydrogen atoms in the structure represented by (V-4-1) are substituted.

[0044] Other, X １ may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic acid dianhydride described in paragraphs 0055 to 0057 of JP-A No. 2023-003421.

[0045] 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. Ｎis 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.

[0046] 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 ３ represents a divalent linking group, and * represents a bonding site to another structure.

[0047] 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.

[0048] Also, X ２ is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. The halogenation is preferably chlorination. In the present invention, a compound having three carboxy groups is 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.

[0049] X ２ It is preferable that X does not contain an imide structure in its structure. ２It 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.

[0050] 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.

[0051] 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(CF ３ ) 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).

[0052] In formula (X-2), L ３is 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) 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.

[0053] 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 １It 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.

[0054] -Y １ - Y １ The 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-4). 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-4), the chemical resistance and flatness of the cured product are improved.

[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-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 to the two nitrogen atoms to which n is bonded, and n1 represents an integer of 1 to 5. Furthermore, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups.

[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-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 may be further substituted with known substituents such as hydrocarbon groups.

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

[0058] 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 to 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 may be further substituted with known substituents such as hydrocarbon groups.

[0059] 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. １It 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.

[0060] 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-4). Preferred aspects of these groups are as described above.

[0061] 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 2.

[0062] The second resin composition includes a resin B containing a repeating unit represented by formula (1-1). Preferred aspects of the resin B are the same as the preferred aspects of the resin A, except that the resin B must contain a repeating unit represented by formula (1-1).

[0063] Resin A preferably contains a repeating unit represented by formula (1-1) and has at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with linear aliphatic hydrocarbon groups having 4 or more carbon atoms. Resin B preferably contains at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with linear aliphatic hydrocarbon groups having 4 or more carbon atoms. Hereinafter, at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with linear aliphatic hydrocarbon groups having 4 or more carbon atoms will also be referred to as a "specific substituent," and a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms will also be referred to as specific substituent A, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with linear aliphatic hydrocarbon groups having 4 or more carbon atoms will also be referred to as specific substituent B. Furthermore, for example, when a specific resin has a substituent X that is a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with linear aliphatic hydrocarbon groups having 6 or more carbon atoms, the linear aliphatic hydrocarbon group having 6 or more carbon atoms of this substituent X can be said to correspond to specific substituent A, and the substituents X as a whole can be said to correspond to specific substituent B.

[0064] -Specific Substituent A- From the viewpoint of resolution, the specific resin preferably has a group corresponding to the specific substituent A. The specific resin preferably has, as the specific substituent A, a linear or branched alkyl group having 6 or more carbon atoms. The specific resin preferably has, as the specific substituent A, a linear monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and more preferably a linear alkyl group having 6 or more carbon atoms. The hydrogen atoms in the specific substituent A are preferably unsubstituted or substituted with a halogen atom. The halogen atom is preferably a fluorine atom. An embodiment in which the hydrogen atoms in the specific substituent A are unsubstituted is also one of the preferred embodiments of the present invention. The number of carbon atoms in the specific substituent A is preferably 6 to 30, and more preferably 6 to 20.

[0065] -Specific Substituent B- The cyclic aliphatic hydrocarbon group in specific substituent B is preferably a cyclic aliphatic saturated hydrocarbon group. The cyclic aliphatic hydrocarbon group in specific substituent B is preferably a 5- to 10-membered ring, more preferably a 5- to 8-membered ring, and even more preferably a 6-membered ring. The cyclic aliphatic hydrocarbon group in specific substituent B may be condensed with another ring structure. The other ring structure is preferably a hydrocarbon ring structure, and more preferably an aliphatic hydrocarbon ring structure. The linear aliphatic hydrocarbon group having 4 or more carbon atoms in specific substituent B is preferably a linear alkyl group having 4 or more carbon atoms. The number of carbon atoms in the linear aliphatic hydrocarbon group having 4 or more carbon atoms in specific substituent B is preferably 4 to 30, more preferably 4 to 10, and even more preferably 4 to 8.

[0066] -Content of specific substituent- The molar amount of the specific substituent relative to the number average molecular weight of the specific resin is preferably 0.01 to 10 mmol / g, more preferably 0.1 to 5 mmol / g, and even more preferably 0.1 to 2 mmol / g.

[0067] When the specific resin has a specific substituent, the resin has a group having the specific substituent in the above-mentioned X １ or Y １ Alternatively, the specific resin may contain the group as a substituent, or may contain the group at the end of the specific resin. Specifically, the specific resin preferably has a structure represented by any one of the following formulas (TA-1) to (TA-3). In formula (TA-1), X ３１ represents a tetravalent organic group, Y ３１ represents a divalent organic group, R ３１ represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms; R ３１ is a group not containing an imide structure, and * represents a bonding site with another structure. ３１ represents a tetravalent organic group, Y ３１represents a divalent organic group, R ３２ represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms; R ３２ is a group not containing an imide structure, and * represents a bonding site with another structure. ３１ represents a tetravalent organic group, Y ３１ represents a divalent organic group, R ３３ and R ３４ each independently represents —OH or a monovalent organic group, and R ３３ and R ３４ at least one of R is a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms; ３３ and R ３４ is a group not containing an imide structure, and * indicates a bonding site with another structure.

[0068] The specific resin preferably has a structure represented by any one of formulas (TA-1) to (TA-3) at the main chain terminal. The specific resin also preferably has a structure represented by formula (TA-1).

[0069] In formulas (TA-1) to (TA-3), X ３１ and Y ３１ A preferred embodiment of the formula is X １ and m R １ and a group consisting of Y １ and n R １ In formula (TA-1), R ３１ is preferably a group represented by the following formula (R-31). In formula (R-31), when a31 is 1, L ３１ represents a single bond or a31+1-valent linking group, and when a31 is 2 or more, L ３１ represents a monovalent linking group; Z ３１is a single bond, —O— or —NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group; １ represents a group having at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a31 represents an integer of 1 or greater.

[0070] In formula (R-31), when a31 is 1, L ３１ In formula (R-31), L is preferably a single bond. ３１ is a 1-valent linking group, L31 is a hydrocarbon group, or a hydrocarbon group and —O—, —C(═O)—, or —NR Ｎ - is preferably a group represented by a combination of at least one selected from the group consisting of R Ｎ In formula (R-31), Z ３１ is preferably a single bond. １ A preferred embodiment of the formula (R-1) is １ In formula (R-31), a31 is preferably an integer of 1 to 4, and more preferably 1 or 2. An embodiment in which a31 is 1 is also one of the preferred embodiments of the present invention.

[0071] In formula (TA-2), R ３２ is preferably a group represented by the following formula (R-32). In formula (R-32), R Ｎ represents a hydrogen atom or a monovalent organic group; when a32 is 1, L ３２ represents a single bond or a32+1-valent linking group, and when a32 is 2 or more, L ３２ represents a monovalent linking group; Z ３２ is a single bond, —O— or —NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group; １represents a group having at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a32 represents an integer of 1 or greater.

[0072] In formula (R-32), R Ｎ In formula (R-32), L ３２ , Z ３２ , A １ and a32 Preferred embodiments are L in the above formula (R-31). ３１ , Z ３１ , A １ and the preferred embodiments of a31 are the same as those of a31.

[0073] In formula (TA-3), R ３３ and R ３４ At least one of the above is preferably a group represented by the following formula (R-33). In formula (R-33), Z ３３ is -O- or -NR Ｎ -, and when a33 is 1, L ３３ represents a single bond or a33+1-valent linking group, and when a33 is 2 or more, L ３３ represents a monovalent linking group; Z ３４ is a single bond, —O— or —NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group; １ represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a33 represents an integer of 1 or more. ３３ Ha-NR Ｎ - is preferred. Ｎ In formula (R-33), L ３３ , Z ３４ , A １ and a33 is preferably L in the above formula (R-31). ３１ , Z ３１, A １ and the preferred embodiments of a31 are the same as those of a31.

[0074] In formula (TA-3), R ３３ and R ３４ One of the groups may be —OH or —OC ２ H ５ It may also be an alkoxy group that does not contain specific substituents such as:

[0075] The specific resin may contain a repeating unit represented by formula (4). A repeating unit that falls under the repeating unit represented by formula (1-1) does not fall under 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.

[0076] R １３１ represents a divalent organic group. As the divalent organic group, R １３１ Examples of the alkyl group include the groups described in paragraphs 0042 to 0053 of JP-A No. 2023-003421, the disclosures of which are incorporated herein by reference.

[0077] R １３２ represents a tetravalent organic group. １３２ Examples of such compounds include those described in paragraphs 0055 to 0057 of JP-A No. 2023-003421, the disclosures of which are incorporated herein by reference.

[0078] The content of the repeating unit represented by formula (1-1) relative to the total mass of the specific resin is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit of this content is not particularly limited and may be 100% by mass. Furthermore, when the specific resin is a polyimide, 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 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 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 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.

[0079] [Dissolution Rate] The resin composition of the present invention preferably contains, as the specific resin, a resin having a dissolution rate in cyclopentanone of 0.01 to 0.2 μm / sec when the resin film has a thickness of 10 μm. The lower limit of the dissolution rate is preferably 0.02 μm / sec or more, and more preferably 0.05 μm / sec or more. The upper limit of the dissolution rate is preferably 0.2 μm / sec or less, and more preferably 0.15 μm / sec or less.

[0080] The film used to measure the dissolution rate of the specific resin can be obtained, for example, by preparing a solution of the specific resin in a solvent, applying the solution to a substrate such as a silicon wafer, and drying it as needed. When drying is performed, the film thickness after drying is 10 μm.

[0081] γ-Butyrolactone can be used as the solvent for dissolving the specific resin used in preparing the solution. If the specific resin is insoluble in γ-butyrolactone, or if the process is difficult to carry out, the solvent may be changed to a solvent that dissolves the specific resin, such as N-methyl-2-pyrrolidone or dimethyl sulfoxide. The content of the specific resin in the solution can be 30% by mass relative to the total mass of the solvent. However, if it is difficult to form a 10 μm film at this content, or if the solubility of the specific resin is low and the film cannot be prepared, the content may be appropriately set between 10 and 60% by mass, for example. Furthermore, if a 10 μm film cannot be obtained, the specific resin content can be determined by measuring a film thickness that can be formed and converting it to a film thickness of 10 μm.

[0082] The substrate may be a silicon wafer. If it is difficult to form a film with a thickness of 10 μm on a silicon wafer, other substrates having different properties such as surface wettability may be used.

[0083] The method for applying the resin composition to the substrate is not particularly limited as long as it can be a method that results in a film thickness of 10 μm, and spin coating can be used. If it is difficult to form a film with a thickness of 10 μm by spin coating, a known method may be appropriately selected from dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, slit coating, inkjet method, etc.

[0084] Drying is preferably carried out until the amount of solvent in the film is 0.1% by mass or less. Drying conditions are not particularly limited, but drying by heating can be performed. Furthermore, if sufficient drying is difficult to achieve by heating alone, further reduction in pressure may be performed. Drying can be carried out in the atmosphere. However, if the resin composition contains components that are easily denatured by oxygen, drying can also be carried out under inert gas such as nitrogen or under vacuum. Drying means are not particularly limited, but examples include a hot plate. However, if the above-mentioned reduction in pressure or inert gas replacement is required, an oven with a reduction in pressure function or an oven with a gas replacement function can also be used. When drying by heating, the heating temperature can be, for example, 110°C. However, if drying at 110°C is difficult, the drying temperature may be appropriately changed between 70°C and 130°C, preferably between 90°C and 120°C, depending on the type of solvent contained in the resin composition. When drying by heating, the drying time (time exposed to the above heating temperature) can be, for example, 5 minutes. However, if drying within 5 minutes is difficult, the drying time may be appropriately changed between 30 seconds and 20 minutes, preferably between 1 minute and 10 minutes, depending on the type of solvent contained in the resin composition, etc. When drying is performed by heating, the temperature rise rate during heating is not particularly limited and can be, for example, 5°C / min. If drying at the above temperature rise rate is difficult, the temperature rise rate may be appropriately changed between 1 and 12°C / min, or between 2 and 10°C / min, depending on the type of solvent contained in the resin composition, etc.

[0085] The dissolution rate of a film in cyclopentanone can be calculated by immersing a silicon wafer on which a film has been formed in cyclopentanone for 15 seconds and measuring the film thickness before and after immersion using an ellipsometer. The film is immersed in cyclopentanone without being subjected to any heating other than the drying process. The amount of cyclopentanone used for immersion is preferably 30 times the volume of the film. The temperature of cyclopentanone, the film, and the silicon wafer during immersion is 23°C. If the film is completely dissolved or if the film thickness does not change at all, the immersion time can be appropriately changed to calculate the dissolution rate.

[0086] [Transmittance] 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 15% 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%. The cured product can be obtained, for example, by applying the resin composition of the present invention to a substrate such as a silicon wafer and then drying it, and then transmitting a light transmittance of 500 mJ / cm ２ The film can be obtained by exposing the entire surface to i-rays at an exposure energy of 1000 kJ / min, then heating at 230°C for 180 minutes in a nitrogen atmosphere at a temperature increase rate of 10°C / min. The transmittance can be measured using a spectrophotometer. The substrate, the method of applying the composition to the substrate, the drying method, etc. can be performed by the same methods as those used to measure the dissolution rate described above, and preferred embodiments are also the same. The heating means used to heat the film at 230°C for 180 minutes can be the same as the drying means used to measure the dissolution rate described above.

[0087] The weight-average molecular weight (Mw) of the specific resin is preferably 3,000 to 100,000. The lower limit of the Mw is preferably 5,000 or more, more preferably 8,000 or more, and even more preferably 10,000 or more. The upper limit of the Mw is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 25,000 or less. By setting the weight-average molecular weight to 3,000 or more, the fold resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (e.g., breaking elongation), the weight-average molecular weight is particularly preferably 5,000 or more. The number-average molecular weight (Mn) of the 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 specific resin is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide is not particularly specified, but for example, it is 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 specific resins, 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.

[0088] [Method for Producing Specific Resin] The specific resin can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and then esterifying the polyamic acid using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting the diester with a diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent and reacting the diamine, etc. Among the above-mentioned production methods, the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent and reacting the diamine is more preferred. 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, trifluoroacetic anhydride, etc. 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 to be obtained as the specific resin, the resin obtained by the above method can be completely imidized using a known imidization reaction method, or the imidization reaction can be stopped midway to introduce a partial imide structure, or a method can be used in which a partial imide structure is introduced by blending a completely imidized polymer with a 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.

[0089] -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. Furthermore, an amino acid in a compound having an amino group and a hydroxy group at the end of a resin, such as p-aminophenol, may be reacted, followed by reaction of the hydroxy group with a compound reactive with a hydroxy group, such as 6-maleimidohexanoic acid chloride. Such a reaction can also introduce a maleimide group into the end of a specific resin. Furthermore, a polymerizable group can also be introduced into a specific resin by using a diamine having a polymerizable group, such as a maleimide group, as the diamine used as a raw material for polymerizing the specific resin.

[0090] Furthermore, by reacting a resin having a terminal carboxylic acid (or carboxylic acid anhydride) with a compound represented by the following formula (T-1), the structure represented by the above formula (TA-1) or formula (TA-3) can be introduced into the resin. In formula (T-1), when a31 is 1, L ３１ represents a single bond or a31+1-valent linking group, and when a31 is 2 or more, L ３１ represents a monovalent linking group; Z ３１ is a single bond, —O— or —NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group; １ represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a31 represents an integer of 1 or more. ３１ , Z ３１ , A １ and a31 is preferably L in formula (R-31). ３１ , Z ３１ , A １ and the preferred embodiments of a31 are the same as those of a31.

[0091] Furthermore, by reacting a resin having an amino group at its terminal with a compound represented by the following formula (T-2), the structure represented by the above formula (TA-2) can be introduced into the resin. In formula (T-2), R Ｔ represents a hydrogen atom or a halogen atom, R Ｎ represents a hydrogen atom or a monovalent organic group; when a32 is 1, L ３２ represents a single bond or a32+1-valent linking group, and when a32 is 2 or more, L ３２ represents a monovalent linking group; Z ３２ is a single bond, —O— or —NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group; １ represents a group having at least one group selected from the group consisting of linear or branched monovalent aliphatic hydrocarbon groups having 6 or more carbon atoms and cyclic aliphatic hydrocarbon groups in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a32 represents an integer of 1 or greater.

[0092] In formula (T-2), R Ｔ is preferably a hydrogen atom or a chlorine atom. ３２ , Z ３２ , A １ and a32 is preferably L in formula (R-32). ３２ , Z ３２ , A １ and a32 are the same as the preferred embodiments.

[0093] Furthermore, by reacting a resin having a terminal carboxylic acid (or carboxylic acid anhydride) with a compound represented by the following formula (T-3), the structure represented by the above formula (TA-3) can be introduced into the resin. In formula (T-3), when a31 is 1, L ３１ represents a single bond or a31+1-valent linking group, and when a31 is 2 or more, L ３１ represents a monovalent linking group; Z ３１ is a single bond, —O— or —NR Ｎ represents -, and R Ｎrepresents a hydrogen atom or a monovalent organic group; １ represents a group having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms, and a31 represents an integer of 1 or more. ３１ , Z ３１ , A １ and a31 is preferably L in formula (R-31). ３１ , Z ３１ , A １ and the preferred embodiments of a31 are the same as those of a31.

[0094] -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.

[0095] [Specific Examples] Specific examples of the specific resin include polyimides SP-1 to SP-23 in the examples described below, but the present invention is not limited to these.

[0096] [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. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0097] The resin composition of the present invention preferably contains at least two resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described later, or may contain two or more specific resins, but preferably contains two or more specific resins.

[0098] <Resin A2> The first resin composition preferably further contains a polyimide precursor, Resin A2, which preferably contains a repeating unit represented by the following formula (3-1). In formula (3-1), X ３ represents an organic group having 4 or more carbon atoms, and Y ３ represents an organic group having 4 or more carbon atoms, A ３ and A ４ are each independently an oxygen atom or —NR Ｎ represents -, and R Ｎ represents a hydrogen atom or a monovalent organic group, R ３ and R ４ each independently represents a hydrogen atom or a monovalent organic group; R ２ each independently represents a group represented by the following formula (R-2), and n represents an integer of 0 or more. In formula (R-2), L ２ represents a b2+1-valent linking group, Z ２ represents a b1+1 valent organic group, A ２represents a methacryloxy group, an acryloxy group, a methacrylamide group, an acrylamide group, a vinyl group, a styryl group, an allyl group, or a vinyl ether group; b1 is 1 or more and Z ２ represents an integer equal to or less than the maximum number of substituents, b2 represents an integer of 1 or more, * represents Y in formula (2-1), ２ Or Y in formula (3-1) ３ represents the binding site with

[0099] In formula (3-1), X ３ and Y ３ A preferred embodiment of the formula (1-1) is X １ and Y １ This is the same as the preferred embodiment of the above.

[0100] In formula (3-1), A ３ and A ４ are preferably oxygen atoms. Ｎ The preferred embodiments are as described above.

[0101] In formula (3-1), R ３ and R ４ Each of R independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. ３ and R ４ Preferably, at least one of R contains a polymerizable group, and more preferably, both of R ３ and R ４It is also preferable that at least one of the groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, or the like, and a radically polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. The radically polymerizable group possessed by the polyimide precursor is preferably a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), with a group represented by the following formula (III) being preferred.

[0102]

[0103] In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with another structure. In formula (III), R ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group. ２０１ Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a dodecamethylene group; a 1,2-butanediyl group, a 1,3-butanediyl group; a —CH ２ CH(OH)CH ２ alkylene groups such as ethylene and propylene; ２ CH(OH)CH ２More preferred are alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When a polyalkyleneoxy group contains multiple alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having an alternating pattern. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent if the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most 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.

[0104] In formula (3-1), R ３is a hydrogen atom, or R ４ When is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0105] In formula (3-1), R ３ and R ４ is a group having an ethylenically unsaturated bond, and X ３ preferably contains a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4). Preferred embodiments of the structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4) are as described above.

[0106] In formula (R-2), L ２ is preferably a group represented by the following formula (L-2). In formula (L-2), L ｘ２ represents a b2+1 valent linking group, b2 represents an integer of 1 or more, * represents Y １ represents a bonding site with Z in formula (R-2), ２ represents the binding site with L ｘ２ is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, still more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group. Preferred embodiments of b2 in formula (L-2) are the same as the preferred embodiments of b2 in formula (R-2).

[0107] Z in formula (R-2) ２represents a b1+1-valent organic group, preferably an aromatic group or an aliphatic hydrocarbon ring group, more preferably an aromatic group. The aromatic group may be either an aromatic hydrocarbon group or a heteroaromatic ring group, but is preferably an aromatic hydrocarbon ring group or a heteroaromatic ring group containing a nitrogen atom as a ring member. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group is preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and even more preferably a benzene ring. Examples of the heteroaromatic ring in the heteroaromatic ring group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an oxazole ring, a pyridine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an indazole ring, a benzimidazole ring, and a purine ring. Examples of the aliphatic ring in the cycloaliphatic group include an aliphatic hydrocarbon ring having 5 to 20 carbon atoms, a pyrrolidine ring, a pyrroline ring, a pyrazolidine ring, an imidazolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a piperazine ring, a tetrahydropyran ring, a dioxane ring, and a morpholine ring. ２ As the ring, a benzene ring, a cyclohexane ring, or an adamantane ring is preferable, and a benzene ring is more preferable.

[0108] A in formula (R-2) ２ is preferably a methacryloxy group, an acryloxy group, a vinyl group, or a vinyl ether group, more preferably a vinyl group or a vinyl ether group, and even more preferably a vinyl group.

[0109] In formula (R-2), b1 is preferably an integer of 1 to 4, and more preferably an integer of 1 or 2. An embodiment in which b1 is 1 is also one of the preferred embodiments of the present invention. In formula (R-2), b2 represents an integer of 1 or more, and is preferably 1 or 2, and more preferably 1.

[0110] The number of ester bonds contained in formula (R-2) is preferably 1 or 0.

[0111] In formula (3-1), n ​​is preferably an integer of 0 to 4, and more preferably an integer of 0 to 2.

[0112] Resin A2 may contain one type of repeating unit represented by formula (3-1), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (3-1). It goes without saying that Resin A2 may also contain other types of repeating units in addition to the repeating unit of formula (3-1).

[0113] In one embodiment of the present invention, the content of the repeating unit represented by formula (3-1) in resin A2 is 50 mol% or more of all repeating units. The content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the content is not particularly limited, and all repeating units in resin A2 except for the terminal repeating units may be repeating units represented by formula (3-1).

[0114] The weight average molecular weight (Mw) of resin A2 is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of resin A2 is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of resin A2 is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Furthermore, when the resin composition contains multiple types of resin A2, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of resin A2 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 plurality of types of resin A2 as one resin, are each within the above ranges.

[0115] [Content] The content of resin A2 in the first resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total solid content of the resin composition. Furthermore, the content is preferably 70% by mass or less, and more preferably 60% by mass or less. The content of resin A relative to the total content of resin A and resin A2 in the first resin composition is preferably 5 to 70% by mass, and even more preferably 20 to 60% by mass.

[0116] <Resin A3> The first resin composition may further contain Resin A3, which is a polyimide that does not fall under the category of Resin A. Resin A3 preferably 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, and R ２ each independently represents a group represented by the following formula (R-2), and n represents an integer of 1 or more. In formula (R-2), L ２ represents a b2+1-valent linking group, Z ２ represents a b1+1 valent organic group, A ２ represents a methacryloxy group, an acryloxy group, a methacrylamide group, an acrylamide group, a vinyl group, a styryl group, an allyl group, or a vinyl ether group; b1 is 1 or more and Z ２ represents an integer equal to or less than the maximum number of substituents, b2 represents an integer of 1 or more, * represents Y in formula (2-1), ２ Or Y in formula (3-1) ３ represents the binding site with

[0117] In formula (2-1), X ２ and Y ２ A preferred embodiment of the formula (1-1) is X １ and Y １ This is the same as the preferred embodiment of the above.

[0118] In formula (2-1), R ２ The preferred embodiments of formula (R-2) in the formula (3-1) are the same as the preferred embodiments of formula (R-2) in the formula (3-1) described above.

[0119] In formula (2-1), n ​​is preferably an integer of 1 to 4, and more preferably 1 or 2.

[0120] Resin A3 may contain one type of repeating unit represented by formula (2-1), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2-1). It goes without saying that Resin A3 may also contain other types of repeating units in addition to the repeating unit of formula (2-1).

[0121] In one embodiment of the present invention, the content of the repeating unit represented by formula (2-1) in resin A3 is 30 mol % or more of all repeating units. This content is more preferably 50 mol % or more. There is no particular upper limit to this content, and all repeating units in resin A3, excluding the terminal repeating units, may be repeating units represented by formula (2-1).

[0122] Resin A3 may have the above-mentioned specific substituent. Preferred embodiments of the specific substituent are the same as the preferred embodiments of the specific substituent in Resin A. Resin A3 also preferably has a structure represented by any one of Formulas (TA-1) to (TA-3) above. Preferred embodiments of the structures represented by these formulas are as described above.

[0123] The weight-average molecular weight (Mw) of Resin A3 is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of Resin A3 is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, but is, for example, preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, the molecular weight dispersity is a value calculated by dividing the weight-average molecular weight by the number-average molecular weight. When the resin composition contains multiple resins A3 as specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one of the resins A3 are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple resins A3 as a single resin are each within the above-mentioned ranges.

[0124] [Content] The content of resin A3 in the first resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total solid content of the resin composition. Furthermore, the content is preferably 70% by mass or less, more preferably 60% by mass or less. The content of resin A relative to the total content of resin A and resin A3 in the first resin composition is preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass.

[0125] <Resin C> The second resin composition contains Resin C containing at least one of the repeating units represented by Formula (2-1) and Formula (3-1). Resin C is a resin that does not fall under Resin B. Preferred aspects of Formula (2-1) and Formula (3-1) in Resin C are as described above. When Resin C is a polyimide containing a repeating unit represented by Formula (2-1), preferred aspects of Resin C are the same as the preferred aspects of Resin A3 described above. When Resin C is a polyimide precursor containing a repeating unit represented by Formula (3-1), preferred aspects of Resin C are the same as the preferred aspects of Resin A2 described above.

[0126] In one embodiment where Resin C is a polyimide precursor, the content of repeating units represented by Formula (3-1) is 50 mol% or more of all repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in Resin C except for the terminal repeating units may be repeating units represented by Formula (3-1).

[0127] The weight average molecular weight (Mw) of resin C is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of resin C is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. Furthermore, when the resin composition contains multiple types of resin C, it is preferable that the weight average molecular weight, number average molecular weight, and dispersity of at least one type of resin C 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 plurality of types of resin C as one resin are each within the above ranges.

[0128] The content of resin C in the second resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total solid content of the resin composition. Furthermore, the content is preferably 70% by mass or less, more preferably 60% by mass or less. The content of resin B in the second resin composition relative to the total content of resins B and C is preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass.

[0129] <Other Resins> The resin composition of the present invention may contain other resins (hereinafter simply referred to as "other resins") different from the above-described specific resin, resin A2, resin A3, and resin C. Examples of other resins include resins different from the specific resin, resin A2, resin A3, and resin C, 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.

[0130] 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. Furthermore, when the resin composition of the present invention contains other resins, the content of the specific resin relative to the total content of the specific resin and the other resins is preferably 10 to 90 mass%, more preferably 10 to 60 mass%, and even more preferably 20 to 50 mass%. 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, it is preferable that the total amount is in the above range.

[0131] <Polymerizable Compound> The resin composition of the present invention contains a polymerizable compound.

[0132] 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.

[0133] 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.

[0134] As used herein, the ClogP value of a compound is defined as follows. Measurement of the octanol-water partition coefficient (logP value) can generally be carried out by the flask shaking method described in JIS Z7260-107 (2000). Alternatively, the octanol-water partition coefficient (logP value) can be estimated by computational chemistry techniques or empirical methods instead of actual measurements. Known calculation methods include Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)), Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 163 (1989)), and Broto's fragmentation method (Eur. J. Med. Chem.-Chim. Theor., 19, 71 (1984)). In the present invention, Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)) is used. 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] Specific examples of polymerizable compounds having a ClogP value of 3.0 or more include, but are not limited to, the following compounds:

[0139] The polymerizable compound may be a radical crosslinking agent or other crosslinking agent.

[0140] [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.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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).

[0148] 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.

[0149] 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.

[0150] 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.

[0151] From the viewpoints of pattern resolution and film stretchability, the resin composition preferably uses a bifunctional methacrylate or acrylate. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexyl ... Examples of usable radical crosslinkers include xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, EO-modified isocyanuric acid dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having urethane bonds. Two or more of these may be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of approximately 200 for the polyethylene glycol chain. From the viewpoint of suppressing warpage of the pattern (cured product), the resin composition of the present invention preferably uses a monofunctional radical crosslinker as the radical crosslinker.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.

[0152] 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.

[0153] 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.

[0154] [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.

[0155] [Polymerization initiator] The resin composition of the present invention contains a polymerization initiator. The polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to contain a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] 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).

[0161] 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).

[0162] 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.

[0163] 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.

[0164] 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.

[0165] 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.

[0166]

[0167] 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.

[0168] 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.

[0169] 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.

[0170] 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.

[0171] [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.

[0172] 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.

[0173] [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.

[0174] 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.

[0175] 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.

[0176] The polymerization initiator is preferably 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 a solvent, the photoacid generator itself, or the like to generate an acid.

[0177] 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.

[0178] 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.

[0179] [Sulfonium Salt] In the present invention, the sulfonium salt means a salt of a sulfonium cation and an anion.

[0180] -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.

[0181] 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.

[0182] -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.

[0183] [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.

[0184] -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.

[0185] 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.

[0186] [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.

[0187] -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):

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] 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 %.

[0193] [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.

[0194] 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.

[0195] 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.

[0196] <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.

[0197] 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.

[0198] 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.

[0199] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0200] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0201] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0202] 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.

[0203] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0204] 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.

[0205] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0206] 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.

[0207] 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.

[0208] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β-ketoester compound, and an amino compound.

[0209] [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.).

[0210]

[0211] 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.).

[0212] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0213] 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.

[0214] 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.

[0215] <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.

[0216] 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.

[0217] 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.

[0218] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0219] 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.

[0220] Specific examples of the migration inhibitor include the following compounds.

[0221]

[0222] 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.

[0223] 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.

[0224] <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.

[0225] 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.

[0226] <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.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] <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, base 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, properties such as film physical properties can be adjusted. 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.

[0231] [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.

[0232] 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.

[0233] [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.

[0234] 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.

[0235] 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.

[0236] 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.

[0237] 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.

[0238] 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.

[0239] 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.

[0240] 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.

[0241] 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(-*)=.

[0242] Specific examples of the compound represented by formula (T-1) include compounds I-5 to I-8 in the examples, but are not limited to these.

[0243] 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.

[0244] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern are improved, and when it is 10 parts by mass or less, the storage stability of the composition is superior. Other additives include the compounds described in paragraphs 0249 to 0282 and 0316 to 0358 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0245] <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.

[0246] <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.

[0247] 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.

[0248] 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.

[0249] 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.

[0250] 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.

[0251] <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

[0252] <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.

[0253] The transmittance of the cured product at a wavelength of 365 nm is preferably 15% 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%. The transmittance is measured using a known spectrophotometer.

[0254] <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.

[0255] 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.

[0256] (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.

[0257] <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.

[0258] [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.

[0259] 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.

[0260] 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.

[0261] <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.

[0262] <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.

[0263] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0264] 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.

[0265] <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 that the heating be carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0266] <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.

[0267] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0268] 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.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0273] [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.

[0274] 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.

[0275] 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.

[0276] [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.

[0277] 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.

[0278] 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.

[0279] 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.

[0280] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0281] [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.

[0282] 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.

[0283] <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.

[0284] The heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of a base or the like generated from the base generator due to heating.

[0285] 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.

[0286] 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.

[0287] 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.

[0288] 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.

[0289] 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 is preferably performed for a short period of time, such as 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, a first pretreatment step may be performed at a temperature in the range of 100 to 150°C, followed by a second pretreatment step at a temperature in the range of 150 to 200°C. Furthermore, cooling may be performed after heating. In this case, the cooling rate is preferably 1 to 5°C / min.

[0290] 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.

[0291] <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.

[0292] <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).

[0293] 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.

[0294] 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.

[0295] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0296] <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).

[0297] 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.

[0298] (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.

[0299] 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.

[0300] 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.

[0301] <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.

[0302] 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.

[0303] 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.

[0304] 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.

[0305] (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.

[0306] (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.

[0307] 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.

[0308] <Synthesis of Resin> [Synthesis of 6-maleimidohexanoic acid chloride (M-1)] In a recovery flask equipped with a thermometer and a calcium chloride tube, 7.92 g (37.5 mmol) of 6-maleimidohexanoic acid was dissolved in 30 g of tetrahydrofuran, 0.1 g of N,N'-dimethylformamide was added, and the mixture was cooled to 0°C while stirring with a magnetic stirrer. Subsequently, 4.85 g (38.25 mmol) of oxalyl chloride was added dropwise, and the mixture was stirred at 0°C to 10°C for 1 hour. Subsequently, the mixture was heated to 25°C and stirred for 2 hours to synthesize 6-maleimidohexanoic acid chloride (M-1).

[0309] [Synthesis of M-2 to M-4] Compounds represented by the following formulae (M-2), (M-3) and (M-4) were synthesized in the same manner as in the synthesis of 6-maleimidohexanoic acid chloride (M-1).

[0310] Synthesis Example SP-1: Synthesis of Polyimide (SP-1) 30.0 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was dissolved in 130 g of N-methylpyrrolidone (NMP). Subsequently, 3.20 g (12.39 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane, 7.89 g (37.18 mmol) of m-tolidine, and 2.78 g (11.53 mmol) of hexadecylamine were added while washing with 50 g of NMP. The mixture was stirred at 20°C to 50°C for 30 minutes, and then 10 g of toluene was added. The mixture was reacted at 200°C for 4 hours under a nitrogen flow and then cooled to 25°C. Next, a THF solution of the 6-maleimidohexanoic acid chloride (M-1) synthesized above (M-1 content: 37.5 mmol), 6.13 g (77.5 mmol) of pyridine, and 0.10 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were added and reacted at 25°C for 2 hours, then the temperature was raised to 45°C and stirred for an additional 10 hours. The reaction solution was then cooled to 25°C, diluted with 200 g of tetrahydrofuran, and the reaction solution was added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water. After stirring for 15 minutes, the polyimide resin was filtered. Next, the resin was reslurried in 1 L of water and filtered, then reslurried again in 1 L of methanol and filtered, and dried under reduced pressure at 40°C for 10 hours. Next, the dried resin was dissolved in 300 g of tetrahydrofuran, and 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added thereto. The mixture was 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 at 45°C under reduced pressure for 1 day to obtain polyimide (SP-1). The weight average molecular weight of the obtained polyimide (SP-1) was 23,700 and the number average molecular weight was 8,900. Polyimide (SP-1) is a resin having a repeating unit represented by the following formula SP-1. The structure of the repeating unit is: １ The molar ratio was determined from the H-NMR spectrum. In the structures below, the subscripts in parentheses represent the molar ratio of each structure.

[0311] [Synthesis Examples SP-2 to SP-6: Synthesis of Polyimides (SP-2 to SP-6)] SP-2 to SP-6 were synthesized in the same manner as SP-1, except that 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and hexadecylamine were appropriately changed so as to give the following structures. Polyimides (SP-2) to (SP-6) are resins having repeating units represented by the following formulae SP-2 to SP-6, 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 weights and number-average molecular weights of these resins are shown in the tables below.

[0312] [Synthesis Examples SP-7 to SP-23: Synthesis of Polyimides (SP-7 to SP-23)] SP-7 to SP-23 were synthesized in the same manner as SP-1, except that 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and hexadecylamine were appropriately changed so as to obtain resins having the following structures. Polyimides (SP-7) to (SP-23) are resins having repeating units represented by the following formulae SP-7 to SP-23, 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 weights and number-average molecular weights of these resins are shown in the tables below.

[0313] Synthesis Example ST-1: Synthesis of Polyimide (ST-1) 30.00 g (57.64 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride was dissolved in 150 g of N-methylpyrrolidone (NMP). Subsequently, while washing with 30 g of NMP, 5.36 g (24.79 mmol) of HAB (manufactured by Wakayama Seika Co., Ltd.), 9.13 g (24.79 mmol) of 4,4'-bis(3-aminophenoxy)biphenyl, 2.51 g (10.38 mmol) of hexadecylamine, and 10 g of toluene were added. After stirring for 15 minutes, the mixture was reacted at 200°C for 4 hours under a nitrogen flow and then cooled to 25°C. Subsequently, 15.3 g (100 mmol) of 4-(chloromethyl)styrene, 16.6 g (120 mmol) of potassium carbonate, 1.66 g (12 mmol) of potassium iodide, and 0.1 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical were added, and the mixture was reacted at 95°C for 15 hours. The mixture was then cooled to 25°C, diluted with 150 g of tetrahydrofuran, and the salt in the reaction solution was filtered with filter paper. Subsequently, the reaction solution was added dropwise to a mixture of 1.8 L of methanol and 0.6 L of water, stirred for 15 minutes, and the polyimide resin was filtered. Next, the resin was reslurried in 1 L of water and filtered, then reslurried again in 1 L of methanol, filtered, and dried under reduced pressure at 40°C for 8 hours. Next, the dried resin was dissolved in 300 g of tetrahydrofuran, 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 (ST-1). The weight average molecular weight of the obtained polyimide resin ST-1 was 19,700 and the number average molecular weight was 8,000. Polyimide (ST-1) is a resin having a repeating unit represented by the following formula ST-1. The structure of the repeating unit is １ The molar ratio was determined from the H-NMR spectrum. In the structures below, the subscripts in parentheses represent the molar ratio of each structure.

[0314] [Synthesis Examples ST-2 to ST-5: Synthesis of Polyimides (ST-2) to (ST-5)] ST-2 to ST-5 were synthesized in the same manner as ST-1, except that the diamine raw material was changed appropriately according to the following structure, and 4-(chloromethyl)styrene was changed to 1-chlorododecane or 3-chloropropyl methacrylate. Polyimides (ST-2) to (ST-5) are resins having repeating units represented by the following formulas ST-2 to ST-5, 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 weights and number-average molecular weights of these resins are shown in the tables below.

[0315]

[0316] Synthesis of Polyimide Precursor Synthesis Example SA-1: Synthesis of Polyimide Precursor (SA-1) 19.83 g (38.1 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 10.12 g (77.8 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 13.40 g (169 mmol) of pyridine, and 70 g of diethylene glycol monomethyl ether were mixed and stirred at a temperature of 60°C for 5 hours to produce a diester of 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride) and glycerol dimethacrylate. The mixture was then cooled to -10°C, and 9.53 g (79.2 mmol) of thionyl chloride was added dropwise over 90 minutes. The mixture was stirred for 2 hours, resulting in a white precipitate of pyridinium hydrochloride. Next, 7.12 g (33.5 mmol) of m-tolidine dissolved in 100 mL of NMP (N-methyl-2-pyrrolidone) was added dropwise over 2 hours. 10.0 g (217 mmol) of ethanol was then added, and the mixture was stirred for 2 hours. The polyimide precursor resin was then precipitated in 4 L of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was collected by filtration, stirred again in 4 L of water for 30 minutes, filtered again, and dried at 40°C for 2 days. The dried resin was then dissolved in 200 g of tetrahydrofuran, and 50 g of ion-exchange resin (MB-1, manufactured by Organo Corporation) was added. The mixture was stirred for 6 hours. Next, the polyimide precursor resin was precipitated in 4 L of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was collected by filtration and dried under reduced pressure at 45°C for 2 days to obtain polyimide precursor (SA-1). The weight-average molecular weight of the obtained polyimide precursor (SA-1) was 24,600 and the number-average molecular weight was 9,400. The imidization rate of polyimide precursor (SA-1) was 3% or less.

[0317] <Synthesis of Diamine> [Synthesis of Dinitro Compound (A-1)] In a flask equipped with a condenser and a stirrer, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 17.4 g (0.22 mol) of dehydrated pyridine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were dissolved in 78 g of ethyl acetate, and the solution was cooled to 5°C or below. Next, 48.4 g (0.21 mol) of 3,5-dinitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 145 g of ethyl acetate, and this solution was added dropwise to the flask using a dropping funnel over 1 hour. After completion of the dropwise addition, the mixture was stirred at 10°C or below for 30 minutes, heated to 25°C, and stirred for 3 hours. Next, the reaction solution was added to ethyl acetate (CH ３ The mixture was diluted with 600 mL of HCl (COOEt), transferred to a separatory funnel, and washed with 300 mL of water, 300 mL of saturated sodium bicarbonate solution, 300 mL of dilute hydrochloric acid, and saturated saline solution, in that order. After separation and washing, the mixture was dried over 30 g of magnesium sulfate, concentrated using an evaporator, and dried in vacuo to obtain 61.0 g of dinitro compound (A-1). The identity of the dinitro compound (A-1) was confirmed by NMR spectrum. Regarding dinitro compound (A-1), １ Analysis by H-NMR was carried out, and the results are shown below. １ H-NMR data (d-chloroform, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 1.97 (s, 3H), 4.55-4.57 (m, 2H), 4.70-4.73 (m, 2H), 5.63 (s, 1H), 6.16 (s, 1H), 9.16-9.17 (d, 2H), 9.24-9.25 (d, 1H)

[0318] <Synthesis of diamine (AA-1)> In a flask equipped with a condenser and a stirrer, 27.9 g (500 mmol) of reduced iron (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 5.9 g (110 mmol) of ammonium chloride (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 3.0 g (50 mmol) of acetic acid (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and 0.03 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were weighed, and 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added and stirred. Next, 16.2 g of the dinitro compound (A-1) was added in small portions over 1 hour and stirred for 30 minutes. Next, the external temperature was raised to 85 ° C., stirred for 2 hours, cooled to 25 ° C. or less, and then filtered using Celite (registered trademark). The filtrate was concentrated using a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separatory funnel and washed twice with 300 mL of saturated aqueous sodium bicarbonate, then with 300 mL of water and 300 mL of saturated brine, in that order. After separation and washing, the mixture was dried over 30 g of magnesium sulfate, concentrated using an evaporator, and dried in vacuo to obtain 11.0 g of diamine (AA-1). Its identity as diamine (AA-1) was confirmed by NMR spectroscopy. １ H-NMR data (d-chloroform, 400 MHz, internal standard: tetramethylsilane) δ (ppm) = 1.95 (s, 3H), 3.68 (s, 4H), 4.45-4.47 (m, 2H), 4.50-4.53 (m, 2H), 5.58 (s, 1H), 6.14 (s, 1H), 6.19-6.20 (t, 1H), 6.77-6.78 (d, 2H)

[0319] Synthesis of Polyimide Precursor Resin (SA-2) In a flask equipped with a condenser and a stirrer, 14.1 g (47.8 mmol) of oxydiphthalic dianhydride was suspended in 100 g of diglyme while removing moisture. 13.4 g (100 mmol) of diethylene glycol monoethyl ether and 16.8 g (132 mmol) of pyridine were subsequently added, and the mixture was stirred at 80°C for 5 hours. The mixture was then cooled to -20°C, and 11.9 g (100 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. The mixture was then warmed to room temperature and stirred for 2 hours. 30 mL of N-methylpyrrolidone (NMP) was added, and 10.3 g (39 mmol) of diamine (AA-1) dissolved in 50 mL of NMP was added dropwise over 1 hour. The viscosity increased during the addition of the diamine. Next, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours. Next, a polyimide precursor resin was precipitated in 3 L of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was collected by filtration, stirred again in 3 L of water for 30 minutes, and filtered again. The resulting polyimide precursor resin was then dried under reduced pressure at 45°C for 1 day. The molecular weight of this polyimide precursor (SA-2) was Mw = 14,300 and Mn = 6,500. The structure of polyimide precursor (SA-2) was represented by the following formula (SA-2). The imidization rate of polyimide precursor (SA-2) was 3% or less.

[0320] [Synthesis of Polyimide Precursor (SA-3)] Polyimide precursor (SA-3) was synthesized in the same manner as in the synthesis of polyimide precursor (SA-2). The molecular weight of polyimide precursor (SA-3) was Mw = 12,500 and Mn = 5,600. The imidization rate of polyimide precursor (SA-3) was 3% or less.

[0321] Synthesis of Comparative Compound A-1: ​​25.6 g (57.64 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride was dissolved in 100 g of N-methylpyrrolidone (NMP). Subsequently, 21.3 g (51.88 mmol) of 4,4'-isopropylidenebis[(4-aminophenoxy)benzene] and 0.76 g (6.92 mmol) of p-aminophenol were added while washing with 60 g of NMP. The mixture was stirred at a temperature ranging from 20 to 50°C for 30 minutes, after which 10 g of toluene was added. The mixture was reacted at 200°C for 4 hours under a nitrogen flow and then cooled to 25°C. Next, the 6-maleimidohexanoic acid chloride THF solution (10.5 mmol), 1.19 g (15 mmol) of pyridine, and 0.10 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical synthesized above were added, and the mixture was allowed to react at 25°C for 2 hours. The mixture was then heated to 45°C and stirred for an additional 10 hours. The reaction solution was then cooled to 25°C, diluted with 200 g of tetrahydrofuran, and the reaction solution was added dropwise to a mixture of 2.0 L of methanol and 0.5 L of water. The mixture was stirred for 15 minutes, and the polyimide resin was filtered. Next, the resin was reslurried in 1 L of water and filtered. The mixture was then reslurried again in 1 L of methanol and filtered, and dried under reduced pressure at 40°C for 10 hours. Next, the dried resin was dissolved in 300 g of tetrahydrofuran, and 40 g of an ion exchange resin (MB-1, manufactured by Organo Corporation) was added thereto. The mixture was 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 at 45°C under reduced pressure for 1 day to obtain polyimide resin (A-1). The weight average molecular weight of the obtained polyimide resin A-1 was 28,800 and the number average molecular weight was 10,900.

[0322] <Synthesis of Comparative Compound A-2> While removing moisture in a dry reactor equipped with a stirrer, a condenser, and a flat-bottom joint equipped with an internal thermometer, 44.43 g (121.3 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, and 492.43 g of γ-butyrolactone was added, followed by stirring at 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 recovered and vacuum-dried at 120°C to obtain 90 g of polymer. Subsequently, 73.86 g (150.0 mmol in terms of hydroxy groups) of the polymer obtained above, 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 condenser. The temperature was then raised to 120°C with stirring, and the mixture was allowed to react for 6 hours. Subsequently, the resulting reaction solution was diluted with acetone to prepare a diluted solution, and the diluted solution was then added dropwise to a 2 / 1 water / methanol mixed solution to precipitate a white solid. The resulting white solid was recovered and vacuum-dried at 40°C to obtain 71.8 g of A-2. The weight-average molecular weight (Mw) of A-2 was 78,500, and the number-average molecular weight (Mn) was 30,200. The structure of A-2 is mainly composed of the structure represented by the following formula (A-2): １ This was confirmed by H-NMR spectrum. １ The results of H-NMR measurement showed that the introduction rate of crosslinking groups was 55%.

[0323] 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 in each column of 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, "-" indicates that the composition did not contain the corresponding component.

[0324]

[0325]

[0326]

[0327] [Resins (cyclized resins or precursors thereof)] SP-1 to SP-23: SP-1 to SP-23 synthesized above, SP-1 to SP-23 correspond to the above-mentioned Resin A and Resin B. ST-1 to ST-5: ST-1 to ST-5 and ST-1 to ST-15 synthesized above correspond to the above-mentioned Resin A3 and Resin C. SA-1 to SA-3: SA-1 to SA-3 synthesized above, SA-1 to SA-3 correspond to the above-mentioned Resin A2 and Resin C. A-1 to A-2: The above-mentioned synthesized products (comparative examples)

[0328] [Polymerizable compounds] B-1: 1,12-dodecanediol dimethacrylate (melting point: 25°C or less) B-2: 1,9-nonanediol dimethacrylate (melting point: 25°C or less) B-3: 1,10-decanediol dimethacrylate (melting point: 25°C or less) B-4: SR-209 (manufactured by Sartomer, melting point: 25°C or less) B-5: ADPH: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., melting point: 25°C or less)

[0329] [Solvents] DMSO: dimethyl sulfoxide GBL: γ-butyrolactone NMP: N-methylpyrrolidone γ-V: γ-valerolactone In the table, the notation "DMSO / GBL" indicates that a mixture of DMSO and GBL was used in a mixing ratio (mass ratio) of DMSO:GBL = 20:80, and the notation "DMSO / γ-V" indicates that a mixture of DMSO and γ-V was used in a mixing ratio (mass ratio) of DMSO:γ-V = 20:80.

[0330] [Polymerization initiators (all trade names)] OXE-01: IRGACURE OXE 01 (manufactured by BASF Corporation) OXE-02: IRGACURE OXE 02 (manufactured by BASF Corporation) OXE-03: IRGACURE OXE 03 (manufactured by BASF Corporation) Irgcure 784: Irgacure 784 (manufactured by BASF Corporation) CPI-310B (manufactured by San-Apro Co., Ltd.) D-1: Benzoyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0331] [Migration inhibitors] E-1 to E-7: Compounds having the following structure

[0332] [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.) F-5: KBM-51073 (manufactured by Shin-Etsu Chemical Co., Ltd.) F-6: X-12-1214A (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0333] [Polymerization inhibitor] 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 (Tokyo Chemical Industry Co., Ltd.)

[0334] [Metal complexes] I-1: TC-750 (manufactured by Matsumoto Fine Chemical) I-2: TC-401 (manufactured by Matsumoto Fine Chemical) I-3: Compound having the following structure

[0335] <Evaluation> [Evaluation of transmittance] When a cured product having a film thickness of 10 μm was formed using the resin composition obtained in each example, the transmittance of the cured product at a wavelength of 365 nm was 15% or more in all cases. The cured product was obtained, for example, by applying the resin composition of the present invention to a substrate such as a silicon wafer, drying it, and then applying a 500 mJ / cm ２ After the entire surface was exposed to i-rays at an exposure energy of 1000 kJ / min, the temperature was increased at a rate of 10° C. / min in a nitrogen atmosphere, and the film was heated at 230° C. for 180 minutes.

[0336] [Evaluation of Resolution] The resin compositions used in each Example and Comparative Example were each 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 ２The film was exposed to light 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 "Development Method (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 to obtain a hole pattern with a diameter of 3 to 20 μm. The formed hole pattern 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 to be resolvable. The smaller the hole pattern that can be formed, the better the resolution; for example, grades A, B, and C are preferred. Furthermore, examples for which no evaluation was performed are marked with a "-" in the "Resolution" column of the table. -Evaluation criteria- A: Hole patterns up to 3 μm in diameter were resolvable. B: Hole patterns of 5 μm in diameter were resolvable, but hole patterns of 3 μm in diameter were not resolvable. C: Hole patterns of 7 μm in diameter were resolvable, but hole patterns of 5 μm in diameter were not resolvable. D: Hole patterns of 10 μm in diameter were resolvable, but hole patterns of 7 μm in diameter were not resolvable. E: Hole patterns of 10 μm in diameter were not resolvable.

[0337] [Evaluation of Flatness] In each Example and Comparative Example, a resin composition or comparative composition was spin-coated onto a silicon wafer having a 1:1 L / S (line and space) pattern of 15 μm high and 20 μm wide copper wiring with a taper angle of 85° to form a resin composition layer. The silicon wafer to which the resulting resin composition layer was applied was dried on a hot plate to obtain a resin composition layer on the silicon wafer with a uniform thickness of approximately 20 μm in the space areas between the copper wiring. The resin composition layer was heated at a rate of 10°C / min under a nitrogen atmosphere, and heated at the temperature specified in the "Temperature" column under "Curing Conditions" in the table for the time specified in the "Curing Time" column under "Curing Conditions" in the table to obtain a cured product. The resulting cured product was measured for the depression X (μm) of the cured product in the space areas between the copper wiring using a scanning electron microscope (S-4800) (manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following criteria. The evaluation results are shown in the "Flatness" column of the table. FIG. 1 shows a schematic cross-sectional view of a cured product formed on a silicon wafer with copper wiring. The silicon wafer 16 in FIG. 1 includes copper wiring 14, and a cured product 12 is formed on the silicon wafer 16. The cured product 12 in the area of ​​the silicon wafer 16 where the copper wiring 14 is not formed has a depression 18 of X μm. The width W of the space between the copper wiring is 20 μm, and the taper angle θ of the copper wiring is 85°. The depression 18 is observed, for example, as the difference between the total thickness h1 of the cured product and the copper wiring at the center of the copper wiring and the thickness h2 of the cured product at the center of the space between the copper wiring. A smaller depression 18 (X) is preferable because it indicates better flatness, and it is preferable to evaluate it as A, B, or C. Evaluation Criteria: A: X was 1 μm or less. B: X was greater than 1 μm and less than 2 μm. C: X was greater than 2 μm and less than 3 μm. D: X was greater than 3 μm.

[0338] [Evaluation of Dielectric Constant and Dielectric Loss Tangent] Each of the resin compositions or comparative compositions prepared in each of the Examples and Comparative Examples was applied to a 12-inch 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 form a resin composition layer with a uniform thickness of 15 µm on the silicon wafer. The resin composition layer on the silicon wafer was then heated to 500 mJ / cm using a stepper (Nikon NSR 2005 i9C). ２ The entire surface was exposed to an exposure energy of 1000 kJ / s, and the exposed resin composition layer (resin layer) was heated at a temperature increase rate of 10°C / min under a nitrogen atmosphere at the temperature specified in the "Temperature" column under "Curing Conditions" in the table for the time specified in the "Curing Time" column under "Curing Conditions" in the table to obtain a cured layer (resin layer) of the resin composition layer. The cured cured layer (resin 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 film sample was measured for its dielectric constant (Dk) and dielectric loss tangent (Df) at 28 GHz using a resonator perturbation method. <Measurement Method> Split Cylinder Resonator (CR-728) (Device Configuration) Network Analyzer: N5230A (Keysight Corporation) (Evaluation Criteria) Dielectric Constant (Dk) A: The film's dielectric constant (Dk) was less than 2.9. B: The film's dielectric constant (Dk) was 2.9 to less than 3.0. C: The relative dielectric constant (Dk) of the film was 3.0 to less than 3.2. D: The relative dielectric constant (Dk) of the film was 3.2 or more.

[0339] Dielectric dissipation factor (Df) A: The dielectric dissipation factor (Df) was less than 0.06. B: The dielectric dissipation factor (Df) was 0.06 to less than 0.08. C: The dielectric dissipation factor (Df) was 0.08 to less than 0.010. D: The dielectric dissipation factor (Df) was 0.010 or more.

[0340] [Evaluation of Moisture Resistance] The resin composition or comparative composition prepared in each Example and Comparative Example was applied to a copper substrate by spin coating to form a layer of the resin composition or comparative composition. The copper substrate on which the resulting resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes to form a resin composition layer or comparative composition layer having a uniform thickness of 5 µm on the copper substrate. The resin composition layer or comparative composition layer on the copper substrate was then heated to 500 mJ / cm using a stepper (Nikon NSR 2005 i9C). ２ The sample was exposed to i-rays using a photomask with a 100 μm square unmasked area formed at an exposure energy of 1000 μm. The sample was then developed for 60 seconds with the developer listed in the "Development Method (Developer)" column of the table, and rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a 100 μm square resin layer. The sample was then heated in a heating oven under a nitrogen atmosphere at the temperature listed in the "Temperature" column of the "Curing Conditions" column of the table for the time listed in the "Curing Time" column of the "Curing Conditions" column of the table to form a resin layer (pattern). The resin composition layer and copper substrate were then left in a chamber at a temperature of 100°C and a humidity of 100% RH for 100 hours. Cross-sectional SEM (scanning electron microscope) measurements were performed to evaluate the void area ratio between the copper substrate and the resin layer. The void area ratio was calculated using the following formula: Void area ratio (%) = (area of ​​voids observed by SEM measurement) / (total area of ​​resin layer) x 100 Evaluation was performed using the obtained void area ratio value according to the following evaluation criteria. The smaller the void area ratio, the better the PCT (wet heat) resistance of the cured film, and the less likely voids are to occur between the metal layer and the cured product even after a long period of time has passed. A: The void area ratio was 0.2% or less. B: The void area ratio was more than 0.2% and 0.5% or less. C: The void area ratio was more than 0.5% and 1% or less. D: The void area ratio exceeded 1%.

[0341] The above results show that the cured products obtained from the resin composition according to the present invention have a low dielectric loss tangent. In comparison, the cured products obtained from the compositions according to Comparative Examples 1 and 2, in which the content of the structure represented by formula (A-1) relative to the mass of resin A is less than 0.2 mmol / g and which do not contain the repeating unit represented by formula (1-1), have a high dielectric loss tangent.

[0342] 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.

[0343] 12 Cured product 14 Copper wiring 16 Silicon wafer 18 Recess H Height of copper wiring h1 Total thickness of the cured product and copper wiring at the center of the copper wiring h2 Thickness of the cured product at the center of the space part of the copper wiring W Width of the space part of the copper wiring θ Taper angle of the copper wiring

Claims

1. A polyimide resin A containing a structure represented by the following formula (A-1) in an amount of 0.20 to 5 mmol / g relative to the mass of resin A, Polymerization initiator, and Contains polymerizable compounds Resin composition. 【Chemistry 1】 In formula (A-1), L Ａ１ represents a single bond or an m+1 valent linking group, R Ｒ１ Each of these independently represents a hydrogen atom or an organic group, and the two R Ｒ１ The elements may be linked together, m represents an integer greater than or equal to 1, and * represents a bonding site with another atom.

2. The resin composition according to claim 1, wherein the structure represented by formula (A-1) is included in the side chain of resin A.

3. The resin composition according to claim 1 or 2, wherein the radical polymerization value of the resin A is 0.20 to 5 mmol / g.

4. L in equation (A-1) Ａ１ The resin composition according to claim 1 or 2, wherein the group comprises an aromatic group or an aliphatic saturated hydrocarbon group having four or more carbon atoms.

5. L A1 in formula (A-1) is a group represented by the following formula (A-1-1) or formula (A-2-2), The resin composition according to claim 1 or 2, wherein * in formula (A-1) is a bonding site with an atom contained in the main chain of resin A. 【Chemistry 2】 In formula (A-1-1), Z1 represents -O- or -NRN-, RN represents a hydrogen atom or a monovalent organic group, RA1 represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms, m represents an integer of 1 or more, * represents a bonding site with an atom included in the main chain of resin A, and # represents a bonding site with the nitrogen atom in formula (A-1). In formula (A-1-2), Z2 represents -O- or -NRN-, RN represents a hydrogen atom or a monovalent organic group, RA2 represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms, m represents an integer of 1 or more, * represents a bonding site with an atom included in the main chain of resin A, and # represents a bonding site with the nitrogen atom in formula (A-1).

6. The resin composition according to claim 1 or 2, further comprising resin A2, which is a polyimide precursor.

7. The resin composition according to claim 1 or 2, wherein the resin A includes a repeating unit represented by the following formula (1-1). 【Transformation 3】 In formula (1-1), X １ represents an organic group with 4 or more carbon atoms, Y １ R represents an organic group with 4 or more carbon atoms. １ Each of these independently represents a structure expressed by the following formula (R-1), where m is an integer from 0 to 4 and n is an integer greater than or equal to 1. 【Chemistry 4】 In formula (R-1), L １ represents a divalent linking group of a2 + 1, and Z １ represents an aromatic group, a cycloaliphatic group, or a linear or branched aliphatic saturated hydrocarbon group. R Ｒ１ each independently represents a hydrogen atom or an organic group, and two Rs Ｒ１ may be linked. a1 represents an integer equal to or less than the maximum number of substituents of Z １ , a2 represents an integer of 1 or more, and * represents the bonding site with X １ or Y １ in formula (1-1).

8. X in equation (1-1) １ and Y １ The resin composition according to claim 7, wherein each of the structures is obtained by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-4). 【Transformation 5】 In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halogen. In formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ They may combine to form a ring structure.

9. L1 in formula (R-1) is a group represented by the following formula (L-1), The resin composition according to claim 7, wherein Y1 in formula (1-1) does not contain an imide bond in its structure. 【Transformation 6】 In formula (L-1), Z L1 represents -O-, -NR N-, -C(=O)O-, or -C(=O)NR N-, R N represents a hydrogen atom or a monovalent organic group, when a2 is 1, L X represents a single bond or a hydrocarbon group, when a2 is 2 or more, L X represents a hydrocarbon group, Z L2 represents a single bond or -O-, -NR N-, -C(=O)O-, or -C(=O)NR N-, R N represents a hydrogen atom or a monovalent organic group, * represents a bonding site with X 1 or Y 1 in formula (1-1), and # represents a bonding site with Z 1 in formula (R-1).

10. The resin composition according to claim 7, comprising a repeating unit represented by formula (1-1), and having at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms.

11. Resin B containing repeating units represented by the following formula (1-1), A resin C containing at least one of the repeating units represented by the following formula (2-1) and the following formula (3-1), Polymerization initiator, and, Contains polymerizable compounds Resin composition. 【Transformation 7】 In formula (1-1), X １ represents an organic group with 4 or more carbon atoms, Y １ represents an organic group with 4 or more carbon atoms, Y １ It is bonded to the nitrogen atom outside the repeating unit without a linking group, R １ Each of these independently represents a structure expressed by the following formula (R-1), where m is an integer from 0 to 4 and n is an integer greater than or equal to 1. 【Transformation 8】 In formula (R-1), L １ represents a² + 1 valent linking group, Z １ R represents an aromatic group, a cyclic aliphatic group, or a linear or branched aliphatic saturated hydrocarbon group. Ｒ１ Each of these independently represents a hydrogen atom or an organic group, and the two R Ｒ１ They may be connected, and a1 is 1 or more Z １ A2 represents an integer less than or equal to the maximum number of substituents in formula (1-1), a2 represents an integer greater than or equal to 1, and * represents X in formula (1-1). １ or Y １ This represents the connection point. 【Chemistry 9】 In formula (2-1), X ２ represents an organic group with 4 or more carbon atoms, Y ２ R represents an organic group with 4 or more carbon atoms. ２ Each of these independently represents a base expressed by the following formula (R-2), where n is an integer greater than or equal to 1. In formula (3-1), X ３ represents an organic group with 4 or more carbon atoms, Y ３ represents an organic group with 4 or more carbon atoms, A ３ and A ４ Each is independently an oxygen atom or -NR Ｎ - represents R Ｎ R represents a hydrogen atom or a monovalent organic group. ３ and R ４ Each of these independently represents a hydrogen atom or a monovalent organic group, R ２ Each of these independently represents a base expressed by the following formula (R-2), where n is a non-negative integer. 【Chemistry 10】 In formula (R-2), L ２ represents a b2+1 valent linking group, Z ２ represents a b1+1 valent organic group, A ２ represents a methacryloxy group, acryloxy group, methacrylamide group, acrylamide group, vinyl group, styryl group, allyl group, or vinyl ether group, and b1 is 1 or more Z ２ b2 represents an integer less than or equal to the maximum number of substituents, b2 represents an integer greater than or equal to 1, and * represents Y in formula (2-1). ２ or Y in equation (3-1) ３ This represents the connection point.

12. In formula (3-1), R ３ and R ４ is a group having an ethylenically unsaturated bond, and X ３ The resin composition according to claim 11, wherein the structure includes a structure obtained by removing two or more hydrogen atoms from a structure represented by any of formulas (V-1) to (V-4).

13. X in equation (1-1) １ and Y １ The resin composition according to claim 11 or 12, wherein each of the structures is obtained by removing two or more hydrogen atoms from a structure represented by any of the following formulas (V-1) to (V-4). 【Chemistry 11】 In formula (V-2), R Ｘ１ Each of these is independently a hydrogen atom, an alkyl group, or an alkyl halogen. In formula (V-3), R Ｘ２ and R Ｘ３ Each of these independently represents a hydrogen atom or a substituent, R Ｘ２ and R Ｘ３ They may combine to form a ring structure.

14. L1 in formula (R-1) is a group represented by the following formula (L-1), The resin composition according to claim 11 or 12, wherein Y1 in formula (1-1) does not contain an imide bond in its structure. 【Chemistry 12】 In formula (L-1), Z L1 represents -O-, -NR N-, -C(=O)O-, or -C(=O)NR N-, R N represents a hydrogen atom or a monovalent organic group, when a2 is 1, L X represents a single bond or a hydrocarbon group, when a2 is 2 or more, L X represents a hydrocarbon group, Z L2 represents a single bond or -O-, -NR N-, -C(=O)O-, or -C(=O)NR N-, R N represents a hydrogen atom or a monovalent organic group, * represents a bonding site with X 1 or Y 1 in formula (1-1), and # represents a bonding site with Z 1 in formula (R-1).

15. The resin composition according to claim 11 or 12, wherein the resin B has at least one group selected from the group consisting of a linear or branched monovalent aliphatic hydrocarbon group having 6 or more carbon atoms, and a cyclic aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with a linear aliphatic hydrocarbon group having 4 or more carbon atoms.

16. The resin composition according to any one of claims 1, 2, 11, and 12, wherein when a cured film with a thickness of 10 μm is formed using the resin composition, the transmittance of light at a wavelength of 365 nm of the cured film is 15% or more.

17. The resin composition according to any one of claims 1, 2, 11, and 12, wherein the melting point of the polymerizable compound is 25°C or lower.

18. The resin composition according to any one of claims 1, 2, 11, and 12, wherein the ClgP of the polymerizable compound is 3 or more.

19. A resin composition according to any one of claims 1, 2, 11, and 12, comprising an azole compound and a silane coupling agent.

20. A resin composition according to any one of claims 1, 2, 11, and 12, used for forming an interlayer insulating film for a redistribution layer.

21. A cured product obtained by curing the resin composition according to any one of claims 1, 2, 11, and 12.

22. A laminate comprising two or more layers made of the cured material described in claim 21, wherein a metal layer is included between any of the layers made of the cured material.

23. A method for producing a cured product, comprising a film-forming step of applying a resin composition according to any one of claims 1, 2, 11, and 12 onto a substrate to form a film.

24. A method for producing a cured product according to claim 23, comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern.

25. A method for producing a cured product according to claim 23, comprising a heating step of heating the film at 50 to 450°C.

26. A method for manufacturing a laminate, comprising the method for manufacturing a cured product described in claim 23.

27. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product as described in claim 23.

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

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