Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, semiconductor device manufacturing method, semiconductor device, polyimide precursor synthesis method, and polyimide precursor

Abstract

Provided are: a resin composition containing a polyimide precursor which is a copolymer comprising a block formed by a repeating unit represented by formula (1-1) and a block formed by a repeating unit represented by formula (1-2); a cured product obtained by curing the resin composition; a laminate comprising the cured product; a method for producing the cured product; a method for producing the laminate; a semiconductor device manufacturing method including the method for producing the cured product; a semiconductor device comprising the cured product; a novel polyimide precursor synthesis method; and a novel polyimide precursor.

Description

Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, semiconductor device, method for synthesizing polyimide precursor, and polyimide precursor

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

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

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

[0004] For example, Patent Document 1 describes a negative photosensitive resin composition containing (A) a polyimide precursor; (B) an active esterifying agent; and (C) a photopolymerization initiator.

[0005] JP 2023-171788 A

[0006] BACKGROUND ART Resin compositions containing polyimide precursors are required to produce cured products with a low coefficient of thermal expansion in response to the miniaturization, high integration, and diversification of device environments.

[0007] The present invention aims to provide a resin composition that can yield a cured product with a low thermal expansion coefficient, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing the cured product, and a semiconductor device including the cured product. Another object of the present invention is to provide a method for synthesizing a novel polyimide precursor.

[0008] Representative embodiments of the present invention are shown below: <1> A resin composition containing a polyimide precursor that is a copolymer containing a block formed by a repeating unit represented by formula (1-1) and a block formed by a repeating unit represented by formula (1-2); Formula (1-1) and in the formula, A １１ and A １２ are each independently —O— or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R １１ and R １２ are each independently a hydrogen atom or a monovalent organic group, and X １ is a tetravalent organic group, and Y １ represents a divalent organic group, and n1 represents the number of repeating units in the block and is an integer of 2 or more; ２１ and A ２２ are each independently —O— or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R ２１ and R ２２ are each independently a hydrogen atom or a monovalent organic group, and X ２ is a tetravalent organic group, and Y ２ represents a divalent organic group, and n2 represents the number of repeating units in the block and is an integer of 2 or more; １ and X in formula (1-2) ２Condition 1: The structures of Y in formula (1-1) are different from each other. １ and Y in formula (1-2) ２ and condition 2 that the repeating units represented by formula (1-1) and (1-2) have different structures. <2> A method for synthesizing a polyimide precursor, which is a copolymer including a block formed by the repeating unit represented by formula (1-1) and a block formed by the repeating unit represented by formula (1-2), the method comprising: synthesizing a first block monomer by amidating a first carboxylic acid dianhydride or a compound derived therefrom with a first diamine; synthesizing a second block monomer by amidating a second carboxylic acid dianhydride or a compound derived therefrom with a second diamine; and bonding the first block monomer and the second block monomer together. Formula (1-1) and in the formula, A １１ and A １２ are each independently —O— or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R １１ and R １２ are each independently a hydrogen atom or a monovalent organic group, and X １ is a tetravalent organic group, and Y １ represents a divalent organic group, and n1 represents the number of repeating units in the block and is an integer of 2 or more; ２１ and A ２２ are each independently —O— or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R ２１ and R ２２ are each independently a hydrogen atom or a monovalent organic group, and X ２ is a tetravalent organic group, and Y ２ represents a divalent organic group, and n2 represents the number of repeating units in the block and is an integer of 2 or more; １ and X in formula (1-2) ２ Condition 1: The structures of Y in formula (1-1) are different from each other. １ and Y in formula (1-2)２ and condition 2 that the structures of the first and second block monomers are different from each other. <3> The method for synthesizing a polyimide precursor according to <2>, wherein the number average molecular weight of the first block monomer is 2000 or more and the number average molecular weight of the second block monomer is 2000 or more. <4> A resin composition comprising a polyimide precursor obtained by the method for synthesizing a polyimide precursor according to <2>. <5> A resin composition comprising a polyimide precursor obtained by the method for synthesizing a polyimide precursor according to <3>. <6> X in formula (1-1) １ is any of the structures represented by the following formulas (2a) to (2e), or a structure containing a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (2f), and X in formula (1-2) ２ is a structure comprising a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulas (V-1) to (V-4): In formulas (2a) to (2e), *1 to *4 respectively represent bonding sites with the carbonyl group in formula (1-1). １ and L ２ is a divalent linking group. In formula (2f), n1 is an integer of 0 or more. In formula (V-2), R Ｘ１ are each independently a hydrogen atom or an alkyl group which may have a substituent. 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. １ and Y in formula (1-2) ２ <8> The composition according to <1>, <4>, or <5>, wherein one of the two groups is a structure derived from an aromatic diamine and the other is a structure derived from an aliphatic diamine. １ and Y in formula (1-2) ２ At least one of the above is a group represented by formula (A-3). In formula (A-3), R １is a hydrogen atom, a halogen atom or a substituent, at least one of which is a bonding site to one of the nitrogen atoms in the formula, R ２ are hydrogen atoms, halogen atoms, or substituents, and at least one of them is a bonding site to the other of the nitrogen atoms in the formula. <9> The resin composition according to <1>, 4, or 5, further comprising a polymerization initiator and a polymerizable compound. <10> The resin composition according to <1>, 4, or 5, further comprising a base generator. <11> The resin composition according to <1>, 4, or 5, used for forming an interlayer insulating film for a redistribution layer. <12> A cured product obtained by curing the resin composition according to <1>, 4, or 5. <13> A laminate comprising two or more layers made of the cured product according to <12>, and a metal layer between any two adjacent layers made of the cured products. <14> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to <1>, 4, or 5 onto a substrate to form a film. <15> A method for producing a cured product according to <14>, comprising an exposure step of selectively exposing the film to light, and a development step of developing the film with a developer to form a pattern. <16> A method for producing the cured product according to <15>, comprising a heating step of heating the film at 50 to 450°C. <17> A method for producing a laminate, comprising the method for producing the cured product according to <14>. <18> A method for producing a semiconductor device, comprising the method for producing the cured product according to <14>. <19> A semiconductor device, comprising the cured product according to <12>. <20> A polyimide precursor obtained by the method for producing a polyimide precursor according to <2> or <3>.

[0009] According to the present invention, there are provided a resin composition that can give a cured product having a small thermal expansion coefficient, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing the cured product, and a semiconductor device containing the cured product. Furthermore, according to the present invention, there are provided a method for synthesizing a novel polyimide precursor and a novel polyimide precursor.

[0010] The following describes the main embodiments of the present invention. However, the present invention is not limited to the explicitly described embodiments. In this specification, a numerical range expressed using the symbol "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits, respectively. In this specification, the term "process" refers not only to an independent process but also to a process that cannot be clearly distinguished from other processes as long as the process achieves its intended effect. In the description of a group (atomic group), a notation that does not specify whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, examples of light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams. As used herein, "(meth)acrylate" refers to either or both of "acrylate" and "methacrylate," "(meth)acrylic" refers to either or both of "acrylic" and "methacrylic," and "(meth)acryloyl" refers to either or both of "acryloyl" and "methacryloyl." In the structural formulae herein, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. As used herein, the term "total solid content" refers to the total mass of all components of the composition excluding the solvent. Furthermore, as used herein, the term "solid content concentration" refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. As used herein, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series. Unless otherwise specified, these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, when NMP is not suitable as the eluent, for example, due to low solubility, THF (tetrahydrofuran) can also be used. Furthermore, unless otherwise specified, detection in GPC measurement is assumed to be performed using a UV (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "above" or "below," it is sufficient that another layer is above or below the reference layer among the multiple layers being considered. In other words, a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "above." Alternatively, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as "above," and the opposite direction is referred to as "below." Note that such vertical directions are defined for convenience in this specification, and in actual embodiments, the "above" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, the composition may contain two or more compounds corresponding to each component contained in the composition. Unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23° C., the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0011] (Resin Composition) The resin composition according to the first aspect of the present invention (hereinafter also simply referred to as the "first resin composition") contains a polyimide precursor that is a copolymer containing a block formed by a repeating unit represented by formula (1-1) and a block formed by a repeating unit represented by formula (1-2). Hereinafter, the polyimide precursor that is a copolymer containing a block formed by a repeating unit represented by formula (1-1) and a block formed by a repeating unit represented by formula (1-2) is also referred to as the "first specific resin." Formula (1-1) and in the formula, A １１ and A １２ are each independently —O— or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R １１ and R １２ are each independently a hydrogen atom or a monovalent organic group, and X １ is a tetravalent organic group, and Y １ represents a divalent organic group, and n1 represents the number of repeating units in the block and is an integer of 2 or more; ２１ and A ２２ are each independently —O— or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R ２１ and R ２２ are each independently a hydrogen atom or a monovalent organic group, and X ２ is a tetravalent organic group, and Y ２ represents a divalent organic group, and n2 represents the number of repeating units in the block and is an integer of 2 or more; １ and X in formula (1-2) ２ Condition 1: The structures of Y in formula (1-1) are different from each other. １ and Y in formula (1-2) ２ and condition 2 that the structures are different from each other.

[0012] A resin composition according to a second aspect of the present invention (hereinafter, also simply referred to as a "second resin composition") comprises a polyimide precursor obtained by a method for synthesizing a polyimide precursor, which is a copolymer comprising a block formed by a repeating unit represented by formula (1-1) and a block formed by a repeating unit represented by formula (1-2), the method comprising: synthesizing a first block monomer by amidating a first carboxylic acid dianhydride or a compound derived therefrom with a first diamine; synthesizing a second block monomer by amidating a second carboxylic acid dianhydride or a compound derived therefrom with a second diamine; and bonding the first block monomer and the second block monomer. Hereinafter, a polyimide precursor obtained by the above-described method for synthesizing a polyimide precursor, which is a copolymer comprising a block formed by a repeating unit represented by formula (1-1) and a block formed by a repeating unit represented by formula (1-2), is also referred to as a "second specific resin." In this specification, a resin composition corresponding to at least one of the first resin composition and the second resin composition is also simply referred to as a "resin composition." Also, a resin corresponding to at least one of the first specific resin and the second specific resin is also simply referred to as a "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 more preferably 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. Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film that is subjected to negative development. In the present invention, negative development refers to development in which non-exposed areas are removed by development in exposure and development, and positive development refers to development in which exposed areas are removed by development. As the exposure method, the developer, and the development method, for example, 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 can be used.

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

[0015] Conventionally, studies have been conducted on anhydride-derived structures, diamine-derived structures, etc. in polyimide precursors, for example, by converting the polyimide precursor into a copolymer, thereby improving the mechanical properties, electrical properties, etc. of the polyimide obtained after curing. The present inventors have discovered that the coefficient of thermal expansion (CTE) of the resulting cured product can be reduced by using a polyimide precursor that is a copolymer containing a block formed by a repeating unit represented by formula (1-1) and a block formed by a repeating unit represented by formula (1-2). The mechanism by which this effect is achieved is unclear, but is presumed to be as follows. The polyimide precursor becomes a polyimide in the cured product, and it is believed that orientation of the polyimides due to interaction between them is important in reducing the CTE. Here, it is believed that the cured product obtained from the resin composition of the present invention containing a polyimide precursor that is a copolymer containing blocks as described above has a reduced CTE due to the increased likelihood of interaction between the polyimides in the cured product. In particular, the X in formula (1-1) １ In the case where the structure itself has a high degree of orientation, such as being any of the structures represented by formula (2a) to formula (2e) or a structure obtained by removing two or more hydrogen atoms from a structure represented by the following formula (2f), the inclusion of this structure as a block further promotes the orientation of polyimides in the cured product, resulting in a significant effect of reducing the CTE. １ is any of the structures represented by formula (2a) to formula (2e), or is a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (2f), and X in formula (1-2) ２ is a structure in which two or more hydrogen atoms have been removed from any of the structures represented by formulas (V-1) to (V-4), the CTE is thought to be further reduced. This is thought to be because the highly oriented repeating units represented by formula (1-1) are linked by the relatively soft structure represented by formula (1-2), which further increases the degree of freedom in resin movement and makes orientation easier. Furthermore, as described above, it is thought that the resin is more likely to be oriented in the cured product, which also increases the glass transition temperature of the cured product.

[0016] It is also possible to use a polyimide precursor containing a repeating unit represented by formula (1-1) in combination with a polyimide precursor containing a repeating unit represented by formula (1-2) instead of a copolymer. However, two types of resins with different resin structures may have low compatibility, and the separation of the resins may become the starting point of breakage. Since the specific resin is a copolymer, it is thought that the problem of separation between the resins is unlikely to occur and that the elongation at break is also excellent. In addition, in the present invention, just as interactions between polyimides in the cured product are likely to occur as described above, interactions between the specific resins themselves are also likely to occur. Therefore, the solvent solubility of the film after exposure is appropriately reduced, and swelling of the film after exposure during development is suppressed. Therefore, when the resin composition of the present invention is a photosensitive resin composition containing a photopolymerization initiator and subjected to exposure development, it is thought that the resolution is also excellent.

[0017] However, Patent Document 1 does not describe a resin composition containing a specific resin.

[0018] The components contained in the resin composition of the present invention will be described in detail below.

[0019] <Specific Resin> The first resin composition of the present invention contains a polyimide precursor (first specific resin) that is a copolymer containing a block formed by a repeating unit represented by formula (1-1) and a block formed by a repeating unit represented by formula (1-2). The second resin composition of the present invention contains a polyimide precursor (second specific resin) obtained by the method for synthesizing a polyimide precursor of the present invention described below.

[0020] A polyimide precursor refers to a resin whose chemical structure changes upon external stimulation to become a polyimide. A resin whose chemical structure changes upon heating to become a polyimide is preferred, and a resin whose ring structure is formed by a ring closure reaction upon heating to become a polyimide is more preferred. In the present invention, polyimide refers to a resin having a repeating unit containing an imide group in the molecular chain, and preferably a resin having a repeating unit containing an imide ring structure in the molecular chain. Furthermore, when the polyimide is a linear resin, the polyimide is preferably a resin having a repeating unit containing an imide group in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain. In this specification, the term "main chain" refers to the relatively longest bonding chain in the resin molecule, and the term "side chain" refers to any other bonding chain. In this specification, the term "imide group" refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site to another structure, preferably a bonding site to a carbon atom, and more preferably a bonding site to a quaternary carbon atom. In this specification, the imide ring structure refers to a ring structure containing two carbon atoms and all of the nitrogen atoms in the imide as ring members. The imide ring structure is preferably a five-membered ring. The polyimide may be a so-called polyamideimide, which has an amide group in the molecular chain in addition to the imide group. In this specification, the amide group refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site to another structure, preferably a bonding site to a carbon atom, and more preferably a bonding site to a quaternary carbon atom. Furthermore, # represents a bonding site to another structure, preferably a bonding site to a hydrogen atom or a bonding site to a carbon atom, and more preferably a bonding site to a hydrogen atom.

[0021] The specific resin preferably has a polymerizable group, more preferably a radically polymerizable group. When the specific resin has a radically polymerizable group, the resin composition of the present invention preferably contains a radical polymerization initiator, more preferably a radical polymerization initiator and a radical crosslinking agent. Furthermore, if necessary, a sensitizer may be included. From such a resin composition, for example, a negative-type photosensitive film is formed. Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film is formed.

[0022] [Formula (1-1)] The specific resin contains a block formed from a repeating unit represented by formula (1-1). In the present invention, a block refers to a molecular chain formed from a series of repeating units composed of the same monomer. For example, when the imidization rate described below is not 0%, the "block formed from a repeating unit represented by formula (1-1)" may contain, in addition to the repeating unit represented by formula (1-1), at least one repeating unit represented by formula (1-1-1), formula (1-1-2), or formula (1-1-3) below. The repeating units represented by formula (1-1-1), formula (1-1-2), or formula (1-1-3) below are all repeating units composed of the same monomer as the repeating unit represented by formula (1-1). That is, when a repeating unit represented by the formula (1-1), a repeating unit represented by the formula (1-1-1), a repeating unit represented by the formula (1-1-2) or a repeating unit represented by the formula (1-1-3) is contained in addition to the repeating unit represented by the formula (1-1), the repeating unit represented by the formula (1-1-1), the repeating unit represented by the formula (1-1-2) and the repeating unit represented by the formula (1-1-3) are the total number of repeating units. In formulas (1-1-1) to (1-1-3), X １ , Y １ , A １１ , A １２ , R １１ and R １２ are X in formula (1-1), respectively. １ , Y １, A １１ , A １２ , R １１ and R １２ is the same as

[0023] -A １１ and A １２ - In formula (1-1), A １１ and A １２ are each independently an oxygen atom or —NR Ｚ -, and an oxygen atom is preferred. Ｚ represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.

[0024] -R １１ and R １２ R in formula (1-1) １１ and R １２ each 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. １１ and R １２ Preferably, at least one of R contains a polymerizable group, and more preferably, both of R １１ and R １２ It is also preferable that at least one of the groups contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, 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.

[0025]

[0026] In formula (III), R ２００ represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and is preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with another structure. In formula (III), R ２０１ represents an alkylene group having 2 to 12 carbon atoms, —CH ２ CH(OH)CH ２ -, a cycloalkylene group or a polyalkyleneoxy group. ２０１ Examples of the alkylene group include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and a dodecamethylene group; a 1,2-butanediyl group, a 1,3-butanediyl group; a —CH ２ CH(OH)CH ２ alkylene groups such as ethylene and propylene; ２ CH(OH)CH ２More preferred are alkylene groups such as ethylene and propylene, or polyalkyleneoxy groups. In the present invention, a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different. When a polyalkyleneoxy group contains multiple alkyleneoxy groups with different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, a block arrangement, or an arrangement having an alternating pattern. The number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent if the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group. In the group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. The preferred embodiments of the number of repeating ethyleneoxy groups and the like in these groups are as described above.

[0027] In formula (1-1), R １１is a hydrogen atom, or R １２ 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.

[0028] In formula (1-1), R １１ and R １２ At least one of the groups may be a polarity conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group. Preferred examples include an acetal group, a ketal group, a silyl group, a silyl ether group, and a tertiary alkyl ester group. From the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0029] -X １ - In formula (1-1), X １ The number of carbon atoms in X is preferably 4 or more, more preferably 4 to 50, and even more preferably 6 to 40. １ is preferably any of the structures represented by the following formulas (2a) to (2e), or a structure containing a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (2f): In formulas (2a) to (2e), *1 to *4 respectively represent bonding sites with the carbonyl group in formula (1-1). １ and L ２ is a divalent linking group. In formula (2f), n1 is an integer of 0 or more.

[0030] In formula (2c), L １ and L２ are each independently —CH ２ - or -O- is preferred.

[0031] The hydrogen atoms in formulas (2a) to (2e) may be substituted with a substituent, and examples of the substituent include an alkyl group, a halogenated alkyl group, etc., and are preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group refers to a group in which at least one hydrogen atom of an alkyl group is substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F.

[0032] In formula (2f), n1 is preferably an integer of 0 to 5, more preferably an integer of 0 to 2, and even more preferably 0 or 1. １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (2f), X １ is preferably a group represented by the following formula (2f-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. In this specification, a bond crossing a side of a ring structure means substituting one of the hydrogen atoms in the ring structure. The definition and preferred embodiments of n1 are as described above. The hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups.

[0033] Also, X １ may be a structure containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4) described below.

[0034] 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.

[0035] Also, X １ It is preferable that X does not contain an imide bond in the structure. １In the present invention, the urethane bond is preferably *—O—C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. Ｎ is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom. Ｎ —C(═O)—NR Ｎ - is a bond represented by *, and R Ｎ R each independently represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. Ｎ The preferred embodiments of X are as described above. １ It is preferable that X does not contain an ester bond in its structure. In the present invention, the ester bond is a bond represented by *--O--C(=O)--*. Among these, X １ It is preferable that the copolymer does not contain an imide bond, a urethane bond, a urea bond, or an amide bond, and it is more preferable that the copolymer does not contain an imide bond, a urethane bond, a urea bond, an amide bond, or an ester bond.

[0036] -Y １ - In formula (1-1), Y １ The number of carbon atoms in the group is preferably 4 or more, more preferably 4 to 50, and even more preferably 6 to 40.

[0037] Y １ may be a structure derived from an aromatic diamine, a structure derived from an aliphatic diamine, or a structure derived from other diamines.

[0038] An aromatic diamine is a compound in which two amino groups of the diamine are both bonded to an aromatic ring by a single bond without a linking group. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but is preferably an aromatic hydrocarbon ring. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 10, and even more preferably 6. Y１ is a structure derived from an aromatic diamine, Y １ is a structure represented by formulas (C-1) to (C-3) described below, and it is preferable that each * is a bonding site with a nitrogen atom.

[0039] Aliphatic diamine refers to a compound in which two amino groups of the diamine are both bonded to an aliphatic group by a single bond without a linking group, and is preferably a compound in which both are bonded to an aliphatic ring by a single bond without a linking group. The aliphatic ring is preferably an aliphatic ring having 4 to 20 ring members, more preferably an aliphatic ring having 4 to 10 ring members. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocycle, but is preferably an aliphatic hydrocarbon ring. Among these, the aliphatic ring is preferably a cyclohexane ring optionally substituted with a hydrogen atom. The cyclohexane ring is preferably a trans-cyclohexane ring. Y １ is a structure derived from an aliphatic diamine, Y １ is a structure represented by formulas (C-4) to (C-7) described below, and each * is preferably a bonding site to a nitrogen atom.

[0040] In formula (1-1), Y １ is preferably a structure containing a structure represented by formula (C-1) to formula (C-3). In formula (C-1), R １ each independently represents a hydrogen atom, a halogen atom or a substituent, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 3, and * represents a bonding site to another structure. １ each independently represents a hydrogen atom, a halogen atom, or a substituent; n1 represents an integer of 0 to 3; n2 represents an integer of 0 to 3; R ２ Each independently represents an alkyl group or a fluoroalkyl group, and * represents a bonding site with another structure. １ each independently represents a hydrogen atom, a halogen atom or a substituent, n1 represents an integer of 0 to 3, and * represents a bonding site to another structure.

[0041] In formula (C-1), R １are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group. The halogen atom in the halogenated alkyl group is preferably F or Cl, and more preferably F. In formula (C-1), n1 is preferably 0 or 1, and more preferably 1. In formula (C-1), n2 is preferably 0 or 1, and more preferably 1.

[0042] In formula (C-2), R １ Preferred embodiments of n1 and n2 are each R １ In formula (C-2), R ２ are each independently preferably an alkyl group having 1 to 4 carbon atoms or a fluoroalkyl group having 1 to 4 carbon atoms, more preferably a methyl group or a trifluoromethyl group.

[0043] In formula (C-3), R １ and n1 are each preferably represented by R １ and n1 are the same as the preferred embodiments.

[0044] In formulas (C-1) to (C-3), * represents Y in formula (1-1). １ is preferably the bonding site with the two nitrogen atoms to which it is bonded.

[0045] Also, Y １ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (C-1), Y １ is preferably a group represented by the following formula (C-1-2) or (C-1-3): In the following formulas, * 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 0 to 5. An embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention. Furthermore, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, halogenated alkyl groups, and halogen atoms.

[0046] Also, Y１ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (C-2), Y １ is preferably a group represented by the following formula (C-2-3) or formula (C-2-4), and from the viewpoint of reducing the dielectric constant of the cured product, it is preferably a group represented by formula (C-2-4). Ｘ１ represents a single bond or —O—, and * represents Y in formula (1-1). １ represents the bonding site with the two nitrogen atoms to which R is bonded. ２ The definitions and preferred embodiments of are as described above. In addition, the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups.

[0047] Among these, from the viewpoint of decreasing the thermal expansion coefficient and increasing the Young's modulus of the cured product, Y １ is preferably a group represented by the following formula (A-3). In formula (A-3), R １ is a hydrogen atom, a halogen atom or a substituent, and at least one of Y １ is a bonding site with one of the nitrogen atoms to which R is bonded, ２ is a hydrogen atom, a halogen atom or a substituent, and at least one of Y １ is the bonding site to the other nitrogen atom in the formula.

[0048] In formula (A-3), R １ is preferably a hydrogen atom or an alkyl group which may have a substituent, more preferably a hydrogen atom, a methyl group or a trifluoromethyl group, and even more preferably a hydrogen atom or a methyl group. ２ is preferably a hydrogen atom or an alkyl group which may have a substituent, more preferably a hydrogen atom, a methyl group or a trifluoromethyl group, and even more preferably a hydrogen atom or a methyl group.

[0049] The group represented by formula (A-3) is preferably a group represented by the following formula (A-4). In formula (A-4), R ３ is a hydrogen atom, a methyl group, or a trifluoromethyl group, and R４ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and * represents Y in (1-1). １ represents the bonding site with the two nitrogen atoms to which they are bonded.

[0050] In formula (1-1), Y １ is preferably a structure containing a structure represented by formula (C-4) to formula (C-7). In formula (C-4), * represents a bonding site to other structures. Furthermore, the hydrogen atoms in formula (C-4) may be further substituted with known substituents such as hydrocarbon groups.

[0051] In formula (C-5), * represents a bonding site to other structures. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups.

[0052] In formula (C-6), * represents a bonding site with other structures. Ｘ５ are each independently a hydrogen atom or an alkyl group which may have a substituent, and are preferably an alkyl group or a halogenated alkyl group; ３ or -CF ３ The hydrogen atom in formula (C-6) may be further substituted with a known substituent such as a hydrocarbon group.

[0053] In formula (C-7), * represents a bonding site to other structures. Furthermore, the hydrogen atom in formula (C-7) may be further substituted with a known substituent such as a hydrocarbon group.

[0054] In formulas (C-4) to (C-7), * represents Y in formula (1-1). １ is preferably the bonding site with the two nitrogen atoms to which it is bonded.

[0055] Among these, Y １ is preferably any one of the following structures: In the following structures, * represents Y in formula (1-1), １ represents the bonding site with the two nitrogen atoms to which they are bonded.

[0056] Others, Y １may have a structure described in paragraphs 0042 to 0053 of JP-A No. 2023-003421. １ It is preferable that Y does not contain an imide structure 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 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.

[0057] -n1- In formula (1-1), n1 represents the number of repeating units in the block, and is preferably an integer of 4 or greater, more preferably an integer of 6 or greater, and even more preferably an integer of 8 or greater. There is no particular upper limit to the number of repeating units, and it may be determined taking into consideration the molecular weight of the resin and the like, but it is preferably an integer of 30 or less, for example.

[0058] [Formula (1-2)] The specific resin contains a block formed from a repeating unit represented by formula (1-2). When the imidization rate described below is not 0%, the "block formed from a repeating unit represented by formula (1-2)" may contain, in addition to the repeating unit represented by formula (1-2), at least one repeating unit represented by formula (1-2-1), formula (1-2-2), or formula (1-2-3) below. The repeating units represented by formula (1-2-1), formula (1-2-2), or formula (1-2-3) below are all repeating units formed from the same monomer as the repeating unit represented by formula (1-2). That is, when a repeating unit represented by the formula (1-2) is contained in addition to a repeating unit represented by the formula (1-2), and a repeating unit represented by the formula (1-2-1), (1-2-2) or (1-2-3) below, the repeating number n2 of the repeating unit in the block described below is the total number of the repeating units represented by the formula (1-2), the repeating units represented by the formula (1-2-1), the repeating units represented by the formula (1-2-2) and the repeating units represented by the formula (1-2-3). In formulas (1-2-1) to (1-2-3), X ２ , Y ２ , A ２１ , A２２ , R ２１ and R ２２ are X in formula (1-2), respectively. ２ , Y ２ , A ２１ , A ２２ , R ２１ and R ２２ is the same as

[0059] -A ２１ , A ２２ , R ２１ , R ２２ - A ２１ , A ２２ , R ２１ and R ２２ A preferred embodiment of each of the above is A in formula (1-1). １１ , A １２ , R １１ and R １２ However, in the description of these preferred embodiments, the expression "formula (1-1)" should be read as "formula (1-2)."

[0060] -X ２ - In formula (1-2), X ２ The number of carbon atoms in X is preferably 4 or more, more preferably 4 to 50, and even more preferably 6 to 40. ２ is preferably a structure containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulas (V-1) to (V-4). In formula (V-2), R Ｘ１ are each independently a hydrogen atom or an alkyl group which may have a substituent. 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.

[0061] In formula (V-2), R Ｘ１are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group. A halogenated alkyl group refers to a group in which at least one hydrogen atom of an alkyl group has been substituted with a halogen atom. The halogen atom is preferably F or Cl, and more preferably F. In formula (V-3), R Ｘ２ and R Ｘ３ are each preferably independently a hydrogen atom. Ｘ２ and R Ｘ３ When R Ｘ２ and R Ｘ３ The structure formed by bonding is a single bond, —O— or —C(R) ２ - is preferred, and -O- or -C(R) ２ R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom.

[0062] X ２ 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 ２ is preferably a group represented by the following formula (V-1-1): In the following formula, * represents X in formula (1-2). ２ represents the bonding sites with the four carbonyl groups to which the carbonyl groups are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups.

[0063] X ２ 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 ２ is preferably a group represented by the following formula (V-2-1): In the following formula, * represents X in formula (1-2). ２ 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.

[0064] X ２ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-3), X ２ 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 (1-2). ２ 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.

[0065] X ２ is a group containing a structure in which two or more hydrogen atoms have been removed from the structure represented by formula (V-4), X ２ is preferably a group represented by the following formula (V-4-1): In the following formula, * represents X in formula (1-2). ２ represents the bonding sites with the four carbonyl groups to which the carbonyl groups are bonded. In addition, the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups.

[0066] Also, X ２ may be any of the structures represented by the above formulas (2a) to (2e), or may be a structure containing a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (2f):

[0067] Other, X ２ 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.

[0068] Also, X ２ It is preferable that X does not contain an imide bond in the structure. ２ It is preferable that X does not contain a urethane bond, a urea bond, or an amide bond in the structure. ２It 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 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.

[0069] -Y ２ - In formula (1-2), Y ２ A preferred embodiment of the formula (1-1) is Y １ However, in the description of these preferred embodiments, the expression "formula (1-1)" should be read as "formula (1-2)."

[0070] In formula (1-2), n2 represents the number of repeating units in the block, and is preferably an integer of 4 or greater, more preferably an integer of 6 or greater, and even more preferably an integer of 8 or greater. There is no particular upper limit to the number of repeating units, and it may be determined taking into consideration the molecular weight of the resin, etc., but it is preferably an integer of 30 or less, for example.

[0071] [Structure of Specific Resin] The specific resin may have only one block formed by the repeating unit represented by formula (1-1), or may have two or more blocks formed by the repeating unit represented by formula (1-2). The specific resin may also have two or more types of blocks formed by the repeating unit represented by formula (1-1), or may have two or more types of blocks formed by the repeating unit represented by formula (1-2). That is, the specific resin may contain three or more types of blocks. The total content of the total mass of the blocks formed by the repeating unit represented by formula (1-1) and the total mass of the blocks formed by the repeating unit represented by formula (1-2) 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 total content is not limited and may be 100% by mass.

[0072] The specific resin is represented by X in formula (1-1). １ is any of the structures represented by the above formulas (2a) to (2e), or a structure containing a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (2f), and X in formula (1-2) ２ is preferably a structure 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). １ The content of repeating units having any of the structures represented by the above formulas (2a) to (2e) or a structure containing a structure obtained by removing two or more hydrogen atoms from a structure represented by the following formula (2f) is preferably 10 to 80 mol %, more preferably 20 to 60 mol %, based on all repeating units in the specific resin. ２ The content of repeating units having a structure 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) is preferably 10 to 90 mol %, and more preferably 30 to 80 mol %, based on all repeating units in the specific resin.

[0073] The specific resin is represented by Y in formula (1-1). １ and Y in formula (1-2) ２Preferably, one of the structures is derived from an aromatic diamine and the other from an aliphatic diamine. This embodiment reduces the absorbance of the specific resin itself (particularly absorbance at ultraviolet light, such as at a wavelength of 365 nm), offering advantages such as allowing the exposure light to penetrate deeper and resulting in a pattern with a more rectangular cross-sectional shape. Furthermore, the content of the aromatic diamine-derived structure in the specific resin is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, even more preferably 40 to 95 mol%, and particularly preferably 50 to 90 mol%, based on all diamine-derived structures contained in the specific resin. Furthermore, the content of the aliphatic diamine-derived structure in the specific resin is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, and even more preferably 10 to 60 mol%, based on all diamine-derived structures contained in the specific resin.

[0074] Y in formula (1-1) １ and Y in formula (1-2) ２ It is preferable that at least one of the following is a group represented by the above formula (A-3). The structure represented by formula (A-3) is a rigid structure, and it is believed that the inclusion of such a structure provides effects such as a decrease in the thermal expansion coefficient and an increase in the elongation at break.

[0075] -Imidization ratio- From the viewpoint of the film strength, insulating properties, etc. of the resulting organic film, the imidization ratio of the specific resin is preferably less than 70%, more preferably 60% or less, even more preferably 50% or less, still more preferably 40% or less, and particularly preferably 30% or less. The lower limit of the imidization ratio is not particularly limited, and it is sufficient as long as it is 0% or more.

[0076] In the present invention, the imidization rate is a value calculated by the following method. The resin is dissolved in γ-butyrolactone, diluted to a viscosity of 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in γ-butyrolactone, the solvent may be changed to another solvent. Examples of such solvents include solvents contained in the resin composition, such as NMP. The viscosity may also be adjusted as appropriate within an adjustable range. The silicon wafer to which the resulting resin layer is applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer on the silicon wafer with a uniform thickness of approximately 15 μm after film formation. Here, if only a resin solution with a low viscosity is obtained and it is difficult to obtain a resin layer with a thickness of 15 μm, the film thickness may be adjusted as appropriate. For example, if the film thickness is 5 μm or greater, a similar imidization rate value can be obtained. The resin layer was measured by the ATR method using NicoletiS20 (manufactured by Thermofisher) in the measurement range of 4000 to 700 cm －１ , the measurement is performed 50 times. －１ Around (1350-1450 cm －１ (If there are multiple peaks, the peak with the greatest intensity) and 1500 cm －１ Around (1460-1550 cm －１ The imidization index A of the resin is calculated by dividing the imidization index B by the peak height of the peak (or the peak with the greatest intensity if there are multiple peaks) in a nitrogen atmosphere at a heating rate of 10°C / min and heated at 350°C for 1 hour. The imidization index B is calculated in the same manner for a film that has been heated at a heating rate of 10°C / min under a nitrogen atmosphere and heated at 350°C for 1 hour. The imidization index A is then divided by the imidization index B to calculate the imidization rate of the resin. In measuring the imidization rate, the resin whose imidization rate is to be measured can be obtained from the composition by, for example, the following method. A solution of 1 g of the composition and 2 g of tetrahydrofuran is added to 50 g of methanol or water to cause crystallization, and the resin is precipitated and filtered. The residue is recovered and dissolved in 3.0 g of THF (tetrahydrofuran), and this is added to 50 g of methanol or water to cause crystallization. The solution is filtered and dried at 40°C for 20 hours to obtain a resin.

[0077] The weight average molecular weight (Mw) of the specific resin 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) of the specific resin 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 the specific resin is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no particular upper limit for the molecular weight dispersity of the specific resin, but, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the molecular weight dispersity is a value calculated by dividing the weight average molecular weight by the number average molecular weight. When the resin composition contains multiple specific resins, it is preferable that the weight-average molecular weight, number-average molecular weight, and dispersity of at least one specific resin are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple specific resins as one resin are each within the above-mentioned ranges.

[0078] [Method for Producing Specific Resin] The first specific resin is preferably produced, for example, by the following method for synthesizing a polyimide precursor. However, the method for producing the specific resin is not limited thereto, and a resin synthesized by another known method may also be used as the specific resin. The second specific resin is produced by the following method for synthesizing a polyimide precursor. This method is a method for synthesizing a polyimide precursor, which is a copolymer including a block formed by a repeating unit represented by formula (1-1) and a block formed by a repeating unit represented by formula (1-2), the method including amidating a first carboxylic acid dianhydride or a compound derived therefrom with a first diamine to synthesize a first block monomer, amidating a second carboxylic acid dianhydride or a compound derived therefrom with a second diamine to synthesize a second block monomer, and bonding the first block monomer to the second block monomer.

[0079] —Step of Synthesizing First Block Monomer— The synthesis method includes synthesizing a first block monomer by amidating a first carboxylic acid dianhydride or a compound derived therefrom with a first diamine (hereinafter also referred to as the “first synthesis step”). Examples of compounds derived from the first carboxylic acid dianhydride include a diester obtained from a tetracarboxylic acid dianhydride and an alcohol, and a compound obtained by acid-halogenating the diester. The first synthesis step can be performed, for example, by reacting a tetracarboxylic acid dianhydride with a diamine at low temperature; by reacting a tetracarboxylic acid 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; by obtaining a diester from a tetracarboxylic acid dianhydride with an alcohol, and then reacting the diester with a diamine in the presence of a condensing agent; or by obtaining a diester from a tetracarboxylic acid dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine with the diamine. Among the above production methods, a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid-halogenated with a halogenating agent and reacted with a diamine is more preferred. In these reactions, the molecular weight (i.e., the number of repeating units) of the first block monomer can be adjusted by appropriately adjusting the amount of diamine used, the reaction temperature, the reaction time, etc.

[0080] In the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting the diester with a diamine in the presence of a condensing agent, or in the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the resulting diamine with a diamine, the diester used is preferably a compound represented by the following formula (DE-1), and the diamine is preferably a compound represented by the following formula (DA-1). In formula (DE-1) or formula (DA-1), A １１ , A １２ , R １１ , R １２ , X １ , Y １are A in formula (1-1), respectively. １１ , A １２ , R １１ , R １２ , X １ , Y １ is synonymous with.

[0081] 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.

[0082] In the first synthesis step, it is preferable to use an organic solvent during the reaction. One type of organic solvent may be used, or two or more types 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 first synthesis step, 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.

[0083] The number average molecular weight of the first block monomer is preferably 2,000 or more, more preferably 2,500 or more, and even more preferably 3,000 or more. The upper limit of the number average molecular weight is not particularly limited, but is preferably 15,000 or less, more preferably 10,000 or less, and even more preferably 8,000 or less.

[0084] -Step of synthesizing a second block monomer- The synthesis method includes synthesizing a second block monomer by amidating a second carboxylic acid dianhydride or a compound derived therefrom with a second diamine (hereinafter also referred to as the "second synthesis step"). Examples of compounds derived from the second carboxylic acid dianhydride include a diester obtained from a tetracarboxylic acid dianhydride and an alcohol, and a compound obtained by converting the diester into an acid halide. The second synthesis step can be carried out by the same method as the first synthesis step.

[0085] In the second synthesis step, in the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting the diester with a diamine in the presence of a condensing agent, or in the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the resulting diamine with a diamine, the diester used is preferably a compound represented by formula (DE-2) below, and the diamine is preferably a compound represented by formula (DA-2) below. In formula (DE-1) or formula (DA-1), A ２１ , A ２２ , R ２１ , R ２２ , X ２ , Y ２ are A in formula (1-2), respectively. ２１ , A ２２ , R ２１ , R ２２ , X ２ , Y ２ is synonymous with.

[0086] The number average molecular weight of the second block monomer is preferably 2,000 or more, more preferably 2,500 or more, and even more preferably 3,000 or more. The upper limit of the number average molecular weight is not particularly limited, but is preferably 15,000 or less, more preferably 10,000 or less, and even more preferably 8,000 or less. Another preferred aspect of the present invention is one in which the number average molecular weight of the first block monomer is 2,000 or more and the number average molecular weight of the second block monomer is 2,000 or more. In the above aspect, preferred aspects of the number average molecular weight of the first block monomer and the number average molecular weight of the second block monomer are as described above.

[0087] -Step of Linking the First Block Monomer and the Second Block Monomer- The synthesis method includes linking the first block monomer and the second block monomer (linking step). The linking step is preferably carried out, for example, by amidating a first block monomer having carboxy groups at both ends, a second block monomer having carboxy groups at both ends, and a diamine. These block monomers can be obtained, for example, by using an excess amount of carboxylic acid dianhydride or a compound derived therefrom compared to the diamine in the synthesis of each block monomer. As the diamine, it is preferable to use a diamine represented by the following formula (DA-3). In formula (DA-3), Y ３ represents a divalent linking group. ３ A preferred embodiment of the formula (1-1) is Y １ The preferred embodiments are the same as those described above. It is also preferable to use the diamine used in the synthesis of the first block monomer or the diamine used in the synthesis of the second block monomer. The amidation is preferably carried out by reacting the carboxyl group in each block monomer with the diamine using the halogenating agent described above, or in the presence of a condensing agent. The preferred embodiments of the halogenating agent and the condensing agent are as described above.

[0088] Alternatively, the bonding step may be performed by amidating one of the first block monomer and the second block monomer with carboxylic acid at both ends and the other with amino groups at both ends. Alternatively, synthesis can be performed by using an excess of the first block monomer with carboxylic acid at both ends and amino groups at both ends of the second block monomer, or by using an excess of the second block monomer with amino groups at both ends and carboxylic acid at both ends of the first block monomer.

[0089] -Other Steps- In the above synthesis method, in order to further improve storage stability, it is also preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the resin obtained by the bonding step. When capping the carboxylic acid anhydride or acid anhydride derivative remaining at the resin terminal, examples of end-capping agents include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and 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.

[0090] The synthesis method may also include a step of precipitating a solid. Specifically, after filtering out the water-absorbing by-product 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.

[0091] [Content] The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one 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.

[0092] It is also preferable that the resin composition of the present invention contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resin described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins. When the resin composition of the present invention contains two or more types of specific resins, for example, it is preferable that the resin composition contains two or more types of polyimide precursors having different dianhydride-derived structures.

[0093] <Other Resins> The resin composition of the present invention may contain the specific resin described above and another resin (hereinafter simply referred to as "other resin") different from the specific resin. Examples of other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, instead of or in addition to the polymerizable compound described below, a resin having a high polymerizable group value and a weight average molecular weight of 20,000 or less (for example, a polymerizable group content of 1×10 per 1 g of resin) can be used. －３ By adding a (meth)acrylic resin (having a molecular weight of at least 100 mol / g) to the resin composition, it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product).

[0094] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. When the resin composition of the present invention contains other resins, the content of the other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. A preferred embodiment of the resin composition of the present invention may also be an embodiment in which the content of the other resin is low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the content is not particularly limited, as long as it is 0% by mass or more. The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0095] The resin composition of the present invention preferably further contains a polymerization initiator and a polymerizable compound, each of which will be described below.

[0096] <Polymerizable Compound> The resin composition of the present invention preferably contains a polymerizable compound. Examples of the polymerizable compound include a radical crosslinking agent and other crosslinking agents.

[0097] [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.

[0098] 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.

[0099] 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.

[0100] 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 polyvalent amine compounds. Also suitable are addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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).

[0105] 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.

[0106] 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.

[0107] 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.

[0108] The radical crosslinking agent is preferably a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U"). Examples of crosslinking agent U include the compounds described in paragraphs 0133 to 0143 of WO 2023 / 190064, the contents of which are incorporated herein by reference.

[0109] From the viewpoints of pattern resolution and film stretchability, the resin composition preferably uses a bifunctional methacrylate or acrylate. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexyl ... Xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, EO-modified isocyanuric acid dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having a urethane bond can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of approximately 200 for the polyethylene glycol chain. From the viewpoint of suppressing warpage of the pattern (cured product), a monofunctional radical crosslinking agent can preferably be used as the radical crosslinking agent in the resin composition of the present invention.Preferred examples of monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. Preferred monofunctional radical crosslinking agents include compounds having a boiling point of 100°C or higher under normal pressure in order to suppress volatilization before exposure. Other examples of bifunctional or higher radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0110] 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.

[0111] 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.

[0112] [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. 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 under the action of an acid or base is more preferred. 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.

[0113] [Polymerization initiator] The resin composition of the present invention preferably 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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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).

[0119] 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).

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124]

[0125] 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.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] [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.

[0130] 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.

[0131] [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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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 %.

[0137] [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.

[0138] 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.

[0139] When a thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. The resin composition may contain only one type of thermal polymerization initiator, or may contain two or more types. When two or more types of thermal polymerization initiators are contained, the total amount is preferably in the above range.

[0140] <Base Generator> The resin composition of the present invention may contain a base generator. Here, the base generator is a compound capable of generating a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a polyimide precursor, the resin composition preferably contains a base generator. By containing a thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in excellent performance as an interlayer insulating film for a rewiring layer included in a semiconductor package. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of non-ionic base generators include the compounds described in paragraphs 0249 to 0275 of WO 2022 / 145355. The above descriptions are incorporated herein by reference.

[0141] Examples of the base generator include, but are not limited to, the following compounds:

[0142]

[0143] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0144] Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018 / 038002.

[0145] Specific examples of ammonium salts include, but are not limited to, the following compounds:

[0146] Specific examples of iminium salts include, but are not limited to, the following compounds:

[0147] The base generator is preferably an amine in which the amino group is protected with a t-butoxycarbonyl group, from the viewpoints of storage stability and generating a base by deprotection during curing.

[0148] Examples of amine compounds protected by a t-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. alcohol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanolamine diamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanolbis(3-aminopropyl)ethanol ter, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown-5-ether, diethylene glycol bis(3-aminopropyl)ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or a derivative thereof is protected with a t-butoxycarbonyl group, but are not limited to these.

[0149] When the resin composition contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.

[0150] <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.

[0151] 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.

[0152] 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.

[0153] Suitable examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

[0154] Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0155] A preferred example of the sulfoxides is dimethyl sulfoxide.

[0156] 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.

[0157] Preferred examples of ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0158] 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.

[0159] From the viewpoint of improving the properties of the coated surface, it is also preferable to mix two or more kinds of solvents.

[0160] 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.

[0161] 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.

[0162] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

[0163] [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.).

[0164]

[0165] 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.).

[0166] [Aluminum-Based Adhesion Aid] Examples of aluminum-based adhesion aids include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.

[0167] 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.

[0168] 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.

[0169] <Compound X1> The resin composition of the present invention may contain compound X1. Compound X1 is a compound having at least one structure selected from the group consisting of a 1,3-dicarbonyl structure and a β-hydroxycarbonyl structure, and having a molecular weight of 1,000 or less. Here, the 1,3-dicarbonyl structure refers to a structure represented by formula (DC-1) below, and the β-hydroxycarbonyl structure refers to a structure represented by formula (HC-1) below.

[0170] In formula (DC-1) or formula (HC-1), * and # each represent a bonding site with another structure. Here, * is preferably a bonding site with a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom. Also, # is preferably a bonding site with a hydrogen atom or a carbon atom. Here, the structure represented by (DC-1) above may be an enol type as shown in formula (DC-2) below. Also, the structure represented by (HC-1) above may be an enol type as shown in formula (HC-2) below. In formula (DC-2) or formula (HC-2), * and # each represent a bonding site to another structure. * is preferably a bonding site to a carbon atom, oxygen atom, nitrogen atom, or sulfur atom. Also, # is preferably a bonding site to a hydrogen atom or carbon atom.

[0171] It is preferable that compound X1 does not contain a metal atom in its structure. The metal atom here does not include metalloid atoms such as silica atoms. Furthermore, it is preferable that compound X1 is not coordinated to a metal atom in the resin composition.

[0172] [Molecular Weight] The molecular weight of compound X1 is 1,000 or less, preferably 100 to 500, more preferably 100 to 400, even more preferably 100 to 350, particularly preferably 100 to 300, and even more preferably 100 to 250.

[0173] [Specific Examples] Specific examples of compound X1 include, but are not limited to, compounds having the following structures.

[0174] [Content] The content of compound X1 relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 30% by mass. The lower limit is more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more. The upper limit is more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less. An embodiment in which the content is 1% by mass or less is also one of the preferred embodiments of the present invention. One type of compound X1 may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the total amount thereof preferably falls within the above range.

[0175] <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.

[0176] 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.

[0177] As the migration inhibitor, an ion trapping agent that traps anions such as halogen ions can also be used.

[0178] 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.

[0179] Specific examples of the migration inhibitor include the following compounds.

[0180]

[0181] 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.

[0182] 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.

[0183] <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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] [Urea Compounds, Carbodiimide Compounds, Isourea Compounds] From the viewpoint of elongation at break and adhesion to a metal or resin layer, the resin composition of the present invention may contain at least one compound selected from the group consisting of a compound having a urea bond (urea compound), a compound having a carbodiimide structure (carbodiimide compound), and a compound having an isourea bond (isourea compound) (hereinafter also referred to as "urea compound, etc."). Among these, it is preferable that the resin composition of the present invention further contains a compound having a urea bond. The urea compounds, etc. referred to here do not include the above-mentioned polymerizable compounds and compounds corresponding to silane coupling agents. Examples of urea compounds include the compounds described in paragraphs 0334 to 0339 of WO 2022 / 070730.

[0188] Specific examples of the urea compound include, but are not limited to, dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea.

[0189] The total content of the urea compounds and the like is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and even more preferably 1.0 to 6.0 parts by mass, per 100 parts by mass of the specific resin. The urea compounds and the like may be used alone or in combination of two or more types. When two or more types of bases are used in combination in the base-containing treatment liquid, it is preferable that the total content thereof be within the above range.

[0190] <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.

[0191] It is also preferable to include a compound having the following structure as the light absorber.

[0192] The content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.

[0193] <Other Additives> The resin composition of the present invention may contain various additives, as needed, within the scope of obtaining the effects of the present invention, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.). By appropriately incorporating these components, it is possible to adjust properties such as film physical properties. For details of these components, please refer to, for example, the descriptions in paragraphs 0183 and after of JP 2012-003225 A (corresponding to paragraph 0237 of U.S. Patent Application Publication No. 2013 / 0034812 ), and the descriptions in paragraphs 0101 to 0104 and 0107 to 0109 of JP 2008-250074 A, the contents of which are incorporated herein by reference. When these additives are blended, the total content thereof is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0194] <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.

[0195] <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.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] <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

[0201] <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.

[0202] <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.

[0203] For the purpose of removing foreign matter such as dust and fine particles from the resin composition of the present invention, it is preferable to perform filtration using a filter. As the filter, for example, the filter described in paragraph 0287 of WO 2023 / 190064 can be used. This description is incorporated herein by reference.

[0204] (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.

[0205] <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.

[0206] [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.

[0207] 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.

[0208] 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 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 various solvents are applied to the substrate before applying the resin composition to improve the wettability of the substrate.

[0209] <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.

[0210] <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.

[0211] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, and is preferably 240 to 550 nm.

[0212] 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.

[0213] <Post-Exposure Bake Step> The film may be subjected to a heating step (post-exposure bake step) after exposure. That is, the method for producing a cured product of the present invention may include a post-exposure bake step in which the film exposed in the exposure step is heated. The post-exposure bake step can be carried out after the exposure step and before the development step. The heating temperature in the post-exposure bake step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure bake step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The temperature rise rate in the post-exposure bake step from the temperature at the start of heating to the maximum heating temperature is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The temperature rise rate may also be changed as appropriate during heating. The heating means in the post-exposure bake step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. may be used. It is also preferable to carry out the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0214] <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.

[0215] [Developer] The developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.

[0216] When the developer is an alkaline aqueous solution, examples of the basic compound that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. For example, the basic compounds described in paragraph 0300 of WO 2023 / 190064 can be used, more preferably TMAH. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer. The description in paragraph 0300 of WO 2023 / 190064 is incorporated herein by reference.

[0217] 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.

[0218] 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.

[0219] 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.

[0220] The developer may further contain other components, such as known surfactants and known defoaming agents.

[0221] [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.

[0222] 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.

[0223] 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.

[0224] [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.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] The rinse liquid may further contain other components, such as known surfactants and known defoaming agents.

[0229] [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 rinse 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, or a combination of these steps.

[0230] 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.

[0231] <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, resins such as polyimides are cyclized to form resins such as polyimides. 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. Alternatively, the heating step can be performed, for example, by the method described in paragraphs 0326 to 0332 of WO 2023 / 190064. This description is incorporated herein by reference.

[0232] <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 / cm２ 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.

[0233] <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).

[0234] 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.

[0235] 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.

[0236] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest part.

[0237] <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).

[0238] 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.

[0239] (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.

[0240] 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.

[0241] 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.

[0242] <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.

[0243] 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.

[0244] 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.

[0245] 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.

[0246] (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 subjected to a surface activation treatment step 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 more preferably 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 a surface activation treatment on the surface of the metal layer, adhesion with the resin composition layer (film) provided on its 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 a surface activation treatment on the surface of the resin composition layer, it is possible to improve adhesion with the metal layer or resin layer provided on the surface that has been surface-activated. In particular, when negative development is performed, for example, when the resin composition layer is cured, it is less susceptible to damage due to the surface treatment and adhesion is likely to be improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021 / 112189. The contents of this specification are incorporated herein.

[0247] (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.

[0248] (Method for Synthesizing Polyimide Precursor) The method for synthesizing a polyimide precursor of the present invention is a method for synthesizing a polyimide precursor, which is a copolymer including a block formed by a repeating unit represented by formula (1-1) and a block formed by a repeating unit represented by formula (1-2), and includes synthesizing a first block monomer by amidating a first carboxylic acid dianhydride or a compound derived therefrom with a first diamine, synthesizing a second block monomer by amidating a second carboxylic acid dianhydride or a compound derived therefrom with a second diamine, and bonding the first block monomer to the second block monomer. Formula (1-1) and in the formula, A １１ and A １２ are each independently —O— or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R １１ and R １２ are each independently a hydrogen atom or a monovalent organic group, and X １ is a tetravalent organic group, and Y １ represents a divalent organic group, and n1 represents the number of repeating units in the block and is an integer of 2 or more; ２１ and A ２２ are each independently —O— or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R ２１ and R ２２ are each independently a hydrogen atom or a monovalent organic group, and X ２ is a tetravalent organic group, and Y ２ represents a divalent organic group, and n2 represents the number of repeating units in the block and is an integer of 2 or more; １ and X in formula (1-2) ２ Condition 1: The structures of Y in formula (1-1) are different from each other. １ and Y in formula (1-2) ２ and condition 2 that the structures are different from each other.

[0249] The preferred embodiment of the method for synthesizing the polyimide precursor of the present invention is the same as the preferred embodiment of the method for producing the characteristic resin described above.

[0250] Preferred aspects of the polyimide precursor obtained by the method for synthesizing a polyimide precursor of the present invention, and preferred aspects of formula (1-1) and formula (1-2) in the method for synthesizing a polyimide precursor of the present invention are the same as the preferred aspects of the above-mentioned specific resin, and the preferred aspects of formula (1-1) and formula (1-2) in the above-mentioned specific resin, respectively.

[0251] (Polyimide precursor) The polyimide precursor of the present invention is a polyimide precursor obtained by the above-mentioned method for producing a polyimide precursor of the present invention. Preferred aspects of the polyimide precursor of the present invention are the same as the preferred aspects of the above-mentioned specific resin.

[0252] 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.

[0253] <Method for Producing Specific Resins> [Synthesis Example P-1: Synthesis of Resin P-1] 13.0 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA), 6.6 g of 2-hydroxyethyl methacrylate, 8.7 g of pyridine, and 28.1 g of diglyme (diglyme, diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 3 hours to synthesize a diester of BPADA and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -5°C, and while maintaining the temperature at -5 to -3°C, a mixed solution of 6.2 g of thionyl chloride and 21.8 g of diglyme was added dropwise over 60 minutes, followed by stirring for an additional 60 minutes. To this mixture, a mixed solution of 3.7 g of m-tolidine and 27.0 g of NMP was added dropwise over 30 minutes, followed by stirring at -2 to 0°C for 30 minutes to prepare Solution B. In a separate flask, 5.4 g of pyromellitic acid (PMDA), 6.6 g of 2-hydroxyethyl methacrylate, 8.7 g of pyridine, and 28.1 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 3 hours to synthesize a diester of PMDA and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -5°C, and while maintaining the temperature at -5 to -3°C, a mixed solution of 6.2 g of thionyl chloride and 21.8 g of diglyme was added dropwise over 60 minutes, followed by stirring for an additional 60 minutes. To this mixture, a mixed solution of 3.7 g of m-tolidine and 27.0 g of NMP was added dropwise over 30 minutes, followed by stirring at -2 to 0°C for 30 minutes to prepare Solution A. Solution A and Solution B were transferred using 12.5 g of N-methyl-2-pyrrolidone (NMP) and mixed at a temperature of -5 to -3°C. A mixed solution of 1.8 g of m-tolidine and 18.2 g of NMP was then added dropwise to the mixed solution over 30 minutes. The mixture was then heated to room temperature (23°C) and stirred for 30 minutes. 9.2 g of ethanol was then added and stirred at room temperature for 1 hour. The reaction solution was then diluted with 74.0 g of acetonitrile. The reaction solution was then added to 2000 g of water to precipitate a polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was collected by filtration and dried in vacuo at 45°C for 15 hours.The dried powder was dissolved in 225.4 g of tetrahydrofuran, and then 40.0 g of ion exchange resin UP6040 (manufactured by AmberTec) was added and stirred for 2 hours. Thereafter, the ion exchange resin was removed by filtration, diluted with 45.0 g of tetrahydrofuran, and then added to 2000 g of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45 ° C. for 24 hours to obtain 35.3 g of resin P-1. The molecular weight of resin P-1 was measured by the following gel permeation chromatography (GPC) measurement, and the weight average molecular weight (Mw) was 30,000. GPC measurements were performed using a high-speed GPC system HLC-8420GPC (manufactured by Tosoh Corporation) with a TSK guard column Super AW-H (4.6 mm x 35 mm) and two TSKgel Super AWM-H (4.6 mm x 150 mm) columns connected in series. A 0.01 mol / L solution of lithium bromide in NMP (N-methyl-2-pyrrolidone) was used as the eluent. Unless otherwise specified, the weight-average molecular weights of the following resins were measured using the same method as for Resin P-1. １ H-NMR confirmed that the structure of resin P-1 was the structure represented by the following formula (P-1): In the following structure, the subscripts in parentheses represent the molar ratio of each repeating unit, and * represents the bonding site with the carbonyl group to which X is bonded.

[0254] [Synthesis Examples P-2 to P-21: Synthesis of Resins P-2 to P-21] Resins P-2 to P-21 were synthesized using the same method as in Synthesis Example P-1. The weight average molecular weight (Mw) of Resins P-2 to P-7 and P-9 to P-21 was 30,000. For Resin P-8, resins with weight average molecular weights (Mw) of 3,000, 5,000, 10,000, 15,000, 20,000, 22,000, 30,000, 45,000, 75,000, and 150,000 were synthesized by adjusting the amount of diamine used, for example. １By H-NMR, it was confirmed that the structures of resins P-2 to P-21 were structures represented by the following formulas (P-2) to (P-21): In the structures below, the subscripts in parentheses represent the molar ratio of each repeating unit, * represents the bonding site with the carbonyl group to which X is bonded, and # represents the bonding site with the nitrogen atom to which Z is bonded.

[0255] [Synthesis of Resin P-22] 13.0 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA), 6.6 g of 2-hydroxyethyl methacrylate, 8.7 g of pyridine, and 28.1 g of diglyme (diglyme, diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 3 hours to synthesize a diester of BPADA and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -5°C, and a mixed solution of 6.2 g of thionyl chloride and 21.8 g of diglyme was added dropwise over 60 minutes while maintaining the temperature at -5 to -3°C, followed by stirring for an additional 60 minutes. A mixed solution of 4.1 g of m-tolidine and 30.3 g of NMP was added dropwise over 30 minutes to the mixture, followed by stirring at -2 to 0°C for 30 minutes to prepare Solution B. In a separate flask, 5.4 g of pyromellitic acid (PMDA), 6.6 g of 2-hydroxyethyl methacrylate, 8.7 g of pyridine, and 28.1 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 3 hours to synthesize a diester of PMDA and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -5°C, and a mixed solution of 6.2 g of thionyl chloride and 21.8 g of diglyme was added dropwise over 60 minutes while maintaining the temperature at -5 to -3°C, followed by stirring for an additional 60 minutes. A mixed solution of 4.1 g of m-tolidine and 30.3 g of NMP was added dropwise over 30 minutes to the mixture, followed by stirring at -2 to 0°C for 30 minutes to prepare Solution A. Solution A and Solution B were transferred using 12.5 g of N-methyl-2-pyrrolidone (NMP) and mixed at a temperature of -5 to -3°C. A mixed solution of 0.9 g of m-tolidine and 5.9 g of NMP was then added dropwise to the mixed solution over 30 minutes. The mixture was then warmed to room temperature and stirred for 30 minutes. 9.2 g of ethanol was then added and stirred at room temperature for 1 hour. The reaction solution was then diluted with 74.0 g of acetonitrile. The reaction solution was then added to 2000 g of water to precipitate a polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was collected by filtration and dried in vacuo at 45°C for 15 hours.The dried powder was dissolved in 225.4 g of tetrahydrofuran, and then 40.0 g of ion exchange resin UP6040 (AmberTec) was added and stirred for 2 hours. The ion exchange resin was then removed by filtration, diluted with 45.0 g of tetrahydrofuran, and added to 2000 g of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45°C for 24 hours to obtain 35.3 g of resin P-22. The molecular weight of resin P-22 was measured by the following gel permeation chromatography (GPC) measurement, and the weight average molecular weight (Mw) was found to be 30,000. １ H-NMR confirmed that the structure of resin P-22 was that of the following formula (P-22): In the following structure, the subscripts in parentheses represent the molar ratio of each repeating unit, and * represents the bonding site with the carbonyl group to which X is bonded.

[0256] [Synthesis of Resin P-23] 18.1 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride (BPADA), 6.6 g of 2-hydroxyethyl methacrylate, 8.7 g of pyridine, and 28.1 g of diglyme (diglyme, diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 3 hours to synthesize a diester of BPADA and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -5°C, and a mixed solution of 8.7 g of thionyl chloride and 21.8 g of diglyme was added dropwise over 60 minutes while maintaining the temperature at -5 to -3°C, followed by stirring for an additional 60 minutes. A mixed solution of 2.6 g of m-tolidine and 27.0 g of NMP was added dropwise over 30 minutes to the mixture, followed by stirring at -2 to 0°C for 30 minutes to prepare Solution B. In a separate flask, 3.3 g of pyromellitic acid (PMDA), 6.6 g of 2-hydroxyethyl methacrylate, 8.7 g of pyridine, and 28.1 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 3 hours to synthesize a diester of PMDA and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -5°C, and while maintaining the temperature at -5 to -3°C, a mixed solution of 3.7 g of thionyl chloride and 21.8 g of diglyme was added dropwise over 60 minutes, followed by stirring for an additional 60 minutes. To this mixture, a mixed solution of 1.1 g of m-tolidine and 27.0 g of NMP was added dropwise over 30 minutes, followed by stirring at -2 to 0°C for 30 minutes to prepare Solution A. Solution A and Solution B were transferred using 12.5 g of N-methyl-2-pyrrolidone (NMP) and mixed at a temperature of -5 to -3°C. A mixed solution of 1.8 g of m-tolidine and 18.2 g of NMP was then added dropwise to the mixed solution over 30 minutes. The mixture was then warmed to room temperature and stirred for 30 minutes. 9.2 g of ethanol was then added and stirred at room temperature for 1 hour. The reaction solution was then diluted with 74.0 g of acetonitrile. The reaction solution was then added to 2000 g of water to precipitate a polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was collected by filtration and dried in vacuo at 45°C for 15 hours.The dried powder was dissolved in 225.4 g of tetrahydrofuran, and then 40.0 g of ion exchange resin UP6040 (AmberTec) was added and stirred for 2 hours. The ion exchange resin was then removed by filtration, diluted with 45.0 g of tetrahydrofuran, and added to 2000 g of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45°C for 24 hours to obtain 35.3 g of resin P-23. The molecular weight of resin P-23 was measured by the following gel permeation chromatography (GPC) measurement, and the weight average molecular weight (Mw) was found to be 30,000. １ The structure of resin P-23 was confirmed by H-NMR to be that represented by the following formula (P-23): In the following structure, the subscripts in parentheses represent the molar ratio of each repeating unit, and * represents the bonding site with the carbonyl group to which X is bonded.

[0257] Synthesis of Synthesis Example P-6B: 15.4 g of BPADA, 7.8 g of 2-hydroxyethyl methacrylate, 4.8 g of pyridine, and 26.8 g of γ-butyrolactone were mixed and stirred at 60°C for 4 hours to synthesize a diester of BPADA and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to 0°C, and a mixed solution of 12.2 g of dicyclohexylcarbodiimide and 12.1 g of γ-butyrolactone was added dropwise over 40 minutes while maintaining the temperature at 0 to 5°C. To this mixture, a mixed solution of 4.6 g of m-tolidine and 18.7 g of NMP was added dropwise over 60 minutes, and the mixture was stirred at 0 to 5°C for 90 minutes to prepare Solution B. In a separate flask, 8.7 g of BPDA, 7.8 g of 2-hydroxyethyl methacrylate, 4.8 g of pyridine, and 26.8 g of γ-butyrolactone were mixed and stirred at 60°C for 4 hours to synthesize a diester of BPADA and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to 0°C, and a mixed solution of 12.2 g of dicyclohexylcarbodiimide and 12.1 g of γ-butyrolactone was added dropwise over 40 minutes while maintaining the temperature at 0 to 5°C. A mixed solution of 4.6 g of m-tolidine and 18.7 g of NMP was added dropwise to the reaction mixture over 60 minutes, and the mixture was stirred at 0 to 5°C for 90 minutes to prepare Solution A. Solution A and Solution B were transferred and mixed at a temperature of 0 to 5°C. A mixed solution of 2.3 g of m-tolidine and 9.4 g of NMP was then added dropwise to the mixed solution over 15 minutes. The mixture was then warmed to room temperature and stirred for 90 minutes. 2.8 g of ethanol was then added and stirred at room temperature for 1 hour. Next, 53.6 g of γ-butyrolactone was added. The reaction solution was refrigerated overnight, then warmed to room temperature, and the precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to 287.9 ​​g of ethyl alcohol to produce a precipitate consisting of a crude polymer. The resulting crude polymer was recovered by decantation and dissolved in 183.4 g of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 3,850 g of water to precipitate the polymer. The resulting precipitate was filtered and then vacuum-dried at 45°C to obtain 41.3 g of powdered P-6B. The weight-average molecular weight (Mw) of P-6B was 25,000. １By H-NMR, it was confirmed that the structure of resin P-6B was the structure represented by the above formula (P-6).

[0258] [Synthesis of Synthesis Examples P-7B to P-9B] Resins P-7B to P-9B were synthesized in the same manner as in Synthesis Example P-6B. The weight average molecular weight (Mw) of P-7B to P-9B was 25,000. １ It was confirmed by H-NMR that the structures of resins P-7B to P-9B were the structures represented by the above formulas (P-7) to (P-9).

[0259] The number average molecular weight (Mn) of the block monomer used to form the left block in the chemical formula is shown as "number average molecular weight A," and the number average molecular weight (Mn) of the block monomer used to form the right block is shown as "number average molecular weight B" in the table below. For example, for the above-mentioned Synthesis Example P-1, the number average molecular weight (Mn) of the block monomer in Solution A is shown as "number average molecular weight A," and the number average molecular weight (Mn) of the block monomer in Solution B is shown as "number average molecular weight B." Furthermore, for Resins P-9 and P-9B, a third block monomer is further used, and therefore the Mn of the block monomer used to form the left block in the chemical formula is shown as "number average molecular weight A," the Mn of the block monomer used to form the central block is shown as "number average molecular weight B," and the Mn of the block monomer used to form the right block is shown as "number average molecular weight C" in the table below. From the Mn of each block polymer shown in the table, it can be said that the final resin contains at least a block in which n1 in Formula (1-1) is 4 or more and n2 in Formula (1-2) is 4 or more.

[0260]

[0261] Synthesis Example PC-1: Synthesis of Resin PC-1: 16.7 g of PMDA, 20.3 g of 2-hydroxyethyl methacrylate, 26.9 g of pyridine, and 86.1 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 4 hours to synthesize a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and a mixed solution of 19.1 g of thionyl chloride and 66.6 g of diglyme was added over 60 minutes while maintaining the temperature at -10±5°C. A solution of 14.4 g of m-tolidine dissolved in 103.8 g of N-methylpyrrolidone was then added dropwise to the reaction mixture over 60 minutes at -10±5°C, and the mixture was stirred at room temperature for 2 hours. Then, 14.1 g of ethanol was added and the mixture was stirred at room temperature for 1 hour. Next, 2423 g of water was added to precipitate the polyimide precursor, and the precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The precipitate (solid polyimide precursor) after stirring was collected by filtration and dried at 45 ° C under reduced pressure for 18 hours. The dried crude polymer powder was dissolved in 281.8 g of tetrahydrofuran, and 50.0 g of ion exchange resin UP6040 (manufactured by AmberTec) was added and stirred for 4 hours. The ion exchange resin was then removed by filtration, and the resulting polymer solution was added to 2439 g of water to obtain a precipitate. The precipitate was collected by filtration and dried at 45 ° C under reduced pressure for 24 hours to obtain resin PC-1. １ By H-NMR, it was confirmed that the structure of Resin PC-1 was a structure represented by the following formula (PC-1): Resin PC-1 had a weight average molecular weight (Mw) of 30,000.

[0262] [Synthesis Example PC-2: Synthesis of Resin PC-2] Resin PC-2 was synthesized in the same manner as in Synthesis Example PC-1. Resin PC-2 had a weight average molecular weight (Mw) of 30,000. １ By H-NMR, it was confirmed that the structure of resin PC-2 was a structure represented by the following formula (PC-2).

[0263] Examples and Comparative Examples In each example, the components listed in the table below were mixed to obtain a resin composition. In the comparative examples, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content (amount) of each component listed in the table other than the solvent was the amount (parts by mass) listed in the "Parts by Mass" column of each column in the table. The solvent content (amount) was adjusted so that the solids concentration of the composition was the value (% by mass) of "Solids Concentration" in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvent was the ratio listed in the "Ratio" column in the table. The obtained resin composition and comparative composition were pressure-filtered using a polytetrafluoroethylene filter with a pore width of 0.8 μm. In the tables, "-" indicates that the composition did not contain the corresponding component.

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272] Details of each component listed in the table are as follows:

[0273] [Resins] P-1 to P-23, P-6B to P-9B, CP-1 to CP-2: Resins P-1 to P-23, P-6B to P-9B, CP-1 to CP-2 obtained by the above synthesis examples. P-1 to P-23, P-6B to P-9B are resins that fall under the category of specific resins.

[0274] [Polymerizable Compounds] M-1 to M-3: Compounds having the following structures, in which the subscripts in parentheses indicate the number of repetitions: DPHA: Dipentaerythritol hexaacrylate

[0275] [Polymerization initiators] I-1 to I-7: Compounds having the following structures

[0276] [Base Generator] F-1 to F-5: Compounds having the following structure

[0277] [Polymerization inhibitors] B-1 to B-10: Compounds having the following structures (however, B-5 ​​is a compound that also functions as a migration inhibitor)

[0278] [Silane coupling agents (metal adhesion improvers)] C-1 to C-4: Compounds having the following structures

[0279] [Migration inhibitors] D-1 to D-5: Compounds having the following structure B-5: Compounds represented by the above formula B-5

[0280] [Additives] E-1 to E-14: Compounds having the following structure F-554: Megafac F-554 (manufactured by DIC Corporation) BYK-333: BYK-333 (manufactured by BYK Corporation) E-7: Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid E-8: The following synthetic product

[0281] <Additive: Synthesis of Diazonaphthoquinone Compound E-8> 29.72 g (70 mmol) of 4,4'-(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene)bisphenol (Tris-PA, manufactured by Honshu Chemical Industry Co., Ltd.) was added to a flask. Subsequently, 46.93 g (174.9 mmol) of 1,2-naphthoquinone diazide-5-sulfonic acid chloride and 17.9 g of triethylamine were dissolved in 300 g of acetone with stirring, and the solution was added dropwise to the flask using a dropping funnel over 30 minutes, followed by stirring for 30 minutes at an internal temperature of 30°C. Subsequently, hydrochloric acid was added dropwise, and the mixture was stirred for an additional 30 minutes. Next, a solution of 1,640 g of pure water and 30 g of hydrochloric acid was prepared in a beaker, and the filtrate obtained by filtering the hydrochloride salt from the reaction solution was added dropwise to the solution. The precipitate was filtered, washed with water, and vacuum-dried at 40°C for 50 hours to obtain diazonaphthoquinone compound E-8.

[0282] [Solvents] NMP: N-methyl-2-pyrrolidone EL: ethyl lactate DMSO: dimethyl sulfoxide GBL: γ-butyrolactone γ-valerolactone MDMPA: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd.) toluene: toluene CP: cyclopentanone CH: cyclohexanone

[0283] <Evaluation> [Evaluation of CTE (Coefficient of Thermal Expansion)] The resin composition or comparative composition prepared in each Example and Comparative Example was applied in the form of a layer on a copper substrate by spin coating, to form a resin composition layer or comparative composition layer. The copper substrate on which the resulting resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes, to form a resin composition layer or comparative composition layer with a uniform thickness of 10 µm on the copper substrate. In examples marked "M" in the exposure conditions column, the resin composition layer or comparative composition layer on the copper substrate was exposed to 500 mJ / cm using a mask with a dumbbell-shaped exposed portion formed thereon and a stepper as a light source. ２The sample was exposed to light having an exposure wavelength (nm) as shown in the "Exposure Wavelength (nm)" column of the table, with an exposure energy of 100 sq. m / s. The dumbbell shape was a dumbbell No. 7 as described in JIS K 6251:2017. In examples marked "D" in the "Exposure Conditions" column, a direct exposure device (Adtec DE-6UH III) was used as the light source, and laser direct imaging exposure was performed on the dumbbell-shaped area without using a photomask. The resulting layer was then developed with cyclopentanone for 60 seconds and rinsed with PGMEA to obtain a resin layer. In examples marked with a numerical value in the "Cure Temperature" column, the exposed resin composition layer was heated at a rate of 10°C / min under a nitrogen atmosphere using a hot plate. After reaching the temperature listed in the "Cure Temperature (°C)" column of the table, the temperature was maintained for the "Cure Time (min)" period in the table to obtain a cured product. In examples where "IR" is listed in the "Cure Temperature (°C)" column, the resin film obtained in each example was heated in a nitrogen atmosphere at a heating rate of 10°C / min using an infrared lamp heating device (RTP-6, manufactured by Advance Riko Co., Ltd.). After reaching 230°C, the temperature was maintained for the "Cure Time (min)" period shown in the table to obtain a cured product. The cured resin layer (cured product) was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and a dumbbell-shaped cured product (test piece) was peeled off from the silicon wafer (sample width: 2 mm, sample length: 35 mm). The CTE of the test piece prepared above was measured at 25°C to 125°C using a TMA450 (TA Instruments). The heating and cooling conditions for evaluation were as follows (1) to (4): (1) The temperature was raised from room temperature to 130°C at a heating rate of 5°C / min. (2) The temperature was lowered from 130°C to 10°C at a rate of 5°C / min. (3) The temperature was raised from 10°C to 300°C at a rate of 5°C / min. (4) The sample was allowed to cool naturally to room temperature. The elongation (displacement) of the sample was measured during the temperature increase and decrease processes (1) to (4) above, and the elongation (displacement) of the sample at 25°C and 125°C in process (3) was divided by the temperature to calculate the thermal expansion coefficient. (For example, if the length of the sample at 25°C was 50 mm and the length of the sample at 125°C was 50.2 mm, the displacement was calculated as 0.4% = 4000 ppm, and the thermal expansion coefficient was calculated as 4000 / (125-25) = 40 ppm / °C.) The obtained thermal expansion coefficient was evaluated according to the following evaluation criteria, and the evaluation results are shown in the "CTE" column of the table. -Evaluation criteria- A: The thermal expansion coefficient was less than 40 ppm / °C. B: The thermal expansion coefficient was 40 ppm / °C or more and less than 50 ppm / °C. C: The thermal expansion coefficient was 50 ppm / °C or more and less than 60 ppm / °C. D: The thermal expansion coefficient was 60 ppm / °C or more.

[0284] [Evaluation of Elongation at Break] In each Example and Comparative Example, a cured product was obtained in the same manner as in the "Evaluation of CTE" above, except that the photomask or laser direct imaging exposure range was set so that the exposed area was a rectangular region 3 mm wide and 30 mm long. The cured resin composition layer (cured product) was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and the cured product was peeled off from the silicon wafer. The longitudinal elongation of the peeled cured product (a test piece having a sample width of 3 mm and a sample length of 30 mm) was measured using a tensile tester (Tensilon) at a crosshead speed of 300 mm / min, 25°C, and 65% RH (relative humidity) in accordance with JIS K 6251:2017. Each measurement was performed five times, and the arithmetic mean value of the elongation at break (elongation at break) of the test piece from the five measurements was used as the index value. Evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the "Elongation at Break" column in the table. The higher the index value, the better the film strength of the cured product. -Evaluation criteria- A: The index value was 65% or more. B: The index value was 55% or more and less than 65%. C: The index value was less than 55%.

[0285] [Evaluation of Glass Transition Temperature] The Tg of the test pieces prepared in the "Evaluation of Elongation at Break" section above was measured using a DMA850 (TA Instruments). Specifically, the glass transition temperature was measured by changing the temperature conditions of the cured product in the following order (1) to (2). (1) The temperature was increased from 25°C to 350°C at a rate of 5°C / min. (2) The temperature was cooled from 350°C to 25°C. The obtained Tg was evaluated according to the following evaluation criteria. -Evaluation criteria- A: The glass transition temperature was 230°C or higher. B: The glass transition temperature was 180°C or higher but less than 230°C. C: The glass transition temperature was less than 180°C.

[0286] From the above results, it can be seen that the resin composition of the present invention can produce a cured product with a low coefficient of thermal expansion. The comparative composition of Comparative Example 1 does not contain the specific resin. It can be seen that the cured product formed from such a comparative composition has a high coefficient of thermal expansion.

[0287] Example 201 The resin composition used in Example 1 was applied in the form of a layer by spin coating to the surface of the thin copper layer of a resin substrate having a thin copper layer formed on its surface. The resulting layer was dried at 100°C for 5 minutes to form a 20 μm-thick photosensitive film, which was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After the exposure, the film was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern. The temperature was then increased at a rate of 10°C / min in a nitrogen atmosphere until it reached 230°C, at which point it was maintained at 230°C for 180 minutes to form an interlayer insulating film for a redistribution layer. This interlayer insulating film for a redistribution layer had excellent insulating properties. Furthermore, a semiconductor device was manufactured using this interlayer insulating film for a redistribution layer, and it was confirmed to operate without any problems.

Claims

1. A resin composition containing a polyimide precursor which is a copolymer containing a block formed by a repeating unit represented by formula (1-1) and a block formed by a repeating unit represented by formula (1-2); Formula (1-1) and in the formula, A １１ and A １２ are each independently —O— or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R １１ and R １２ are each independently a hydrogen atom or a monovalent organic group, and X １ is a tetravalent organic group, and Y １ represents a divalent organic group, and n1 represents the number of repeating units in the block and is an integer of 2 or more; ２１ and A ２２ are each independently —O— or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R ２１ and R ２２ are each independently a hydrogen atom or a monovalent organic group, and X ２ is a tetravalent organic group, and Y ２ represents a divalent organic group, and n2 represents the number of repeating units in the block and is an integer of 2 or more; １ and X in formula (1-2) ２ Condition 1: The structures of Y in formula (1-1) are different from each other. １ and Y in formula (1-2) ２ and condition 2 that the structures are different from each other.

2. A method for synthesizing a polyimide precursor, which is a copolymer containing a block formed by a repeating unit represented by formula (1-1) and a block formed by a repeating unit represented by formula (1-2), comprising: synthesizing a first block monomer by amidating a first carboxylic acid dianhydride or a compound derived therefrom with a first diamine; synthesizing a second block monomer by amidating a second carboxylic acid dianhydride or a compound derived therefrom with a second diamine; and bonding the first block monomer and the second block monomer. Formula (1-1) and in the formula, A １１ and A １２ are each independently —O— or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R １１ and R １２ are each independently a hydrogen atom or a monovalent organic group, and X １ is a tetravalent organic group, and Y １ represents a divalent organic group, and n1 represents the number of repeating units in the block and is an integer of 2 or more; ２１ and A ２２ are each independently —O— or —NR Ｚ - and R Ｚ is a hydrogen atom or a monovalent organic group, and R ２１ and R ２２ are each independently a hydrogen atom or a monovalent organic group, and X ２ is a tetravalent organic group, and Y ２ represents a divalent organic group, and n2 represents the number of repeating units in the block and is an integer of 2 or more; １ and X in formula (1-2) ２ Condition 1: The structures of Y in formula (1-1) are different from each other. １ and Y in formula (1-2) ２ and condition 2 that the structures are different from each other.

3. The method for synthesizing a polyimide precursor according to claim 2, wherein the number average molecular weight of the first block monomer is 2,000 or more, and the number average molecular weight of the second block monomer is 2,000 or more.

4. A resin composition comprising a polyimide precursor obtained by the method for synthesizing a polyimide precursor according to claim 2.

5. A resin composition comprising a polyimide precursor obtained by the method for synthesizing a polyimide precursor according to claim 3.

6. X in formula (1-1) １ is any of the structures represented by the following formulas (2a) to (2e), or a structure containing a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (2f), and X in formula (1-2) ２ is a structure containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulas (V-1) to (V-4): In formulas (2a) to (2e), *1 to *4 respectively represent bonding sites with the carbonyl group in formula (1-1). １ and L ２ is a divalent linking group. In formula (2f), n1 is an integer of 0 or more. In formula (V-2), R Ｘ１ are each independently a hydrogen atom or an alkyl group which may have a substituent. 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.

7. Y in formula (1-1) １ and Y in formula (1-2) ２ 6. The resin composition according to claim 1, wherein one of the above is a structure derived from an aromatic diamine and the other is a structure derived from an aliphatic diamine.

8. Y in formula (1-1) １ and Y in formula (1-2) ２ The resin composition according to claim 1, 4 or 5, wherein at least one of the above is a group represented by formula (A-3): In formula (A-3), R １ is a hydrogen atom, a halogen atom or a substituent, at least one of which is a bonding site to one of the nitrogen atoms in the formula, R ２ are hydrogen atoms, halogen atoms or substituents, and at least one of them is a bonding site to the other nitrogen atom in the formula.

9. The resin composition according to claim 1, 4 or 5, further comprising a polymerization initiator and a polymerizable compound.

10. The resin composition according to claim 1, 4 or 5, further comprising a base generator.

11. The resin composition according to claim 1, 4 or 5, which is used to form an interlayer insulating film for a rewiring layer.

12. A cured product obtained by curing the resin composition according to claim 1, 4 or 5.

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

14. A method for producing a cured product, comprising a film-forming step of applying the resin composition according to claim 1, 4 or 5 onto a substrate to form a film.

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

16. The method for producing the cured product according to claim 15, further comprising a heating step of heating the film at 50 to 450°C.

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

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

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

20. A polyimide precursor obtained by the method for synthesizing a polyimide precursor according to claim 2 or 3.

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