Resin compositions, cured materials, laminates, methods for manufacturing cured materials, methods for manufacturing laminates, methods for manufacturing semiconductor devices and semiconductor devices, and compounds.

Abstract

A resin composition, a cured material, a laminate, a method for manufacturing the cured material, a method for manufacturing the laminate, a method for manufacturing a semiconductor element, and a semiconductor element, wherein the aforementioned resin composition comprises: a precursor of a cyclized resin; an alkali generating agent having a structure that generates an alkaline compound by means of at least one of light, heat, acid, and alkali, and having two or more polymerizable groups; and a photopolymerization initiator.

Description

Technical Field

[0001] The present invention relates to a resin composition, a cured product, a laminate, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor element, a semiconductor element, and a compound. Prior Art

[0002] Nowadays, resin materials made of resin compositions containing resin are used in various fields. For example, cyclized resins such as polyimide have excellent heat resistance and insulation properties, making them useful in a wide variety of applications. While these applications are not particularly limited, examples include applications in insulating films and sealants for mounting semiconductor devices, as well as protective films. They are also used as base films and cover layers for flexible substrates.

[0003] For example, in the above-mentioned applications, a cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of the cyclized resin such as a polyimide precursor. Such a resin composition is applied to a substrate, for example, by coating to form a photosensitive film, and then subjected to exposure, development, heating, etc. as needed to form a cured product on the substrate. The precursor of the cyclized resin such as a polyimide precursor is cyclized by heating, for example, and becomes a cyclized resin such as polyimide in the cured product. Because resin compositions can be applied using known coating methods, they offer a high degree of design freedom in terms of shape, size, and application location, resulting in excellent manufacturing adaptability. This superior manufacturing adaptability, in addition to the high performance of cyclized resins such as polyimide, further fuels the growing industrial application of these resin compositions.

[0004] For example, Patent Document 1 describes a curable resin composition comprising (A) an alkali-soluble resin, (B) a copolymer resin, (C) a photopolymerization initiator that generates free radicals and a base, (D) an epoxy resin, and (E) a black colorant. The composition is characterized in that the alkali-soluble resin (A) contains (A1) a carboxyl group-containing imide resin, and the content of the black colorant (E) is 1.0% by mass or more relative to the total solid content of the curable resin composition. For example, Patent Document 2 describes a photosensitive resin composition comprising a base generator and a polymer precursor. The base generator generates a base upon exposure to electromagnetic waves and is characterized by having one or more reactive cyclic ether groups and / or reactive cyclic thioether groups as substituents in one molecule. The polymer precursor reacts with an alkaline substance or by heating in the presence of an alkaline substance to promote the reaction of the polymer precursor with the final product.

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2020-148815 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-092329

[0006] In a resin composition used to obtain a cured product, it is desirable that the cured product have excellent elongation at break. Summary of the Invention

[0007] The present invention has as its object to provide a resin composition capable of producing a cured product having excellent elongation at break, 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 a semiconductor device including the method for producing the laminate, and a semiconductor device including the cured product or the laminate; and to provide a novel compound.

[0008] Representative embodiments of the present invention are shown below. <1> A resin composition comprising: Precursor of cyclized resin; A base generator having a structure that generates a basic compound by the action of at least one of light, heat, acid, and base, and having two or more polymerizable groups; and Photopolymerization initiator. <2> like <1> The resin composition, wherein The base generator contains at least one group selected from the group consisting of an amide group, a carbamate group, a urea group, and a quaternary ammonium group. <3> A resin composition comprising: Precursor of cyclized resin; A base generator represented by any one of the following formulas (1-1) to (1-4); and Photopolymerization initiator. [Chemical Formula 1] In formula (1-1), R 11 and R 12 each independently represent a hydrogen atom or a monovalent organic group, R 11 and R 12 may be bonded to form a ring structure, n represents an integer greater than 1, R 13 represents a monovalent organic group, and at least one of the following conditions 1 and 2 is satisfied. Condition 1: n R 11 and n R 12 have a total of 2 or more polymerizable groups Condition 2: R 13 has a total of 2 or more polymerizable groups In formula (1-2), R 21 to R 24 each independently represent a hydrogen atom or a monovalent organic group, R 21 to R 24 have a total of two or more polymerizable groups, at least two of R 21 to R 24 may be bonded to form a ring structure, and A 1 represents a counter anion. In formula (1-3), R 31 to R 33 each independently represent a hydrogen atom or a monovalent organic group, R 31 to R 33 have a total of two or more polymerizable groups, at least two of R 31 to R 33 may be bonded to form a ring structure, and A 2 represents a counter anion. In formula (1-4), R41, R42, R43 and R44 each independently represent a hydrogen atom or a monovalent organic group, R41 and R42 may be bonded to form a ring structure, R43 and R44 may be bonded to form a ring structure, and R41~R44 have a total of two or more polymerizable groups. <4> like <1> to <3> The resin composition of any one of the items The basic compound generated by the above-mentioned base generator does not have a polymerizable group. <5> like <1> to <4> The resin composition of any one of the items The polymerizable group contained in the base generator is an addition-polymerizable group or a ring-opening-polymerizable group. <6> like <1> to <5> The resin composition of any one of the items The polymerizable group contained in the base generator is a group having an ethylenically unsaturated bond. <7> like <1> to <6> The resin composition of any one of the items The polymerizable group contained in the base generator is a (meth)acryloyloxy group. <8> like <1> to <7> The resin composition of any one of the items The above-mentioned base generator is a nonionic compound. <9> A resin composition comprising: Precursor of cyclized resin; A compound represented by the following formula (X); and Photopolymerization initiator. [Chemical Formula 2] In formula (X), R1 and R2 each independently represent a monovalent organic group, R1 and R2 may be bonded to form a ring structure, L1 represents a divalent linking group, X represents a hydroxyl group or a carboxyl group, Cy represents a ring structure, and R3 represents a structure containing a group having two or more ethylenically unsaturated bonds. <10> like <1> to <9> The resin composition of any one of the items The precursor of the cyclized resin is a polyimide precursor. <11> like <1> to <10> The resin composition of any one of the items The precursor of the cyclized resin has a polymerizable group. <12> like <1> to <11> The resin composition described in any one of the above is used to form an interlayer insulating film for a redistribution layer. <13> A hardening material that <1> to <12> The resin composition described in any one of the above is hardened. <14> A laminate comprising two or more layers of <13> The layers are formed by the hardened material, and a metal layer is included between any layers of the layers formed by the hardened material. <15> A method for manufacturing a hardened material, comprising: <1> to <12> The resin composition described in any one of the above is suitable for use in a film forming step of forming a film on a substrate. <16> like <15> The method for manufacturing the cured product comprises an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern. <17> like <15> or <16> The method for manufacturing the cured product includes a heating step of heating the film at 50-450°C. <18> A method for manufacturing a laminate, comprising: <15> to <17> A method for producing a cured product according to any one of the above. <19> A method for manufacturing a semiconductor device, comprising: <15> to <17> A method for producing a cured product according to any one of the preceding claims or <18> A method for manufacturing the laminate. <20> A semiconductor element comprising <13> The hardened material or <14> The laminated body. <21> A compound represented by the following formula (X). [Chemical Formula 3] In formula (X), R1 and R2 each independently represent a monovalent organic group, R1 and R2 may be bonded to form a ring structure, L1 represents a divalent linking group, X represents a hydroxyl group or a carboxyl group, Cy represents a ring structure, and R3 represents a structure containing a group having two or more ethylenically unsaturated bonds. [Effects of the Invention]

[0009] According to the present invention, there are provided a resin composition capable of producing a cured product having excellent elongation at break, a cured product formed 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 a semiconductor device including the method for producing the laminate, a semiconductor device including the cured product or the laminate, and a novel compound. Implementation Method

[0010] Hereinafter, the main embodiments of the present invention will be described. However, the present invention is not limited to the embodiments described. In this specification, a numerical range expressed using the symbol “~” means a range including the numerical values ​​before and after “~” as the lower limit and the upper limit, respectively. In this specification, the term "step" includes not only independent steps, but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved. In this specification, groups (atomic groups) not labeled as substituted or unsubstituted include groups (atomic groups) without substituents and also include groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (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. Examples of light used for exposure include the bright line spectrum of mercury lamps, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams, and other actinic rays or radiation. In this specification, “(meth)acrylate” means both or either “acrylate” and “methacrylate”, “(meth)acrylic acid” means both or either “acrylic acid” and “methacrylic acid”, and “(meth)acryl” means both or either “acryl” and “methacryl”. In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the term "total solids" refers to the total mass of the components of a composition excluding the solvent. Furthermore, the term "solids concentration" refers to the mass percentage of the components other than the solvent relative to the total mass of the composition. Unless otherwise specified, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene-equivalent values. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) connected in series. Furthermore, unless otherwise specified, these molecular weights are measured using THF (tetrahydrofuran) as the eluent. However, in cases where THF is not suitable as an eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can be used. In addition, unless otherwise specified, a UV (ultraviolet) ray detector with a wavelength of 254 nm was used for detection in GPC measurement. In this specification, when the positional relationship of the layers constituting a laminate is described as "upper" or "lower," it suffices that other layers exist above or below the reference layer in the plurality of layers in question. In other words, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer does not need to be in contact with the other layers. Furthermore, unless otherwise specified, the direction in which layers are stacked on a substrate is referred to as "upper," or, in the case of a resin composition layer, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." These up-and-down directions are defined for convenience of explanation in this specification; in actual practice, the "upper" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to that component as each component contained in the composition. Furthermore, unless otherwise specified, the content of each component in the composition represents the total content of all compounds corresponding to that component. In this manual, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, a combination of preferred aspects is a more preferred aspect.

[0011] (Resin composition) The first aspect of the present invention comprises a resin composition comprising: a precursor of a cyclized resin; a base generator (hereinafter also referred to as a "first specific compound") having a structure capable of generating a basic compound by the action of at least one of light, heat, acid, and base, and having two or more polymerizable groups; and a photopolymerization initiator. The second aspect of the present invention comprises a resin composition comprising: a precursor of a cyclized resin; a base generator represented by any one of the following formulas (1-1) to (1-4) (hereinafter also referred to as the "second specific compound"); and a photopolymerization initiator. [Chemical Formula 4] In formula (1-1), R 11 and R 12 each independently represent a hydrogen atom or a monovalent organic group, R 11 and R 12 may be bonded to form a ring structure, n represents an integer greater than 1, R 13 represents a monovalent organic group, and at least one of the following conditions 1 and 2 is satisfied. Condition 1: n R 11 and n R 12 have a total of 2 or more polymerizable groups Condition 2: R 13 has a total of 2 or more polymerizable groups In formula (1-2), R 21 to R 24 each independently represent a hydrogen atom or a monovalent organic group, R 21 to R 24 have a total of two or more polymerizable groups, at least two of R 21 to R 24 may be bonded to form a ring structure, and A 1 represents a counter anion. In formula (1-3), R 31 to R 33 each independently represent a hydrogen atom or a monovalent organic group, R 31 to R 33 have a total of two or more polymerizable groups, at least two of R 31 to R 33 may be bonded to form a ring structure, and A 2 represents a counter anion. In formula (1-4), R41, R42, R43 and R44 each independently represent a hydrogen atom or a monovalent organic group, R41 and R42 may be bonded to form a ring structure, R43 and R44 may be bonded to form a ring structure, and R41~R44 have a total of two or more polymerizable groups.

[0012] The resin composition of the third aspect of the present invention contains: a precursor of a cyclized resin; a compound represented by the following formula (X) (hereinafter also referred to as the "third specific compound"); and a photopolymerization initiator. [Chemical Formula 5] In formula (X), R1 and R2 each independently represent a monovalent organic group, R1 and R2 may be bonded to form a ring structure, L1 represents a divalent linking group, X represents a hydroxyl group or a carboxyl group, Cy represents a ring structure, and R3 represents a structure containing a group having two or more ethylenically unsaturated bonds.

[0013] In the present invention, unless otherwise specified, the first aspect of the resin composition, the second aspect of the resin composition, and the third aspect of the resin composition may be collectively referred to as a "resin composition." Furthermore, unless otherwise specified, the base generator corresponding to any one of the first specific compound, the second specific compound, and the third specific compound may be simply referred to as a "specific compound."

[0014] The resin composition of the present invention is preferably used to form a photosensitive film for exposure and development, and is preferably used to form a film for exposure and development using a developer containing an organic solvent. The resin composition of the present invention can be used to form, for example, insulating films of semiconductor elements, interlayer insulating films for redistribution layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for redistribution layers. In particular, using the resin composition of the present invention to form an interlayer insulating film for a redistribution layer is also one of the preferred aspects of the present invention. Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film for negative-tone development. In the present invention, negative-tone development refers to development in which non-exposed portions are removed by development during exposure and development, and positive-tone development refers to development in which exposed portions 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 later can be used.

[0015] According to the resin composition of the present invention, a cured film having excellent elongation at break can be obtained. The mechanism by which the above effects are achieved is not yet clear, but is speculated as follows.

[0016] Conventionally, polymerizable compounds and polymerization initiators have been used in resin compositions containing cyclized resin precursors to introduce crosslinking structures into the resulting cured product, thereby improving its chemical resistance. To increase the crosslink density in the cured product, the use of polyfunctional polymerizable compounds as the polymerizable compound has been investigated. However, while using a polyfunctional polymerizable compound can increase the crosslink density in the cured product, it can sometimes hinder the cyclization reaction of the cyclized resin precursor, resulting in a decrease in the resulting cured product's elongation at break. This is presumably due to the crosslinked structure reducing the mobility of the ring-closing reaction sites in the precursor and, even when a base generator is used, inhibiting the diffusion of the basic compound due to the crosslinked structure. However, the specific compound in the present invention is a compound that has two or more polymerizable groups and generates a basic compound. By using such a compound, a basic compound can be generated from the polymer obtained after polymerization, and the basic compound can be generated in a nearly uniform state throughout the film, effectively promoting the cyclization reaction of the precursor of the cyclized resin. As a result, it is speculated that a cured product with excellent elongation at break can be obtained. In particular, after the specific compound is polymerized, for example, when developing with a developer, the polymerized specific compound forms a high molecular weight and a cross-linked structure, which is less likely to dissolve in the developer. This is believed to increase the amount of the basic compound generated during cyclization, resulting in a cured product having excellent elongation at break. Furthermore, as described above, the specific compound after polymerization is less likely to dissolve in a developer. Therefore, it is believed that a cured product with excellent elongation at break can be obtained under a wide range of development conditions (e.g., developer type, development time, development temperature, etc.). In other words, when the resin composition of the present invention is used to obtain a cured product through a process including exposure and development, it is believed that the cured product has a wide range of robustness to development conditions.

[0017] Furthermore, by using the above-mentioned multifunctional polymerizable compound together with a photopolymerization initiator, it is possible to easily implement an embodiment in which the multifunctional polymerizable compound is polymerized by exposure and developed, and then the precursor of the cyclized resin is cyclized by heating or the like. By performing polymerization by exposure and cyclization by heating or the like in separate steps, both the crosslinking density and the cyclization reaction rate can be increased. That is, it is believed that the resin composition of the present invention can provide a cured product having both excellent elongation at break and excellent chemical resistance. Furthermore, since the specific compound has two or more polymerizable groups, the crosslinking density in the cured product is also increased as described above. Therefore, it is believed that the cured product obtained from the resin composition of the present invention also has excellent chemical resistance.

[0018] Here, Patent Documents 1 and 2 do not describe a composition containing all of a precursor of a cyclized resin, a specific compound, and a photopolymerization initiator.

[0019] Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

[0020] <Specific resin> The resin composition of the present invention contains a precursor of a cyclized resin (specific resin). The cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure. In the present invention, the main chain refers to the relatively longest bond chain in the resin molecule. Examples of the cyclized resin include polyimide, polybenzoxazole, and polyamidoimide. The precursor of the cyclized resin refers to a resin that undergoes a change in chemical structure due to external stimulation to become a cyclized resin. A resin that undergoes a change in chemical structure due to heat to become a cyclized resin is preferred, and a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a cyclized resin is even more preferred. Examples of the precursor of the cyclized resin include polyimide precursors, polybenzoxazole precursors, and polyamide imide precursors. That is, the resin composition of the present invention preferably contains at least one resin (specific resin) selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamide imide precursor as the specific resin. The resin composition of the present invention preferably contains a polyimide precursor as the specific resin. Furthermore, the specific resin preferably has a polymerizable group, and more preferably contains a radical polymerizable group. When the specific resin has a free radical polymerizable group, the resin composition of the present invention preferably contains a free radical polymerization initiator, as described below. It is more preferred that the resin composition contains both the free radical polymerization initiator and the free radical crosslinker, as described below. Furthermore, if necessary, a sensitizer, as described below, may be contained. For example, a negative-type photosensitive film can be formed from such a resin composition of the present invention. Furthermore, the specific resin may have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-degradable group, the resin composition of the present invention preferably contains a photoacid generator as described below. Such a resin composition of the present invention can be used to form, for example, a chemically amplified positive-type photosensitive film or a negative-type photosensitive film.

[0021] 〔Polyimide precursor〕 The type of polyimide precursor used in the present invention is not particularly limited, but preferably contains a repeating unit represented by the following formula (2). [Chemical Formula 6] In formula (2), A1 and A2 each independently represent an oxygen atom or -NH-, R111 represents a divalent organic group, R115 represents a tetravalent organic group, and R113 and R114 each independently represent a hydrogen atom or a monovalent organic group.

[0022] In formula (2), A1 and A2 each independently represent an oxygen atom or -NH-, preferably an oxygen atom. R in formula (2) represents a divalent organic group. Examples of the divalent organic group include groups containing linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. A linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred. The hydrocarbon group in the chain of the linear or branched aliphatic group may be substituted with a group containing a heteroatom, and the hydrocarbon group of the ring member of the cyclic aliphatic group and aromatic group may be substituted with a group containing a heteroatom. As a preferred embodiment of the present invention, groups represented by -Ar- and -Ar-L-Ar- can be exemplified, and a group represented by -Ar-L-Ar- is particularly preferred. However, Ar is independently an aromatic group, and L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a group consisting of two or more of the foregoing. The preferred ranges are as described above.

[0023] R 111 is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. A single diamine may be used, or two or more may be used. Specifically, diamines containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof are preferred, and diamines containing an aromatic group having 6 to 20 carbon atoms are even more preferred. The hydrocarbon groups in the linear or branched aliphatic groups may be substituted with groups containing heteroatoms, and the hydrocarbon groups in the ring members of the cyclic aliphatic and aromatic groups may be substituted with groups containing heteroatoms. Examples of groups containing aromatic groups include the following aromatic groups.

[0024] [Chemical Formula 7] In the formula, A represents a single bond or a divalent linking group, preferably a single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, -SO2-, -NHCO-, or a combination thereof, more preferably a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C(=O)-, -S-, or -SO2-, further preferably -CH2-, -O-, -S-, -SO2-, -C(CF3)2-, or -C(CH3)2-. Where * indicates the bonding site with other structures.

[0025] Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, or 1,6-diaminohexane; 1,2-diaminocyclopentane, 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, or isophoronediamine; m-phenylenediamine, p-phenylenediamine, diaminotoluene, 4,4'-diamino Biphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane or 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfonium or 3,3'-diaminodiphenylsulfonium, 4,4'-diaminodiphenyl sulfide or 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy- 4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfonium, bis(4-amino-3-hydroxyphenyl)sulfonium, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfonium, bis[4-(3-aminophenoxy)phenyl]sulfonium, bis[4-(2-aminophenoxy)phenyl]sulfonium, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfonium, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminoisopropylbenzene or 2,5-diaminoisopropylbenzene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2, 7-Diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetradecafluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2 -bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis At least one diamine selected from the group consisting of (4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2',5,5',6,6'-hexafluorotoluidine, and 4,4'-diaminoquaterphenyl.

[0026] Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017 / 038598 are also preferred.

[0027] Furthermore, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017 / 038598 can also be preferably used.

[0028] From the perspective of the flexibility of the resulting organic film, R is preferably represented by -Ar-L-Ar-. However, each Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO2-, or -NHCO-, or a combination of two or more of the foregoing. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms that may be substituted with a fluorine atom, -O-, -CO-, -S-, or -SO2-. The aliphatic hydrocarbon group is preferably an alkylene group.

[0029] Furthermore, from the viewpoint of i-ray transmittance, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and easy availability, a divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 8] In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in formula (2). Examples of the monovalent organic group represented by R 50 to R 57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. [Chemical Formula 9] In formula (61), R 58 and R 59 are each independently a fluorine atom, a methyl group or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in formula (2). Examples of the diamine that imparts the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These can be used alone or in combination of two or more.

[0030] R 115 in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * independently represents a bonding site with other structures. [Chemical Formula 10] In formula (5), R 112 is a single bond or a divalent linking group. A single bond or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO 2-, and -NHCO-, and a combination thereof is preferred. A single bond, a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, and -SO 2- is more preferred. A divalent group selected from the group consisting of -CH 2-, -C(CF 3) 2-, -C(CH 3) 2-, -O-, -CO-, -S-, and -SO 2- is further preferred.

[0031] Specifically, R 115 includes a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride. The polyimide precursor may contain only one tetracarboxylic dianhydride residue as a structure corresponding to R 115, or may contain two or more. Tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 11] In formula (O), R 115 represents a tetravalent organic group. The preferred range of R 115 is the same as that of R 115 in formula (2), and the preferred range is also the same.

[0032] Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-6 alkyl derivatives and C1-6 alkoxy derivatives thereof.

[0033] Furthermore, as preferred examples, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017 / 038598 can also be mentioned.

[0034] In formula (2), at least one of R 111 and R 115 may also have an OH group. More specifically, R 111 includes a residue of a bisaminophenol derivative.

[0035] In formula (2), R 113 and R 114 each independently represent 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. Furthermore, it is preferred that at least one of R 113 and R 114 contains a polymerizable group, and it is even more preferred that both contain polymerizable groups. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, free radicals, or the like, and a free radical 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 free radical 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., vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III). The group represented by the following formula (III) is preferred.

[0036] [Chemical Formula 12]

[0037] In formula (III), R 200 represents a hydrogen atom, a methyl group, an ethyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site with other structures. In formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2CH(OH)CH 2-, a cycloalkylene group, or a polyalkyleneoxy group. Preferred examples of R 201 include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, -CH 2 CH (OH) CH 2 -, and polyalkylene groups. Alkylene groups such as ethylene and propylene, -CH 2 CH (OH) CH 2 -, cyclohexyl, and polyalkylene groups are more preferred. Alkylene groups such as ethylene and propylene, or polyalkylene groups are even more preferred. In the present invention, a polyalkoxyl group refers to a group formed by directly bonding two or more alkoxyl groups. The alkylene groups in the multiple alkoxyl groups contained in the polyalkoxyl group may be the same or different. When the polyalkoxyl group contains a plurality of alkoxyl groups having different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be random, block-like, or alternating. The carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the above-mentioned alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. The number of alkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the perspective of solvent solubility and solvent resistance, polyalkyleneoxy groups are preferably polyethyleneoxy groups, polypropyleneoxy groups, polytrimethyleneoxy groups, polytetramethyleneoxy groups, or groups formed by bonding multiple ethyleneoxy groups to multiple propyleneoxy groups. Polyethyleneoxy groups or polypropyleneoxy groups are more preferred, and polyethyleneoxy groups are even more preferred. In these groups formed by bonding multiple ethyleneoxy groups to multiple propyleneoxy groups, the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, in blocks, or in an alternating pattern. Preferred aspects of the number of repetitions of the ethyleneoxy group and the like in these groups are as described above.

[0038] In formula (2), when R 113 is a hydrogen atom or when R 114 is a hydrogen atom, the polyimide precursor can form a conjugate base 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.

[0039] In formula (2), at least one of R113 and R114 may be a polarity-converting group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is a group that decomposes by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. An acetal group, a ketal group, a silyl group, a silyl ether group, or a tertiary alkyl ester group is preferred. From the perspective of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-degradable group include a tertiary butoxycarbonyl group, an isopropyloxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tertiary butoxycarbonylmethyl group, and a trimethylsilyl ether group. From the perspective of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

[0040] Furthermore, the polyimide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more and preferably 20% by mass or less.

[0041] Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

[0042] The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including a repeating unit represented by formula (2-A) in the polyimide precursor, the exposure latitude can be further expanded. Formula (2-A) [Chemical Formula 13] In formula (2-A), A1 and A2 represent oxygen atoms, R111 and R112 each independently represent a divalent organic group, R113 and R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of R113 and R114 is a group containing a polymerizable group, and it is preferred that both are groups containing a polymerizable group.

[0043] A1, A2, R111, R113 and R114 are independently synonymous with A1, A2, R111, R113 and R114 in formula (2), and the preferred ranges are also the same. R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.

[0044] The polyimide precursor may contain one or more repeating units represented by formula (2). Furthermore, it may contain structural isomers of the repeating units represented by formula (2). Furthermore, in addition to the repeating units of formula (2), the polyimide precursor may also contain other types of repeating units.

[0045] In one embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all the repeating units. A total content of 70 mol% or more is more preferred, 90 mol% or more is even more preferred, and greater than 90 mol% is particularly preferred. There is no particular upper limit to the total content, and all repeating units in the polyimide precursor, excluding the terminal units, may be repeating units represented by formula (2).

[0046] The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000-100,000, more preferably 10,000-50,000, and even more preferably 15,000-40,000. Furthermore, the number average molecular weight (Mn) is preferably 2,000-40,000, more preferably 3,000-30,000, and even more preferably 4,000-20,000. The molecular weight dispersity of the polyimide precursor is preferably 1.5 or greater, more preferably 1.8 or greater, and even more preferably 2.0 or greater. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited; for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. In this specification, the molecular weight dispersity is a value calculated by weight average molecular weight / number average molecular weight. Furthermore, when the resin composition contains multiple polyimide precursors as specific resins, it is preferred that the weight average molecular weight, number average molecular weight, and dispersibility of at least one polyimide precursor be within the aforementioned ranges. Furthermore, it is also preferred that the weight average molecular weight, number average molecular weight, and dispersibility of the multiple polyimide precursors, calculated as a single resin, be within the aforementioned ranges.

[0047] 〔Polybenzoxazole precursor〕 As the polybenzoxazole precursor, the compounds described in paragraphs 0049 to 0074 of International Publication No. 2021 / 172420 can be used. The contents of these publications are incorporated into this specification.

[0048] [Polyamide imide precursor] As polyamide imide precursors, compounds described in paragraphs 0075 to 0093 of International Publication No. 2021 / 172420 can be used. The contents of these compounds are incorporated into this specification.

[0049] [Method for producing polyimide precursors, etc.] Polyimide precursors and the like can be obtained by, for example, reacting tetracarboxylic dianhydride with a diamine at low temperature, reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamide, and then esterifying the obtained product using a condensing agent or an alkylating agent, obtaining a diester from tetracarboxylic dianhydride and an alcohol, and then reacting the obtained product with a diamine in the presence of a condensing agent, or obtaining a diester from tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the obtained product with a diamine. Among the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and then reacting the obtained product with a diamine is more preferred. Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroxyquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agent include thionyl chloride, oxalyl chloride, and phosphine chloride. In the method for producing a polyimide precursor, etc., it is preferred to use an organic solvent during the reaction. The organic solvent may be one or more. The organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing a polyimide precursor, it is preferred to add a basic compound during the reaction. One basic compound may be used, or two or more basic compounds may be used. The basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

[0050] -Capping agent- In methods for producing polyimide precursors, etc., it is preferable to seal the carboxylic anhydride, anhydride derivative, or amine group remaining at the resin terminal of the polyimide precursor, etc., to improve storage stability. When sealing the carboxylic anhydride and anhydride derivative remaining at the resin terminal, examples of the capping agent include those described in paragraph 0131 of International Publication No. 2021100768. This content is incorporated into this specification.

[0051] -Solid precipitation- The production of a polyimide precursor, etc., may include a solid precipitation step. Specifically, after filtering out the water absorption byproducts of the dehydration condensation agent present in the reaction solution, as needed, the resulting polymer component is placed in a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof to precipitate the polymer component as a solid. The solid is then dried to obtain the polyimide precursor, etc. To increase the degree of purification, the steps of redissolving the polyimide precursor, reprecipitating, and drying may be repeated. Furthermore, the step of removing ionic impurities using an ion exchange resin may be included.

[0052] 〔content〕 The content of the specific resin in the resin composition of the present invention is preferably 20% by mass or greater, more preferably 30% by mass or greater, even more preferably 40% by mass or greater, and even more preferably 50% by mass or greater, relative to the total solids 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, relative to the total solids content of the resin composition. The resin composition of the present invention may contain one specific resin or two or more. When containing two or more specific resins, it is preferred that the total amount falls within the above range.

[0053] Furthermore, the resin composition of the present invention preferably contains at least two types of resins. Specifically, the resin composition of the present invention may contain a total of two or more specific resins and other resins described below, or may contain two or more specific resins. It is preferred that the resin composition contain two or more specific resins. When the resin composition of the present invention contains two or more specific resins, for example, it is preferable to contain a polyimide precursor, that is, two or more polyimide precursors having different structures (R 115 in the above formula (2)) derived from dianhydrides.

[0054] <Other resins> The resin composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also simply referred to as "other resins"). 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, styrene-based resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylic resin, a resin composition having excellent coating properties can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained. For example, by adding a (meth)acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizability value (e.g., a polymerizable group content of 1×10-3 mol / g or more per 1g of the resin) to the resin composition, instead of or in addition to the polymerizable compound described below, the coating properties of the resin composition and the solvent resistance of the pattern (cured product) can be improved.

[0055] 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, relative to the total solid content of the resin composition. Furthermore, the content of the other resin in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the resin composition. In a preferred embodiment of the resin composition of the present invention, the content of other resins can also be low. In this embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less relative to the total solids content of the resin composition. The lower limit of this content is not particularly limited, as long as it is 0% by mass or greater. The resin composition of the present invention may contain only one other resin or two or more. When containing two or more resins, it is preferred that the total amount falls within the above range.

[0056] <Specific Compounds> The resin composition of the present invention contains a specific compound.

[0057] The base generator (first specific compound) contained in the resin composition of the first aspect of the present invention has a structure that generates a basic compound by the action of at least one of light, heat, acid, and base, and has two or more polymerizable groups.

[0058] It is preferred that the first specific compound has a structure that generates a basic compound by the action of heat. The second specific compound and the third specific compound each preferably have a structure that generates a basic compound by the action of at least one of light, heat, acid, and base, and more preferably have a structure that generates a basic compound by the action of heat. When the first specific compound has a structure that generates a basic compound by the action of heat, the first specific compound is preferably a structure represented by Formula (1-1) to Formula (1-4) described later or a structure represented by Formula (X). When the specific compound has a structure that generates a basic compound by the action of heat, it is preferably generated by heating at 250°C, more preferably by heating at 220°C, even more preferably by heating at 200°C, particularly preferably by heating at 190°C, and most preferably by heating at 180°C. The lower limit of the temperature for generating the basic compound is not particularly limited; however, from the perspective of storage stability of the composition, for example, a temperature of 100°C or higher is preferred. The following method is used to determine whether a compound A has a structure that generates a basic compound at a certain temperature X°C. After heating 1 mol of Compound A at X°C for 3 hours under 1 atmosphere in a sealed container, the amount of decomposition is quantified by HPLC (high performance liquid chromatography) or other methods. If 0.01 mol or more of a basic compound is produced, Compound A is determined to have produced a basic compound upon heating at X°C. For example, 1H-NMR can be used to confirm whether the produced compound is a basic compound. The amount of the alkaline compound generated is preferably 0.1 mol or more, more preferably 0.5 mol or more. The upper limit of the amount of the alkaline compound generated is not particularly limited, and can be, for example, 1000 mol or less.

[0059] When the first specific compound has a structure that generates a basic compound by the action of light, the first specific compound is preferably a structure represented by Formula (1-1) to Formula (1-4) described below, or a structure represented by Formula (X). Alternatively, the first specific compound may have a structure in which a basic group (e.g., an amino group) is protected by a known photodegradable group. Whether or not a specific compound has a structure that generates a basic compound under the action of light can be determined by the following method. A composition A is prepared by dissolving a specific compound in a solvent. The composition is then irradiated with light having a wavelength of 190 to 800 nm at 1 atmosphere, 25°C, and an illumination intensity of 25 W / cm² for 30 seconds. The decomposition amount is then quantified using methods such as HPLC (high performance liquid chromatography). If 0.01 mol% or more of a basic compound is produced relative to the total molar amount of the specific compound, the specific compound is determined to have produced a basic compound under the action of light. The amount of basic compound produced is preferably 0.1 mol% or more, and more preferably 0.5 mol% or more. The upper limit of the amount of basic compound produced is not particularly limited, but can be, for example, 1000 mol% or less. When the resin composition contains a solvent, the concentration of the specific compound in composition A can be set to the same concentration as that in the resin composition, and the type of solvent in the composition can be set to the same as the solvent contained in the resin composition. Alternatively, when the resin composition does not contain a solvent, the concentration of the specific compound in composition A can be set to approximately 1.0% by mass relative to the total mass of composition A, and the solvent can be N-methyl-2-pyrrolidone, for example.

[0060] When the specific compound has a structure that generates a basic compound by the action of a base, it is preferred that the specific compound has a structure in which a basic group (preferably an amino group) is protected by a base-decomposable protecting group. As the base-degradable protecting group, for example, a known protecting group for an amino group that can be deprotected with a base can be used. As the group in which the amino group is protected by such a protecting group, a group having a carbamate structure is preferred, with 9-fluorenylmethylcarbamate, 1,1-dimethyl-2-cyanomethylcarbamate, p-nitrobenzylcarbamate, or 2,4-dichlorobenzylcarbamate being more preferred. Furthermore, when the specific compound has a structure that generates a basic compound by the action of a base, the specific compound may also be a compound that generates a basic compound by the action of heat. Whether a specific compound generates a basic compound by the action of a base can be determined by the following method. After adding a basic compound to a solution of a specific compound, titration is performed to measure the amine value and make the determination. Specifically, when a composition A is prepared by dissolving a specific compound in a solvent, piperidine or triethylamine is added to composition A at 1 mol / L under 1 atmosphere and 25°C, and conversion with one of the bases produces at least 0.01 mol% of a basic compound relative to the total molar amount of the specific compound, the specific compound is determined to have produced a basic compound by the action of the base. The amount of the basic compound produced is preferably at least 0.1 mol%, and more preferably at least 0.5 mol%. The upper limit of the amount of the basic compound produced is not particularly limited and can be, for example, 1000 mol% or less. The amount of the basic compound produced can be measured by titration and amine value measurement using known methods. When the resin composition contains a solvent, the concentration of the specific compound in composition A can be set to the same concentration as that in the resin composition, and the type of solvent in the composition can be set to the same as the solvent contained in the resin composition. Alternatively, when the resin composition does not contain a solvent, the concentration of the specific compound in composition A can be set to approximately 1.0% by mass relative to the total mass of composition A, and the solvent can be N-methyl-2-pyrrolidone, for example.

[0061] When the specific compound has a structure that generates a basic compound by the action of an acid, it is preferred that the specific compound has a structure in which a basic group (preferably an amino group) is protected by an acid-decomposable protecting group. As the acid-degradable protecting group, for example, a known protecting group for an amino group that is deprotected with acid can be used. As the group protecting the amino group with such a protecting group, a group having a carbamate structure is preferred, and a carbamate group derived from a tertiary alkoxy group having 5 to 10 carbon atoms is more preferred. In addition, a structure in which the amino group is protected by a tertiary butoxycarbonyl group can also be preferably used. Furthermore, when the specific compound has a structure that generates a basic compound by the action of an acid, the specific compound may also be a compound that generates a basic compound by the action of heat. Whether a specific compound generates a basic compound by the action of an acid can be determined by the following method. After adding an acid to a solution of a specific compound, titration is performed and the acid value is measured. This is done by measuring how much of the added acid is neutralized by the generated basic compound. Specifically, when a composition A is prepared by dissolving a specific compound in a solvent, and p-toluenesulfonic acid is added to composition A at 1 mol / L under 1 atmosphere and 25°C, and a basic compound is produced at a concentration of 0.01 mol% or more relative to the total molar amount of the specific compound, the specific compound is determined to have produced a basic compound through the action of a base. The amount of the basic compound produced is preferably 0.1 mol% or more, and more preferably 0.5 mol% or more. The upper limit of the amount of the basic compound produced is not particularly limited and can be, for example, 1000 mol% or less. The amount of the basic compound produced can be measured by titration and acid value measurement using a known method. When the resin composition contains a solvent, the concentration of the specific compound in composition A can be set to the same concentration as that in the resin composition, and the type of solvent in the composition can be set to the same as the solvent contained in the resin composition. Alternatively, when the resin composition does not contain a solvent, the concentration of the specific compound in composition A can be set to approximately 1.0% by mass relative to the total mass of composition A, and the solvent can be N-methyl-2-pyrrolidone, for example.

[0062] The first specific compound contains two or more polymerizable groups. Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a hydroxymethyl group. The polymerizable group contained in the first specific compound is preferably an addition-polymerizable group such as a group having an ethylenically unsaturated bond or a ring-opening polymerizable group such as an epoxy group or an oxetane group, more preferably an addition-polymerizable group, and even more preferably a group having an ethylenically unsaturated bond. Preferred groups 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., vinylphenyl group), a (meth)acrylamide group, or a (meth)acryloxy group. Vinylphenyl group or a (meth)acryloxy group is more preferred, and a (meth)acryloxy group is even more preferred. The structures of the two or more polymerizable groups contained in the first specific compound may be the same or different. Here, the embodiment in which the first specific compound contains two or more (meth)acryloyloxy groups is also one of the preferred embodiments of the present invention. The number of polymerizable groups contained in the first specific compound is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4. Furthermore, an aspect in which the first specific compound has only two polymerizable groups is also one of the preferred aspects of the present invention.

[0063] It is preferred that the first specific compound contains at least one group selected from the group consisting of an amide group, a carbamate group, a urea group, and a quaternary ammonium group. Furthermore, the first specific compound is preferably a compound that generates a basic compound by cleavage of the amide group, the carbamate group, or the urea group.

[0064] In the present invention, an amide group is represented by *-NR AC(=O)-*, where RA represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrocarbon group. Examples of the hydrocarbon group include alkyl groups and aromatic hydrocarbon groups, with alkyl groups being more preferred. Alkyl groups are preferably those having 1 to 10 carbon atoms, and more preferably those having 1 to 4 carbon atoms. RA may also form a ring structure by bonding to a structure bonded to the nitrogen atom side of the amide group. *Preferably, they are all bonded to a carbon atom, and more preferably, they are all bonded to -CR B 2-. RB each independently represents a hydrogen atom or a monovalent organic group. Here, when the first specific compound has an amide group, the structure on the side bonded to the carbon atom of the amide group has two or more polymerizable groups, and it is also a preferred aspect of the present invention that the structure on the side bonded to the nitrogen atom of the amide group does not have the above-mentioned polymerizable group. When the first specific compound has an amide group, it is preferred that amine is generated by cleavage between the nitrogen atom to which RA in the amide group is bonded and the carbon atom in the adjacent carbonyl group.

[0065] In the present invention, the carbamate group is a group represented by *-NR AC(=O)O-*, and RA is as described above. *Preferably, they are all bonded to a carbon atom, and more preferably, they are all bonded to -CR B 2-. RB is as described above. When the first specific compound has a carbamate group, it is preferred that amine is generated by cleavage between the nitrogen atom to which RA in the carbamate group is bonded and the carbon atom in the adjacent carbonyl group.

[0066] In the present invention, the urea group is a group represented by *-NR AC(=O)NR A-*, and RA is as described above. In addition, two RA may be the same or different. *Preferably, they are all bonded to a carbon atom, and more preferably, they are all bonded to -CR B 2-. RB is as described above. When the first specific compound has a urea group, it is preferred that amine is generated by cleavage between at least one of the nitrogen atoms to which RA is bound contained in the urea group and the carbon atom in the adjacent carbonyl group.

[0067] In the present invention, when the first specific compound contains at least one group selected from the group consisting of an amide group, a carbamate group, and a urea group, the first specific compound preferably has a structure represented by Formula (1-1) described below. Furthermore, when the first specific compound contains a urea group, the first specific compound preferably has a structure represented by Formula (1-4) described below.

[0068] In the present invention, the quaternary ammonium group is a group having a structure in which four carbon atoms are bonded to a nitrogen atom, and it is preferred that all of the carbon atoms are part of a hydrocarbon group. In the present invention, when the first specific compound contains a quaternary ammonium group, the first specific compound preferably has a structure represented by the following formula (1-2).

[0069] Furthermore, from the perspective of insulation reliability, the first specific compound is preferably a nonionic compound. Nonionic means that the charge in the composition is less than 1 meq / g. Furthermore, in cases where charge measurement in the composition is difficult, this refers to a charge in N-methyl-2-pyrrolidone of less than 1 meq / g.

[0070] [Formula (1-1) to Formula (1-4)] The base generator (second specific compound) contained in the resin composition of the second aspect of the present invention is a base generator represented by any one of the following formulas (1-1) to (1-4). From the perspective of elongation at break and chemical resistance, the base generator represented by the following formula (1-1) is preferred. That is, it is preferred that the second specific compound is a nonionic compound. The first specific compound is preferably a base generator represented by any one of the following formulas (1-1) to (1-4). Preferred aspects of the polymerizable group contained in the second specific compound are the same as preferred aspects of the polymerizable group in the above-mentioned first specific compound. [Chemical Formula 14] In formula (1-1), R 11 and R 12 each independently represent a hydrogen atom or a monovalent organic group, R 11 and R 12 may be bonded to form a ring structure, n represents an integer greater than 1, R 13 represents a monovalent organic group, and at least one of the following conditions 1 and 2 is satisfied. Condition 1: n R 11 and n R 12 have a total of 2 or more polymerizable groups Condition 2: R 13 has a total of 2 or more polymerizable groups In formula (1-2), R 21 to R 24 each independently represent a hydrogen atom or a monovalent organic group, R 21 to R 24 have a total of two or more polymerizable groups, at least two of R 21 to R 24 may be bonded to form a ring structure, and A 1 represents a counter anion. In formula (1-3), R 31 to R 33 each independently represent a hydrogen atom or a monovalent organic group, R 31 to R 33 have a total of two or more polymerizable groups, at least two of R 31 to R 33 may be bonded to form a ring structure, and A 2 represents a counter anion. In formula (1-4), R41, R42, R43 and R44 each independently represent a hydrogen atom or a monovalent organic group, R41 and R42 may be bonded to form a ring structure, R43 and R44 may be bonded to form a ring structure, and R41~R44 have a total of two or more polymerizable groups.

[0071] -R 11 and R 12- In formula (1-1), at least one of R 11 and R 12 is preferably a monovalent organic group, more preferably R 11 and R 12 are each independently a monovalent organic group, and further preferably R 11 and R 12 are each independently a hydrocarbon group which may have a substituent, or R 11 and R 12 in formula (1-1) are bonded to form a nitrogen-containing aliphatic heterocyclic structure which may have a substituent. When R 11 or R 12 is a hydrocarbon group which may have a substituent, an alkyl group, an aromatic hydrocarbon group, or a group represented by a combination thereof is more preferred, an alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group represented by a combination thereof is further preferred, and an alkyl group having 1 to 10 carbon atoms is particularly preferred. The alkyl group may be linear, branched, or cyclic, but branched alkyl groups (e.g., isopropyl, isobutyl, 2-ethylhexyl, etc.) or cyclic alkyl groups (e.g., cyclohexyl, etc.) are preferred from the perspective of improving elongation at break. The substituent in the above hydrocarbon group is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, and a hydroxyl group.

[0072] Furthermore, R 11 and R 12 in formula (1-1) may be linked to form a ring structure. In the above embodiment, it is preferred that R 11 and R 12 bonded to the same nitrogen atom are linked to form a ring structure. The resulting ring structure is preferably a nitrogen-containing aliphatic heterocyclic structure. Examples thereof include pyrrolidine rings, piperidine rings, quinoline rings, and nortropine rings, each with the nitrogen atom directly bonded to R 11 and R 12 as a ring member. These ring structures may further have substituents. Examples of the substituents include the same substituents as those for the above-mentioned hydrocarbon groups and monovalent hydrocarbon groups.

[0073] Furthermore, when R 11 and R 12 have a total of two or more polymerizable groups, R 11 may have two or more polymerizable groups, R 12 may have two or more polymerizable groups, R 11 and R 12 may each have one polymerizable group, one of R 11 and R 12 may have one polymerizable group and the other may have two or more polymerizable groups, or both R 11 and R 12 may have two or more polymerizable groups. In the above embodiment, at least one of R 11 and R 12 is preferably a hydrocarbon group containing a group having a polymerizable group as a substituent. Preferred embodiments of the hydrocarbon group are the same as those for R 11 and R 12 being hydrocarbon groups. The group having a polymerizable group is preferably a group represented by a combination of one or more polymerizable groups, one or more hydrocarbon groups, and at least one structure selected from the group consisting of -O- and -C(=O)-. Furthermore, as the group having a polymerizable group, a group represented by the following formula (R-1) is preferred. Furthermore, when R 11 and R 12 are linked to form a ring structure, the ring structure may contain a group having a polymerizable group as a substituent. Preferred aspects of the ring structure are the same as those for the ring structure formed by R 11 and R 12. The group having a polymerizable group is preferably a group represented by a combination of one or more polymerizable groups, one or more hydrocarbon groups, and at least one structure selected from the group consisting of -O- and -C(=O)-. Furthermore, the group having a polymerizable group is preferably a group represented by the following formula (R-1). [Chemical Formula 15] In formula (R-1), RP each independently represents a polymerizable group, n represents an integer of 2 or greater, LP represents an n+1-valent linking group, and * represents a bonding site to the above-mentioned hydrocarbon group or ring structure. In formula (R-1), preferred aspects of RP are the same as preferred aspects of the polymerizable group in the first specific compound, and (meth)acryloyloxy is particularly preferred. In formula (R-1), n ​​is preferably an integer of 2 to 10, more preferably an integer of 2 to 6, and even more preferably an integer of 2 to 4. Furthermore, an aspect in which n is 2 is also one of the preferred aspects of the present invention. In formula (R-1), LP is preferably a group represented by a combination of one or more hydrocarbon groups and at least one structure selected from the group consisting of -O- and -C(=O)-. Specific examples of the group represented by formula (R-1) include the following groups, but are not limited thereto. In the following specific examples, * has the same meaning as * in formula (R-1). [Chemical Formula 16]

[0074] -n- In formula (1-1), n ​​is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.

[0075] -R 13- In formula (1-1), R 13 preferably has a ring structure, more preferably has an aromatic ring structure, and even more preferably has a benzene ring structure. In formula (1-1), R 13 preferably contains at least one group selected from the group consisting of a hydroxyl group and a carboxyl group. Among them, in formula (1-1), it is preferred that R 13 contains a ring structure and at least one group selected from the group consisting of hydroxyl and carboxyl groups, and it is even more preferred that it has a ring structure in which at least one group selected from the group consisting of hydroxyl and carboxyl groups is directly bonded or bonded via a methylene group.

[0076] Furthermore, the site of bonding in R13 to the carbonyl group in formula (1-1) is preferably a carbon atom, an oxygen atom, or -NRN-, more preferably a carbon atom. The carbon atom is preferably a carbon atom contained in a hydrocarbon group. RN represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.

[0077] In formula (1-1), when n is 1, from the viewpoint of elongation at break, R 13 is preferably a group represented by the following formula (R-2). [Chemical Formula 17] In formula (R-2), L1 represents a divalent linking group, X represents a hydroxyl group or a carboxyl group, Cy represents a ring structure, and * represents a bonding site to the carbonyl group in formula (1-1).

[0078] In formula (R-2), L1 is preferably a hydrocarbon group or a group consisting of one or more hydrocarbon groups and at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O2)-, and -NR-N-. More preferably, L1 is a hydrocarbon group or a group consisting of one or more hydrocarbon groups and at least one structure selected from the group consisting of -O-, -S-, and -NR-N-. RN above represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group. As the above-mentioned hydrocarbon group, an aliphatic hydrocarbon group is preferred. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, further preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0079] In formula (R-2), Cy represents a ring structure, which may be any of a heterocyclic structure, an aliphatic hydrocarbon ring structure, and an aromatic hydrocarbon ring structure, with an aromatic hydrocarbon ring structure being preferred. As the above-mentioned heterocyclic structure, a heteroaromatic ring structure is preferred. In addition, examples of heteroatoms contained in the heterocyclic structure include oxygen atoms, sulfur atoms, nitrogen atoms, and the like. The aliphatic hydrocarbon ring structure may be a saturated aliphatic hydrocarbon ring structure or an unsaturated aliphatic hydrocarbon ring structure, with a saturated aliphatic hydrocarbon ring structure being preferred. Furthermore, a 6-membered ring or a composite ring structure containing a 6-membered ring structure is preferred. As the aromatic hydrocarbon ring structure, an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms is preferred, and a benzene ring structure is more preferred. In addition, the aromatic hydrocarbon ring structure may have a substituent or may form a condensed ring with another ring structure. Among them, Cy is preferably a 1,2-phenylene group which may have a substituent or a condensed ring.

[0080] In formula (R-2), a hydrogen atom in the hydrocarbon group in L or a hydrogen atom in the ring structure represented by Cy may be substituted with a group having a polymerizable group. The group having a polymerizable group is preferably a group having two or more polymerizable groups, and more preferably a group represented by formula (R-1) above. Among them, it is preferred that the hydrogen atom in the ring structure represented by Cy be substituted by a group having a polymerizable group, more preferred that the hydrogen atom be substituted by a group having two or more polymerizable groups, and even more preferred that the hydrogen atom be substituted by a group represented by the above formula (R-1).

[0081] It is preferred that X in formula (R-2) is a hydroxyl group. Furthermore, in formula (R-2), X and L are preferably present at adjacent positions in ring Cy. Adjacent positions refer to the ring member to which a substituent is bonded and the ring member to which another substituent is bonded in the ring structure being adjacent to each other. In the case of a benzene ring, this refers to the ortho position.

[0082] Furthermore, when X in formula (R-2) is a hydroxyl group, the number of atoms in the shortest path of the linking chain between X and * in L1 and Cy (linking chain length) is preferably 3 to 6, more preferably 3 or 4. When X in formula (R-2) is a carboxyl group, the number of atoms in the shortest path of the linking chain between X and * in L1 and Cy (linking chain length) is preferably 2 to 5, more preferably 2 or 3. Furthermore, it is also preferred that L1 contains an oxygen atom or a sulfur atom in the shortest path. For example, in the following structure, L1 is -CH2-O-, Cy is a benzene ring structure, and the above-mentioned chain length is 4. In the following structure, the hydrogen atom in Cy is substituted by a group represented by formula (R-1). [Chemical Formula 18]

[0083] Specific examples of the group represented by formula (R-2) include the following structures, but are not limited thereto. In the following specific examples, * represents the bonding site to X in formula (R-2), and # represents the bonding site to -C(=O)- in formula (1-1). In these structures, hydrogen atoms in the hydrocarbon group may be substituted with a group having a polymerizable group. [Chemical Formula 19]

[0084] In formula (1-1), when n is 2 or greater, R 13 is preferably a group represented by the following formula (R-3) or a group represented by formula (R-4). [Chemical Formula 20] In formula (R-3), L2 represents an n-valent linking group, Cy represents a ring structure, X represents a hydroxyl group or a carboxyl group, * represents the bonding site to the carbonyl group in formula (1-1), and n represents the same number as in the above formula (1-1). In formula (R-4), Cy represents a ring structure, X represents a hydroxyl group or a carboxyl group, m represents an integer greater than or equal to 1, * represents the bonding site to the carbonyl group in formula (1-1), and n represents the same number as in the above formula (1-1).

[0085] In formula (R-3), L2 is preferably a hydrocarbon group or a group consisting of one or more hydrocarbon groups and at least one structure selected from the group consisting of -O-, -C(=O)-, -S-, -S(=O2)-, and -NR-N-. More preferably, L2 is a hydrocarbon group or a group consisting of one or more hydrocarbon groups and at least one structure selected from the group consisting of -O-, -S-, and -NR-N-. RN above represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group. As the above-mentioned hydrocarbon group, an aliphatic hydrocarbon group is preferred. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, further preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. Furthermore, the hydrogen atoms contained in the hydrocarbon group in L 2 may be substituted with a polymerizable group or a group having a polymerizable group. Specific examples of the group having a polymerizable group include the group represented by the above formula (R-1). In formula (R-3), preferred aspects of the ring structure represented by Cy are the same as preferred aspects of the ring structure represented by Cy in formula (R-2) above. In formula (R-3), preferred aspects of X are the same as preferred aspects of X in formula (R-2) above. In formula (R-3), preferred aspects of n are the same as preferred aspects of n in formula (1-1) above.

[0086] In formula (R-4), preferred aspects of the ring structure represented by Cy are the same as preferred aspects of the ring structure represented by Cy in formula (R-2) above. In formula (R-4), preferred aspects of X are the same as preferred aspects of X in formula (R-2) above. In formula (R-4), preferred aspects of n are the same as preferred aspects of n in formula (1-1) above. In formula (R-4), m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1. Furthermore, m being the same number as n is also a preferred aspect of the present invention.

[0087] Specific examples of the group represented by formula (R-3) or formula (R-4) include the following structures, but are not limited thereto. In the following specific examples, * represents the bonding site to X in formula (R-3) or formula (R-4), and # represents the bonding site to -C(=O)- in formula (1-1). In these structures, hydrogen atoms in the hydrocarbon group may be substituted with a group having a polymerizable group. [Chemical Formula 21]

[0088] Furthermore, the carbonyl group bonded to R 13 and R 13 in formula (1-1) may be an acid-decomposable group or a base-decomposable group. As an aspect of the acid-decomposable group, there can be mentioned an aspect in which R 13 is a tertiary butoxy group. Examples of the alkali-decomposable group include an embodiment in which R 13 is a 9-fluorenylmethoxy group, a 1,1-dimethyl-2-cyanomethoxy group, a p-nitrobenzyloxy group, a 2,4-dichlorobenzyloxy group, and the like.

[0089] -Condition 1, Condition 2- The base generator represented by formula (1-1) may satisfy only condition 1 or both condition 1 and condition 2. From the viewpoint of elongation at break, it is preferable to satisfy only condition 2. Furthermore, it is preferred that the base generator represented by formula (1-1) cleaves between the nitrogen atom to which R 11 and R 12 are bonded and the carbon atom to which R 13 is bonded to generate a basic compound.

[0090] [Formula (1-2)] In formula (1-2), R 21 to R 24 each independently represent a hydrogen atom or a monovalent organic group, preferably at least three of them are monovalent organic groups, and even more preferably all of them are monovalent organic groups. Here, the polymerizable group may be present in two or more of R 21 to R 24. It is also a preferred aspect of the present invention that one of R 21 to R 24 has two or more polymerizable groups. As the group not having a polymerizable group among R 21 to R 24, a hydrocarbon group is preferred, and an alkyl group is more preferred. As the group having a polymerizable group in R21 to R24, a group represented by a combination of one or more polymerizable groups, one or more hydrocarbon groups, and at least one structure selected from the group consisting of -O- and -C(=O)- is preferred. A group represented by a combination of two or more polymerizable groups, one or more hydrocarbon groups, and at least one structure selected from the group consisting of -O- and -C(=O)- is more preferred. Furthermore, as the group having a polymerizable group among R21 to R24, it is preferred that, among the groups represented by a combination of one or more hydrocarbon groups and at least one structure selected from the group consisting of -O- and -C(=O)-, a hydrogen atom of the hydrocarbon group is substituted with a group represented by the above formula (R-1). A1 is preferably at least one selected from the group consisting of carboxylic acid anions, phenolic anions, phosphate anions, and sulfate anions. Carboxylic acid anions are more preferred for the sake of balancing salt stability and thermal decomposition. Specific examples of carboxylic acid anions include maleic acid anions, phthalic acid anions, N-phenyliminodiacetic acid anions, and oxalic acid anions.

[0091] [Formula (1-3)] In formula (1-3), R 31 to R 33 each independently represent a hydrogen atom or a monovalent organic group, preferably at least two of them are monovalent organic groups, and even more preferably all of them are monovalent organic groups. Here, the polymerizable group may be present in two or more of R 31 to R 33. It is also a preferred aspect of the present invention that one of R 31 to R 33 has two or more polymerizable groups. As the group not having a polymerizable group among R 31 to R 33, a hydrocarbon group is preferred, and an alkyl group is more preferred. As the group having a polymerizable group in R 31 to R 33, a group represented by a combination of one or more polymerizable groups, one or more hydrocarbon groups, and at least one structure selected from the group consisting of -O- and -C(=O)- is preferred. A group represented by a combination of two or more polymerizable groups, one or more hydrocarbon groups, and at least one structure selected from the group consisting of -O- and -C(=O)- is more preferred. Furthermore, as the group having a polymerizable group among R 31 to R 33, it is preferred that, among the groups represented by a combination of one or more hydrocarbon groups and at least one structure selected from the group consisting of -O- and -C(=O)-, a hydrogen atom of the hydrocarbon group is substituted with a group represented by the above formula (R-1). Preferred aspects of A2 are the same as preferred aspects of A1 in the above formula (1-2).

[0092] [Formula (1-4)] In formula (1-4), preferred aspects of R 41, R 42, R 43, and R 44 are the same as preferred aspects of R 11 and R 12 in the above formula (1-1). Furthermore, preferred aspects of the ring structure formed by bonding R 41 and R 42 are the same as preferred aspects of the ring structure formed by bonding R 11 and R 12. Furthermore, preferred aspects of the ring structure formed by bonding R 43 and R 44 are the same as preferred aspects of the ring structure formed by bonding R 11 and R 12.

[0093] [Formula (X)] The resin composition according to the third aspect of the present invention contains a compound (third specific compound) represented by the following formula (X). It is also a preferred aspect that the first specific compound and the second specific compound are each a compound represented by formula (X). [Chemical Formula 22] In formula (X), R1 and R2 each independently represent a monovalent organic group, R1 and R2 may be bonded to form a ring structure, L1 represents a divalent linking group, X represents a hydroxyl group or a carboxyl group, Cy represents a ring structure, and R3 represents a structure containing a group having two or more ethylenically unsaturated bonds. In formula (X), preferred aspects of R 1 and R 2 are the same as preferred aspects of R 1 and R 2 in formula (1-1). In formula (X), preferred aspects of L1, Cy and R2 are the same as preferred aspects of L1, Cy and R2 in formula (R-2). In formula (X), R<3> is a group represented by formula (R-1) above, and the polymerizable group is preferably a group having an ethylenically unsaturated bond. Preferred embodiments of the group represented by formula (R-1) and the group having an ethylenically unsaturated bond are as described above.

[0094] [Basic compounds] It is preferred that the basic compound generated from the specific compound is a compound having an amino group. The above-mentioned basic compound may be a compound having two or more amino groups, and preferably a compound having only one amino group. The above-mentioned amine group is preferably a secondary amine group. The basic compound of the amino group-containing compound may be an aliphatic amine or an aromatic amine, with aliphatic amines being preferred. Aliphatic amines are more basic than aromatic amines and therefore are believed to have a greater curing-promoting effect. Furthermore, the basic compound is preferably a cyclic aliphatic amine such as pyrrolidine, piperidine, quinoline, nortropine, or a cyclic aliphatic amine in which a portion of the hydrogen atoms of these compounds are substituted with a substituent. The substituent is not particularly limited, but is preferably an alkyl group, an aromatic hydrocarbon group, or a hydroxyalkyl group. An alkyl group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms is more preferred. An alkyl group having 1 to 4 carbon atoms, a phenyl group, or a hydroxyalkyl group having 2 to 4 carbon atoms is further preferred. Aliphatic amines refer to amines in which all carbon atoms bonded to the nitrogen atom of the amine group are carbon atoms contained in an aliphatic hydrocarbon group. Aromatic amines refer to amines in which at least one of the carbon atoms bonded to the nitrogen atom of the amine group is a carbon atom contained as a ring member in an aromatic group. Furthermore, cyclic aliphatic amines refer to aliphatic amines in which the nitrogen atom of the amine group is contained in an aliphatic ring structure.

[0095] From the viewpoint of elongation at break, it is also preferred that the basic compound generated from the specific compound does not have a polymerizable group. Examples of the polymerizable group include polymerizable groups contained in the above-mentioned specific compounds.

[0096] Furthermore, the basic compound generated from the specific compound may also form a ring structure having the nitrogen atom contained in the amino group as a ring member. The ring structure may be an aliphatic ring structure or an aromatic ring structure, with an aliphatic ring structure being preferred and a saturated aliphatic ring structure being more preferred. The ring structure is preferably a 5-membered or 6-membered ring. Furthermore, the ring structure may be a single ring or a composite ring. Composite rings include condensed rings, cross-linked rings, and spiro rings. The ring structure is preferably a ring structure containing at least one group selected from the group consisting of a ketone group, an ester group, an ether group, an amide group, an imide group, a sulfide group and a ketoxime group, or a ring structure bonded to a hydroxyl group or a carboxyl group. Furthermore, when geometric isomers exist in the above-mentioned ring structure, the cis (cis) isomer is preferred from the viewpoint of the elongation at break of the obtained cured product. The trans isomer has a slightly larger volume around the nitrogen atom than the cis isomer. This is thought to facilitate the proximity of the host compound to the nitrogen atom in the active site of the generated basic compound, enhancing the effect of promoting imidization. Furthermore, since the isomer has sufficient volume to resist reaction with the resin, it is thought that the rectangular shape of the pattern is also maintained. Therefore, it is speculated that the cis isomer maintains other properties compared to the trans isomer and exhibits superior elongation at break.

[0097] The molecular weight of the basic compound generated from the specific compound is preferably 70-1,000, more preferably 80-800, and even more preferably 85-500. The basic compound generated from the specific compound is preferably a basic compound having a conjugate acid pKa of 0 or greater, more preferably 3 or greater, and even more preferably 6 or greater. The upper limit of the pKa of the conjugate acid is not particularly limited, but is preferably 30 or less. pKa refers to the equilibrium constant, Ka, expressed as the negative common logarithm of the dissociation reaction that releases hydrogen ions from an acid. In this specification, unless otherwise specified, pKa values ​​are calculated using ACD / ChemSketch (registered trademark). When there are multiple pKa values ​​of the conjugate acid, it is preferred that at least one of them is within the above range.

[0098] Specific examples of the basic compound generated from the specific compound are not particularly limited, and examples thereof include basic compounds having the following structures. [Chemical Formula 23] Furthermore, the dimethylpiperidine and dimethylpiperidine in the above structure exist as cis and trans isomers, and either isomer may be used. However, the cis isomer is preferred from the perspective of the elongation at break of the resulting cured product. The trans isomer has a slightly larger volume around the nitrogen atom than the cis isomer. This is presumably because the cis isomer allows the substrate compound to more easily approach the nitrogen atom in the active site, enhancing the effect of promoting imidization. Therefore, it is believed that the cis isomer maintains other properties compared to the trans isomer and exhibits superior elongation at break. Furthermore, for structures not included in the above specific examples and having geometric isomers, if the volume around the nitrogen atom increases in the case of the cis isomer, the cis isomer is preferred for the same reason.

[0099] 〔Molecular weight〕 The molecular weight of the specific compound is preferably 200 to 2,000, more preferably 250 to 1,000, and even more preferably 300 to 1,000.

[0100] [Synthesis Method] The specific compound can be synthesized, for example, by the synthesis method described in the Examples below. Alternatively, it can be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.

[0101] Specific examples of the specific compound are not particularly limited, but include M-1 to M-17 used in the Examples.

[0102] The content of the specific compound is preferably 0.1 to 30% by mass relative to the total solids content of the resin composition of the present invention. The lower limit is more preferably 0.2% by mass or greater, more preferably 0.5% by mass or greater, and particularly preferably 2% by mass or greater. The upper limit is more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The specific compound may be used alone or in combination of two or more. When two or more are used in combination, it is preferred that the total amount thereof fall within the above range. Furthermore, in the resin composition of the present invention, the content of the specific compound is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of the specific resin.

[0103] <Organometallic Complex> From the viewpoint of chemical resistance, it is also preferred that the resin composition of the present invention contains an organometallic complex. The organometallic complex may be any organic complex compound containing a metal atom, preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated with a metal atom, and still more preferably a metallocene compound. In the present invention, the metallocene compound refers to an organic metal complex having two cyclopentadienyl anion derivatives which may have substituents as η5-ligands. The organic group is not particularly limited, but is preferably a hydrocarbon group or a group consisting of a hydrocarbon group and a heteroatom. As the heteroatom, an oxygen atom, a sulfur atom, or a nitrogen atom is preferred. In the present invention, it is preferred that at least one of the organic groups is a cyclic group, and it is more preferred that at least two of the organic groups are cyclic groups. The cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and a 5-membered cyclic group is more preferably. The cyclic group may be a hydrocarbon ring or a heterocyclic ring, and a hydrocarbon ring is preferred. As the 5-membered cyclic group, cyclopentadienyl is preferred. Furthermore, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

[0104] The metal contained in the organometallic complex is not particularly limited, but metals corresponding to Group 4 elements are preferred, at least one metal selected from the group consisting of titanium, zirconium and hafnium is more preferred, at least one metal selected from the group consisting of titanium and zirconium is further preferred, and titanium is particularly preferred.

[0105] The organometallic complex may contain two or more metal atoms, or only one metal atom, preferably only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one metal atom or two or more metal atoms.

[0106] The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, further preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.

[0107] The organometallic complex having the ability to initiate photo-radical polymerization is also a preferred aspect of the present invention. In the present invention, "having the ability to initiate photoradical polymerization" means being able to generate free radicals capable of initiating free radical polymerization upon irradiation with light. For example, when a composition containing a free radical crosslinker and an organometallic complex is irradiated with light in a wavelength range where the organometallic complex absorbs light but the free radical crosslinker does not, the ability to initiate photoradical polymerization can be confirmed by confirming whether the free radical crosslinker disappears. To confirm whether this disappearance occurs, appropriate methods can be selected depending on the type of free radical crosslinker, such as IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography). When the organometallic complex has the ability to initiate photoradical polymerization, the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, further preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound. In the case where the organometallic complex does not have the ability to initiate photoradical polymerization, the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds, and hafnocene compounds; more preferably, at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds, and hafnocene compounds; further preferably, at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds; and particularly preferably, a titanocene compound.

[0108] The molecular weight of the organometallic complex is preferably 50-2,000, more preferably 100-1,000.

[0109] Preferred examples of the organometallic complex include compounds represented by the following formula (P). [Chemical Formula 24] In formula (P), M is a metal atom, and R is each independently a substituent. Preferably, the R groups are independently selected from aromatic groups, alkyl groups, halogen atoms and alkylsulfonyloxy groups.

[0110] In formula (P), the metal atom represented by M is preferably an iron atom, a titanium atom, a zirconium atom or a hafnium atom, more preferably a titanium atom, a zirconium atom or a hafnium atom, further preferably a titanium atom or a zirconium atom, and particularly preferably a titanium atom. Examples of the aromatic group in R in formula (P) include aromatic groups having 6 to 20 carbon atoms, preferably aromatic hydrocarbon groups having 6 to 20 carbon atoms, and examples thereof include phenyl, 1-naphthyl, and 2-naphthyl. As the alkyl group in R in formula (P), an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred, and examples thereof include methyl, ethyl, propyl, octyl, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, and cyclopentyl. Examples of the halogen atom in the above-mentioned R include F, Cl, Br, and I. As the alkyl group constituting the alkylsulfonyloxy group in the above-mentioned R, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred, and examples thereof include methyl, ethyl, propyl, octyl, isopropyl, tertiary butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, and cyclopentyl. The above-mentioned R may further have a substituent. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, monoalkylamino groups, dialkylamino groups, monoarylamino groups, and diarylamino groups.

[0111] Specific examples of the organometallic complex are not particularly limited, but include tetraisopropoxytitanium, tetra(2-ethylhexyloxy)titanium, diisopropoxybis(ethyl acetylacetonate)titanium, diisopropoxybis(acetylacetonate)titanium, tetraacetylacetonate titanium, bis(η5-2,4-cyclopentadienyl-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, trimethoxypentamethylcyclopentadienyltitanium, bis(η5-2,4-cyclopentadienyl-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds. [Chemical Formula 25]

[0112] In addition, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018 / 025738 can also be used, but are not limited thereto.

[0113] The content of the organometallic complex is preferably 0.1 to 30% by mass relative to the total solids content of the resin composition of the present invention. The lower limit is more preferably 1.0% by mass or greater, more preferably 1.5% by mass or greater, and particularly preferably 3.0% by mass or greater. The upper limit is more preferably 25% by mass or less. The organometallic complex can be used alone or in combination. When two or more are used, the total amount is preferably within the above range.

[0114] <Polymerizable Compound> The resin composition of the present invention preferably contains a polymerizable compound. Here, the resin composition of the present invention preferably contains a photopolymerization initiator and a polymerizable compound as described below. Furthermore, the polymerizable compounds mentioned here do not include compounds corresponding to the above-mentioned specific compounds. Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.

[0115] 〔Free radical crosslinker〕 The resin composition of the present invention preferably contains a free radical crosslinking agent. A free radical crosslinking agent is a compound having a free radical polymerizable group. Preferred free radical polymerizable groups include those containing an ethylenically unsaturated bond. Examples of such groups include vinyl, allyl, vinylphenyl, (meth)acryl, maleimide, and (meth)acrylamide. Among them, as the group containing an ethylenically unsaturated bond, a (meth)acryl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryl group is more preferred.

[0116] The free 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 free radical crosslinking agent may have three or more ethylenically unsaturated bonds. As the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 6 ethylenically unsaturated bonds is further preferred. Furthermore, from the viewpoint of film strength of the obtained pattern (cured product), it is also preferred that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0117] 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.

[0118] Specific examples of free radical crosslinking agents include the compounds described in paragraphs 0232 to 0238 of International Publication No. 2021 / 172420.

[0119] Commercially available free radical crosslinking agents include, for example, the compounds described in paragraph 0211 of International Publication No. 2021 / 112189, the contents of which are incorporated herein by reference.

[0120] In addition, as free radical crosslinking agents, the compounds described in paragraphs 0241 to 0243 of International Publication No. 2021 / 172420 can be cited.

[0121] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, etc. can be used. Alkene, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO (propylene oxide) adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, other bifunctional acrylates having a urethane bond, and bifunctional methacrylates having a urethane bond. Two or more of these may be used in combination as needed. In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate, and the formula weight of the polyethylene glycol chain is about 200. From the perspective of suppressing warpage associated with elastic modulus control of the pattern (cured product), the resin composition of the present invention can preferably use a monofunctional radical crosslinking agent as the radical crosslinking agent. Preferred examples of monofunctional radical crosslinking agents include 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-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylic acid derivatives; N-vinyl pyrrolidone, N-vinyl caprolactam, and other N-vinyl compounds; and alkenyl glycidyl ethers. As a monofunctional free radical crosslinking agent, a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatilization before exposure. Examples of bifunctional or higher-functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl 1,2,4-benzenetricarboxylate.

[0122] Furthermore, as the free radical crosslinking agent, a free radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U") is also preferred. In the present invention, the urea bond is a bond represented by *-NRNC(=O)-NRN-*, where RN each independently represents a hydrogen atom or a monovalent organic group, and * each represents a bonding site to a carbon atom. In the present invention, the urethane bond is a bond represented by *-OC(=O)-NR N-*, where RN represents a hydrogen atom or a monovalent organic group, and * represents a bonding site to a carbon atom. When the resin composition contains a crosslinking agent U, chemical resistance, resolution, etc. may be improved. The mechanism by which this effect is achieved is not yet clear, but it is thought that, for example, during curing by heating, a portion of the crosslinking agent U is thermally decomposed to generate amines, which promote the cyclization of a precursor of a cyclized resin such as a polyimide precursor. The crosslinking agent U may have only one urea bond or one urethane bond, may have one or more urea bonds and one or more urethane bonds, may have no urethane bond but have two or more urea bonds, or may have no urea bond but have two or more urethane bonds. The total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. Furthermore, when the crosslinking agent U does not have a urethane bond, the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. Furthermore, when the crosslinking agent U does not have a urea bond, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.

[0123] The free radical polymerizable group in the crosslinking agent U is not particularly limited, and examples thereof include vinyl, allyl, (meth)acryl, (meth)acryloxy, (meth)acrylamide, vinylphenyl, and maleimide. Preferred are (meth)acryloxy, (meth)acrylamide, vinylphenyl, and maleimide, and more preferred are (meth)acryloxy. When the crosslinking agent U has two or more free radical polymerizable groups, the structures of the free radical polymerizable groups may be the same or different. The number of radical polymerizable groups in the crosslinking agent U may be only one or two or more, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

[0124] It is also preferred that the crosslinking agent U has at least one of a hydroxyl group, an alkoxy group, an amide group, and a cyano group. From the viewpoint of chemical resistance of the obtained cured film, the hydroxyl group may be an alcoholic hydroxyl group or a phenolic hydroxyl group, but an alcoholic hydroxyl group is preferred. From the viewpoint of chemical resistance of the resulting cured film, the alkoxy group is preferably an alkoxy group having 2 to 20 carbon atoms, more preferably an alkoxy group having 2 to 10 carbon atoms, even more preferably an alkoxy group having 2 to 4 carbon atoms, further preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. The alkoxylene group may be contained as a polyalkoxylene group in the crosslinking agent U. In this case, the number of repetitions of the alkoxylene group is preferably 2 to 10, more preferably 2 to 6. An amide group refers to a bond represented by -C(=O)-NR N-. RN is as described above. When the crosslinker U has an amide group, the crosslinker U may contain, for example, a group represented by RC(=O)-NR N-* or a group represented by *-C(=O)-NR NR. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group. The crosslinking agent U may have two or more structures selected from the group consisting of hydroxyl groups, alkoxy groups (in the case of a polyalkoxy group, a polyalkoxy group), amide groups, and cyano groups in the molecule, but having only one structure in the molecule is also a preferred aspect of the present invention.

[0125] From the viewpoint of compatibility with the specific resin, etc., it is preferred that the crosslinking agent U contains an aromatic group. The aromatic group is preferably directly bonded to the urea bond or urethane bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferably that one of the urea bonds or urethane bonds is directly bonded to the aromatic group. The aromatic group may be an aromatic hydrocarbon group, an aromatic heterocyclic group, or a condensed ring structure thereof, but an aromatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group obtained by removing two or more hydrogen atoms from a benzene ring structure. The aromatic heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocyclic ring in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrilium, pyrimidine, pyrimidinium, and triironium. These rings may be further fused with other rings, such as indole and benzimidazole. Furthermore, as the hetero atom contained in the above aromatic heterocyclic group, a nitrogen atom, an oxygen atom or a sulfur atom is preferred. The aromatic group is preferably included in a linking group that links two or more free radical polymerizable groups, a linking group containing a urea bond or a urethane bond, or a linking group that links at least one group selected from the group consisting of the above-mentioned hydroxyl group, alkoxy group, amide group and cyano group and at least one free radical polymerizable group contained in the crosslinking agent U.

[0126] 〔Molecular weight〕 The molecular weight of the crosslinking agent U is preferably 100-2,000, more preferably 150-1500, and even more preferably 200-900.

[0127] When a free radical crosslinking agent is included, its content is preferably greater than 0% by mass and not more than 60% by mass relative to the total solids content of the resin composition of the present invention. A lower limit of 5% by mass or greater is more preferred. An upper limit of 50% by mass or less is even more preferred, and 30% by mass or less is even more preferred.

[0128] The free radical crosslinking agent may be used alone or in combination of two or more. When two or more are used simultaneously, it is preferred that the total amount thereof fall within the above range.

[0129] 〔Other crosslinking agents〕 The resin composition of the present invention preferably contains other crosslinking agents different from the above-mentioned free radical crosslinking agents. In the present invention, other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents. Preferably, the compound has a plurality of groups in the molecule that accelerate the reaction of forming covalent bonds with other compounds in the composition or their reaction products by the photosensitization of the above-mentioned photoacid generator or photobase generator. Preferably, the compound has a plurality of groups in the molecule that accelerate the reaction of forming covalent bonds with other compounds in the composition or their reaction products by the action of an acid or a base. The acid or base is preferably an acid or base generated by a photoacid generator or a photobase generator in the exposure step. As other crosslinking agents, compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred. Other crosslinking agents include compounds having a structure obtained by reacting amino-containing compounds such as melamine, acetylene carbamide, urea, alkylene urea, and benzoguanamine with formaldehyde or formaldehyde and alcohol, whereby the hydrogen atoms of the amino groups are replaced with acyloxymethyl, hydroxymethyl, or alkoxymethyl groups. The production methods for these compounds are not particularly limited; any compound having the same structure as the compound produced by the above methods may be used. Alternatively, oligomers formed by self-condensation of the hydroxymethyl groups of these compounds may be used. As the above-mentioned amino-containing compounds, a crosslinking agent using melamine is referred to as a melamine-based crosslinking agent, a crosslinking agent using acetylene carbamide, urea or alkylene urea is referred to as a urea-based crosslinking agent, a crosslinking agent using alkylene urea is referred to as an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is referred to as a benzoguanamine-based crosslinking agent. Among them, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of acetylene urea-based crosslinking agents and melamine-based crosslinking agents described below.

[0130] Examples of the compounds containing at least one of an alkoxymethyl group and an acyloxymethyl group in the present invention include compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on a nitrogen atom or a triazole of an aromatic group or the following urea structure. The alkoxymethyl or acyloxymethyl group in the above-mentioned compound preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms, and even more preferably 2 carbon atoms. The total number of alkoxymethyl and acyloxymethyl groups in the above-mentioned compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of the above compound is preferably below 1500, preferably 180-1200.

[0131] [Chemical Formula 26]

[0132] R 100 represents an alkyl group or an acyl group. R 101 and R 102 each independently represent a monovalent organic group, and may be bonded to each other to form a ring.

[0133] Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted with an aromatic group include compounds represented by the following general formula.

[0134] [Chemical Formula 27]

[0135] In the formula, X represents a single bond or a divalent organic group, each R 104 independently represents an alkyl group or an acyl group, and R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to produce an alkali-soluble group (for example, a group that is dissociated by the action of an acid, a group represented by -C(R 4) 2COOR 5 (R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that is dissociated by the action of an acid)). R 105 each independently represents an alkyl group or an alkenyl group, a, b, and c each independently represent 1 to 3, d represents 0 to 4, e represents 0 to 3, f represents 0 to 3, a+d represents 5 or less, b+e represents 4 or less, and c+f represents 4 or less. Examples of R 5 in the group that decomposes to generate an alkali-soluble group by the action of an acid, the group that is dissociated by the action of an acid, and the group represented by -C(R 4) 2COOR 5 include -C(R 36)(R 37)(R 38), -C(R 36)(R 37)(OR 39), and -C(R 01)(R 02)(OR 39). In the formula, R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R 36 and R 37 may be bonded to each other to form a ring. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. The alkyl group may be linear or branched. The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and more preferably a cycloalkyl group having 3 to 8 carbon atoms. The cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring. The aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group. The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and more preferably an aralkyl group having 7 to 16 carbon atoms. The above-mentioned aralkyl group means an aryl group substituted by an alkyl group, and preferred aspects of the alkyl group and the aryl group are the same as those of the above-mentioned alkyl group and the aryl group. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and more preferably an alkenyl group having 3 to 16 carbon atoms. Furthermore, these groups may have a known substituent within the range that the effects of the present invention can be obtained.

[0136] R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0137] As the group that decomposes by the action of an acid to generate an alkali-soluble group, or the group that is dissociated by the action of an acid, a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, etc. are preferred. A tertiary alkyl ester group and an acetal group are more preferred.

[0138] Specific examples of compounds having an alkoxymethyl group include the following structures. Examples of compounds having an acyloxymethyl group include compounds in which the alkoxymethyl group in the following compounds is replaced with an acyloxymethyl group. Examples of compounds having an alkoxymethyl group or an acyloxymethyl group in the molecule include the following compounds, but are not limited to these.

[0139] [Chemical Formula 28]

[0140] [Chemical Formula 29]

[0141] As the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group, a commercially available compound or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a tricyclic ring are preferred.

[0142] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

[0143] Specific examples of the urea-based crosslinking agent include monomethylolated acetylene carbamide, dimethylolated acetylene carbamide, trimethylolated acetylene carbamide, tetramethylolated acetylene carbamide, monomethoxymethylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monoethoxymethylated acetylene carbamide, diethoxymethylated acetylene carbamide, triethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, tripropoxymethylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide, or tetrabutoxymethylated acetylene carbamide; Urea-based crosslinking agents such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, and bisbutoxymethyl urea; Ethylene urea crosslinking agents such as monomethylolated ethylene urea or dimethylolated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea; Propylene urea crosslinking agents such as monomethylolated propylene urea, dimethylolated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea; 1,3-bis(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

[0144] Specific examples of the benzoguanamine-based crosslinking agent include monomethylolated benzoguanamine, dimethylolated benzoguanamine, trimethylolated benzoguanamine, tetramethylolated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

[0145] Furthermore, as the compound having at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used. Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl) benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, and the like.

[0146] As other cross-linking agents, commercially available products can be used. Preferred commercially available products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, and DMOM PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (each manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, hereinafter the same) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (each manufactured by SANWA CHEMICAL CO., LTD.), and the like.

[0147] Furthermore, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another crosslinking agent.

[0148] -Epoxy compounds (compounds having epoxy groups)- Epoxy compounds preferably have two or more epoxy groups per molecule. Epoxy groups undergo crosslinking reactions below 200°C and do not cause dehydration reactions associated with crosslinking, thus minimizing film shrinkage. Therefore, the inclusion of epoxy compounds effectively suppresses low-temperature curing and warping of the resin composition of the present invention.

[0149] The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group refers to a group containing 2 or more repeating ethylene oxide units, preferably 2 to 15 repeating units.

[0150] Specific examples of epoxy compounds include the compounds described in paragraph 0256 of International Publication No. 2021 / 172420.

[0151] Specific examples of the oxetane compound include the compounds described in paragraph 0257 of International Publication No. 2021 / 172420.

[0152] -Benzoxazone compounds (compounds having a benzoxazolyl group)- Benzooxane compounds are preferred because they produce no outgassing during curing due to the cross-linking reaction caused by the ring-opening addition reaction, thereby reducing thermal shrinkage and suppressing warping.

[0153] Preferred examples of benzoxazolium compounds include the compounds described in paragraphs 0258 to 0259 of International Publication No. 2021 / 172420.

[0154] The content of the other crosslinking agent is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, even more preferably 0.5-15% by mass, and particularly preferably 1.0-10% by mass relative to the total solids content of the resin composition of the present invention. The other crosslinking agent may be present in a single species or in two or more species. When two or more other crosslinking agents are present, their total content is preferably within the above range.

[0155] 〔Photopolymerization initiator〕 The resin composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light from the ultraviolet region to the visible region is preferred. Alternatively, an activator that reacts with a photoexcited sensitizer to generate active radicals may be used.

[0156] The photoradical polymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 L·mol-1·cm-1 within a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using known methods. For example, it is preferably measured using a UV-visible spectrophotometer (Varian Cary-5 spectrophotometer) using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0157] As photoradical polymerization initiators, any known compound can be used. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a trioxane skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazoles and oxime derivatives, organic peroxides, sulfur 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, organoboron compounds, and iron arene complexes. For details, see paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, the contents of which are incorporated herein. In addition, examples include paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, photopolymerization initiators described in International Publication No. 2018 / 221177, photopolymerization initiators described in International Publication No. 2018 / 110179, photopolymerization initiators described in JP-A-2019-043864, photopolymerization initiators described in JP-A-2019-044030, and peroxide-based initiators described in JP-A-2019-167313, the contents of which are also incorporated into this specification.

[0158] Examples of ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

[0159] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Laid-Open No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and the contents of these initiators are incorporated into this specification.

[0160] As the α-hydroxyketone-based initiator, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade names: all manufactured by BASF) can be used.

[0161] As the α-aminoketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins BV), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

[0162] As aminoacetophenone-based initiators, acylphosphine oxide-based initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be preferably used. The contents of these compounds are incorporated into this specification.

[0163] Oxime compounds are more preferred as photoradical polymerization initiators. Oxime compounds can effectively improve exposure latitude. Oxime compounds are particularly preferred because they have a wider exposure latitude (exposure margin) and also function as photohardening accelerators.

[0164] Specific examples of oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, compounds described in Japanese Patent Application Laid-Open No. 2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. The compounds described in Technology (1995, pp. 202-232), the compounds described in Japanese Patent Application Laid-Open No. 2000-066385, the compounds described in Japanese Translation of PCT International Publication No. 2004-534797, the compounds described in Japanese Patent Application Laid-Open No. 2017-019766, the compounds described in Japanese Patent No. 6065596, the compounds described in International Publication No. 2015 / 152153, the compounds described in International Publication No. 2017 / 051680, the compounds described in Japanese Patent Application Laid-Open No. 2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, the compounds described in International Publication No. 2013 / 167515, etc., the contents of which are incorporated into this specification.

[0165] Preferred oxime compounds include, for example, compounds having the following structures, or 3-benzyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the resin composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photoradical polymerization initiator) as the photoradical polymerization initiator. Oxime-based photoradical polymerization initiators have a linking group >C=NOC(=O)- in the molecule.

[0166] [Chemical formula 30]

[0167] Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF) and ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, a photoradical polymerization initiator 2 described in JP-A-2012-014052) can also be preferably used. Furthermore, TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. Furthermore, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used. Furthermore, oxime compounds having the following structures can also be used. [Chemical Formula 31]

[0168] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring in a carbazole ring is replaced by a naphthalene ring, and oxime compounds having a fluorine atom, as described in paragraphs 0169-0171 of International Publication No. 2021 / 112189, can also be used. These contents are incorporated into this specification.

[0169] In addition, as photopolymerization initiators, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group-containing substituent bonded to a carbazole skeleton, as described in paragraphs 0208-0210 of International Publication No. 2021 / 020359, can also be used. These contents are incorporated into this specification.

[0170] As a photopolymerization initiator, an oxime compound having an aromatic ring group ArOX1 with an electron-withdrawing group introduced into the aromatic ring (hereinafter also referred to as an oxime compound OX) can also be used. Examples of the electron-withdrawing group possessed by the aromatic ring group ArOX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl and nitro groups are preferred. Acyl groups are more preferred, and benzoyl groups are even more preferred, as they facilitate the formation of a film with excellent light resistance. The benzoyl group may have a substituent. As the substituent, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkenyl group, an alkylthio group, an arylthio group, an acyl group or an amino group is preferred; an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclicoxy group, an alkylthio group, an arylthio group or an amino group is more preferred; and an alkoxy group, an alkylthio group or an amino group is further preferred.

[0171] The oxime compound OX is preferably at least one selected from the group consisting of a compound represented by formula (OX1) and a compound represented by formula (OX2), and more preferably a compound represented by formula (OX2). [Chemical Formula 32] In the formula, RX1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphonyl group, a carbamoyl group, or a sulfonamido group. RX2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthio group, an arylthio group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group, R X3 to R X14 each independently represent a hydrogen atom or a substituent. However, at least one of RX10~RX14 is an electron-withdrawing group.

[0172] In the above formula, RX12 is an electron-withdrawing group, and RX10, RX11, RX13, and RX14 are preferably hydrogen atoms.

[0173] Specific examples of the oxime compound OX include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.

[0174] As the most preferred oxime compounds, there are oxime compounds having specific substituents disclosed in Japanese Patent Application Laid-Open No. 2007-269779 and oxime compounds having thioaryl groups disclosed in Japanese Patent Application Laid-Open No. 2009-191061, the contents of which are incorporated into this specification.

[0175] From the perspective of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyl trisulphite compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.

[0176] More preferred photoradical polymerization initiators are trihalomethyl triphosphine compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. It is further preferred to use at least one compound selected from the group consisting of trihalomethyl triphosphine compounds, α-amino ketone compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds. It is even more preferred to use metallocene compounds or oxime compounds.

[0177] Furthermore, as a photoradical polymerization initiator, the compounds described in paragraphs 0175 to 0179 of International Publication No. 2021 / 020359 can also be used. The contents of these compounds are incorporated into this specification.

[0178] In addition, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015 / 125469 can also be used as the photoradical polymerization initiator, and the contents are incorporated into this specification.

[0179] As a photoradical polymerization initiator, a difunctional, trifunctional, or higher-functional photoradical polymerization initiator can be used. Using such a photoradical polymerization initiator generates two or more free radicals per molecule, thereby achieving excellent sensitivity. Furthermore, when using a compound with an asymmetric structure, crystallinity is reduced, while solubility in solvents is improved, making precipitation less likely over time and thus improving the temporal stability of the resin composition. Specific examples of bifunctional or trifunctional or higher-functional photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015 / 004565, paragraphs 0407 to 0412 of JP-A-2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, and compound (E) described in JP-A-2013-522445. The invention also includes the following: a photopolymerization initiator (G), Cmpd1 to 7 described in International Publication No. 2016 / 034963, an oxime ester photoinitiator described in paragraph 0007 of JP-A-2017-523465, a photoinitiator described in paragraphs 0020 to 0033 of JP-A-2017-167399, a photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342, an oxime ester photoinitiator described in Japanese Patent No. 6469669, and the like, the contents of which are incorporated into this specification.

[0180] When a photopolymerization initiator is present, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, further preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, relative to the total solids content of the resin composition of the present invention. A single photopolymerization initiator may be present, or two or more may be present. When two or more photopolymerization initiators are present, the total amount is preferably within the above range. Furthermore, since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further promoted by heating in an oven or on a hot plate.

[0181] 〔Sensitizer〕 The resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. When the electronically excited sensitizer comes into contact with a thermal radical polymerization initiator or a photoradical polymerization initiator, electron transfer, energy transfer, and heat generation occur. This chemical reaction causes the thermal radical polymerization initiator or the photoradical polymerization initiator to decompose, generating free radicals, acids, or bases. As sensitizers that can be used, compounds such as benzophenone, Michler's ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenathiophene, pyrrolopyrazole azo methine, dibenzopyran, phthalocyanine, benzopyran, and indigo can be used. Examples of the sensitizer include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallyldihydroindanone, and 4,4'-bis(dimethylamino)chalcone. indanone), p-dimethylaminobenzylidenedihydroindanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7 4-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 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-dimethylaminobenzyl)styrene, diphenylacetamide, benzoaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc. In addition, other sensitizing pigments can also be used. For details about the sensitizing dye, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, which is incorporated into this specification.

[0182] When the resin composition contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass relative to the total solids content of the resin composition. The sensitizer may be used alone or in combination of two or more.

[0183] 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, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds containing -SS-, -SO2-S-, -NO-, SH, PH, SiH, and GeH within their molecules, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds containing thiocarbonylthio groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds can generate free radicals by donating hydrogen to low-activity free radicals or by deprotonating them after oxidation. Thiol compounds are particularly preferred.

[0184] Furthermore, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015 / 199219 can also be used as chain transfer agents, and the contents are incorporated into this specification.

[0185] When the resin composition of the present invention 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 solids content of the resin composition of the present invention. The chain transfer agent may be a single type or two or more types. When two or more chain transfer agents are used, their total content is preferably within the above range.

[0186] <Base Generator> The resin composition of the present invention may contain a base generator. Here, a base generator refers to a compound capable of generating a base through physical or chemical action. Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators. However, the base generator corresponding to the above-mentioned specific compound does not correspond to the base generator mentioned here. In particular, when the resin composition contains a precursor for a cyclized resin, it is preferable to include a base generator in the resin composition. By including a thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be accelerated by heating, thereby improving the mechanical properties and chemical resistance of the cured product. This improves the performance of the cured product as an interlayer insulating film for redistribution layers in semiconductor packages, for example. The base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated by the base generator include secondary amines and tertiary amines. The base generator of the present invention is not particularly limited, and known base generators can be used. Examples of known base generators include aminoformyl oxime compounds, aminoformylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, phthalimide derivative compounds, and acyloimide compounds. As the non-ionic base generator, for example, the compound represented by formula (B1) or formula (B2) described in paragraphs 0275 to 0285 of International Publication No. 2021 / 112189, or the compound represented by formula (N1) described in paragraphs 0102 to 00162 of International Publication No. 2020 / 066416 is preferred. Alternatively, the base generator is preferably a thermal base generator described in paragraphs 0013 to 0041 of International Publication No. 2020 / 054226. These contents are incorporated into this specification.

[0187] Examples of the base generator include the following, but the present invention is not limited thereto.

[0188] [Chemical Formula 33]

[0189] 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.

[0190] Specific preferred compounds as ionic base generators include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018 / 038002.

[0191] Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto. [Chemical Formula 34]

[0192] Specific examples of the imide salt include the following compounds, but the present invention is not limited thereto. [Chemical Formula 35]

[0193] When the resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition of the present invention. The lower limit is more preferably 0.3 parts by mass or greater, and even more preferably 0.5 parts by mass or greater. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. The content may be 5 parts by mass or less, or even 4 parts by mass or less. One or more base generators can be used. When two or more base generators are used, the total amount is preferably within the above range. Furthermore, the resin composition of the present invention may be configured to be substantially free of base generators other than the specific compound. Specifically, the content of the base generator excluding the specific compound is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less relative to the total mass of the resin composition. The lower limit is not particularly limited and may be 0% by mass.

[0194] <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, sulfones, amides, ureas, and alcohols.

[0195] Specific examples of the solvent include those described in International Publication No. 2021 / 112189. Examples include ethylene 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, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, and N-cyclohexyl-2-pyrrolidone.

[0196] Regarding the solvent, a mixture of two or more types is also preferred from the viewpoint of improving the properties of the coating surface.

[0197] In the present invention, one solvent selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellulose acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levoglucosinone, and dihydrolevoglucosinone, or a mixed solvent consisting of two or more of these solvents is preferred. The combined use of dimethyl sulfoxide and γ-butyrolactone, or the combined use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

[0198] From the perspective of coating properties, the solvent content is preferably such that the total solids concentration of the resin composition of the present invention is 5-80% by mass, more preferably 5-75% by mass, even more preferably 10-70% by mass, and even more preferably 20-70% by mass. The solvent content can be adjusted depending on the desired coating thickness and coating method.

[0199] The resin composition of the present invention may contain only one solvent or two or more. When containing two or more solvents, it is preferred that the total amount of the solvents is within the above range.

[0200] <Metal Adhesion Improver> The resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivatives, β-ketoester compounds, and amino compounds.

[0201] 〔Silane coupling agent〕 Examples of silane coupling agents include the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Laid-Open No. 2018-173573, the contents of which are incorporated herein. Furthermore, it is also preferred to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358. Furthermore, the following compounds are also preferred as silane coupling agents. In the following formula, Me represents a methyl group, and Et represents an ethyl group.

[0202] [Chemical Formula 36]

[0203] Other silane coupling agents include the compounds described in paragraph 0318 of International Publication No. 2021 / 112189. This content is incorporated into this specification. These can be used alone or in combination of two or more.

[0204] 〔Aluminum-based adhesive additive〕 Examples of aluminum-based adhesion promoters include tris(ethyl acetylacetonate)aluminum, tris(acetylacetonate)aluminum, and ethyl acetylacetonate aluminum diisopropoxide.

[0205] In addition, as other metal adhesion improvers, the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can also be used, and these contents are incorporated into this specification.

[0206] 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. A content above this lower limit improves adhesion between the pattern and the metal layer, while a content below this upper limit improves the pattern's heat resistance and mechanical properties. The metal adhesion improver may be used alone or in combination. When using two or more, their total content is preferably within the above range.

[0207] <Migration Inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By containing the migration inhibitor, the migration of metal ions from the metal layer (metal wiring) into the film can be effectively suppressed.

[0208] Migration inhibitors are not particularly limited, but include compounds having heterocyclic rings (pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, isoxazole, isothiazole, tetrazole, pyridine, thiazolidine, pyrimidine, pyridine, piperidine, piperidine, thiazolidine, 2H-pyran, 6H-pyran, triazolidine), compounds having thioureas and sulfhydryl groups, hindered phenol compounds, salicylic acid derivatives, and hydrazide derivatives. 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.

[0209] Alternatively, an ion capture agent that captures anions such as halogen ions can also be used.

[0210] Other migration inhibitors include, for example, the compounds described in paragraph 0304 of International Publication No. 2021 / 112189. The contents of these are incorporated into this specification.

[0211] Specific examples of the migration inhibitor include the following compounds.

[0212] [Chemical Formula 37]

[0213] 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 %, relative to the total solid content of the resin composition of the present invention.

[0214] The number of migration inhibitors may be one or more. When there are two or more migration inhibitors, the total amount thereof is preferably within the above range.

[0215] <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 radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0216] Specific examples of polymerization inhibitors include compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 2,2,6,6-tetramethylpiperidinyl 1-oxyl radical, and phenoxathiolate. The contents of these compounds are incorporated herein by reference.

[0217] When the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass relative to the total solid content of the resin composition of the present invention.

[0218] The polymerization inhibitor may be one or more. When there are two or more polymerization inhibitors, the total amount thereof is preferably within the above range.

[0219] <Other additives> The resin composition of the present invention may contain various additives as needed, within the scope of achieving 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-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers, and other additives (e.g., defoamers, flame retardants, etc.). Furthermore, the resin composition of the present invention may also contain urea compounds, carbodiimide compounds, or isourea compounds. By appropriately incorporating these components, film properties and other characteristics can be adjusted. For information on these components, see, for example, paragraphs 0183 and later of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013 / 0034812), and paragraphs 0101-0104 and 0107-0109 of Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein. When these additives are incorporated, their total amount is preferably 3% by mass or less of the solids content of the resin composition of the present invention.

[0220] 〔Surfactants〕 As the surfactant, various surfactants can be used, such as fluorine-based surfactants, silicone-based surfactants, hydrocarbon-based surfactants, etc. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0221] By including a surfactant in the resin composition of the present invention, the liquid properties (particularly, fluidity) during preparation of the coating liquid are further enhanced, further improving coating thickness uniformity and liquid conservation. Specifically, when a film is formed using a coating liquid containing a surfactant-containing composition, the interfacial tension between the coating surface and the coating liquid is reduced, improving wettability to the surface and enhancing coating properties. Consequently, a film with a uniform thickness and minimal thickness variations can be more effectively formed.

[0222] Examples of fluorine-based surfactants include compounds described in paragraph 0328 of International Publication No. 2021 / 112189. The contents of these compounds are incorporated into this specification. Fluorine-based surfactants can also preferably be used as fluorine-containing polymer compounds containing repeating units derived from a (meth)acrylate compound having fluorine atoms and repeating units derived from a (meth)acrylate compound having 2 or more (preferably 5 or more) alkoxy groups (preferably ethyleneoxy and propyleneoxy groups). The following compounds can also be exemplified as the fluorine-based surfactants used in the present invention. [Chemical Formula 38]

[0223] The weight average molecular weight of the compound is preferably 3,000-50,000, more preferably 5,000-30,000. Fluorine-based surfactants can also be fluorinated polymers having ethylenically unsaturated bonds in their side chains. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of JP-A-2010-164965, the contents of which are incorporated herein. Commercially available products include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

[0224] The fluorine content of the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass. Fluorine-based surfactants with fluorine contents within this range are effective in terms of uniformity of coating film thickness and liquid conservation, and also have good solubility in the composition.

[0225] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include compounds described in paragraphs 0329 to 0334 of International Publication No. 2021 / 112189. These contents are incorporated into this specification.

[0226] The surfactant may be used alone or in combination of two or more. The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0227] [Higher fatty acid derivatives] In order to prevent polymerization inhibition caused by oxygen, a higher fatty acid derivative such as behenic acid or behenyl amide may be added to the resin composition of the present invention so that it is locally present on the surface of the resin composition of the present invention during the drying process after coating.

[0228] Furthermore, as higher fatty acid derivatives, compounds described in paragraph 0155 of International Publication No. 2015 / 199219 can also be used, and the contents thereof are incorporated into this specification.

[0229] When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solids content of the resin composition of the present invention. The higher fatty acid derivative may be a single type or two or more types. When two or more types of higher fatty acid derivatives are present, their total content is preferably within the above range.

[0230] [Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates free radicals using thermal energy, thereby initiating or accelerating the polymerization reaction of a polymerizable compound. The addition of a thermal radical polymerization initiator further promotes the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance. Furthermore, the aforementioned photopolymerization initiator may also function to initiate polymerization by heat and may be added as a thermal polymerization initiator.

[0231] Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.

[0232] When a thermal polymerization initiator is present, its content is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, and even more preferably 0.5-15% by mass, relative to the total solids content of the resin composition of the present invention. A single thermal polymerization initiator may be present, or two or more may be present. When two or more thermal polymerization initiators are present, the total amount is preferably within the above range.

[0233] 〔Inorganic particles〕 The resin composition of the present invention may also contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, boron nitride, and the like.

[0234] The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The average particle size of the inorganic particles is a primary particle size and a volume average particle size. The volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). In the case of the above measurement difficulties, it can also be measured by centrifugal sedimentation light transmission method, X-ray transmission method, laser diffraction / scattering method.

[0235] 〔UV absorber〕 The composition of the present invention may also contain a UV absorber. Examples of UV absorbers include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and tris(III)-based UV absorbers. Specific examples of ultraviolet absorbers include the compounds described in paragraphs 0341 to 0342 of International Publication No. 2021 / 112189, the contents of which are incorporated into this specification.

[0236] In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may or may not contain a UV absorber. However, when containing a UV absorber, the content of the UV absorber is preferably from 0.001% by mass to 1% by mass, and more preferably from 0.01% by mass to 0.1% by mass, relative to the total solids content of the composition of the present invention.

[0237] [Organic titanium compounds] The resin composition of this embodiment may contain an organic titanium compound. By containing the organic titanium compound, a resin layer with excellent chemical resistance can be formed even when the resin composition is cured at low temperatures.

[0238] Examples of the organic titanium compound that can be used include compounds in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds include compounds described in paragraphs 0345 to 0346 of International Publication No. 2021 / 112189, the contents of which are incorporated into this specification.

[0239] When an organotitanium compound is added, the amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the amount is 0.05 parts by mass or greater, the resulting cured pattern more effectively exhibits excellent heat resistance and chemical resistance. On the other hand, when the amount is 10 parts by mass or less, the storage stability of the composition is further improved.

[0240] [Antioxidant] The composition of the present invention may also contain an antioxidant. By including an antioxidant as an additive, the elongation properties of the cured film and its adhesion to metal materials can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. Specific examples of antioxidants include the compounds described in paragraphs 0348-0357 of International Publication No. 2021 / 112189. This content is incorporated into this specification.

[0241] The antioxidant is preferably added in an amount of 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. An addition amount of 0.1 parts by mass or greater facilitates improved elongation and adhesion to metal materials, even in high-temperature and high-humidity environments. Furthermore, an addition amount of 10 parts by mass or less enhances the sensitivity of the resin composition, for example, through interaction with the photosensitizer. A single antioxidant may be used, or two or more may be used. When two or more antioxidants are used, their combined amount preferably falls within the above range.

[0242] 〔Anti-agglomerating agent〕 The resin composition of this embodiment may contain an anti-agglomerating agent as needed. Examples of the anti-agglomerating agent include sodium polyacrylate.

[0243] In the present invention, the anti-agglomerating agent may be used alone or in combination of two or more. The composition of the present invention may or may not contain an anti-agglomerating agent. When an anti-agglomerating agent is contained, the content of the anti-agglomerating agent is preferably from 0.01% by mass to 10% by mass, and more preferably from 0.02% by mass to 5% by mass, relative to the total solid content of the composition of the present invention.

[0244] 〔Phenolic compounds〕 The resin composition of this embodiment may contain a phenolic compound as needed. Examples of the phenolic compound include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, and BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Yukizai Corporation).

[0245] In the present invention, the phenolic compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain a phenolic compound. When a phenolic compound is contained, the content of the phenolic compound is preferably from 0.01% by mass to 30% by mass, and more preferably from 0.02% by mass to 20% by mass, relative to the total solid content of the composition of the present invention.

[0246] 〔Other polymer compounds〕 Other polymer compounds include silicone resins, (meth)acrylic acid copolymers obtained by copolymerizing (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may also be modified to incorporate crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

[0247] In the present invention, other polymer compounds may be used alone or in combination of two or more. The composition of the present invention may or may not contain other polymer compounds. When containing other polymer compounds, the content of the other polymer compounds is preferably from 0.01% by mass to 30% by mass, and more preferably from 0.02% by mass to 20% by mass, relative to the total solid content of the composition of the present invention.

[0248] <Characteristics of Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by adjusting the solids concentration of the resin composition. From the perspective of coating film thickness, a viscosity of 1,000 mm² / s to 12,000 mm² / s is preferred, 2,000 mm² / s to 10,000 mm² / s is more preferred, and 2,500 mm² / s to 8,000 mm² / s is even more preferred. Within this range, a highly uniform coating film is easily obtained. A viscosity of 1,000 mm² / s or higher facilitates coating to the thickness required for, for example, a redistribution insulation film. A viscosity of 12,000 mm² / s or lower produces a coating film with excellent surface finish.

[0249] <Regarding Restrictions on Substances Contained in Resin Compositions> The resin composition of the present invention preferably has a water content of less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If the water content is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the storage container during storage.

[0250] From the perspective of insulation properties, the metal content of the resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but exclude metals contained as complexes of organic compounds and metals. When multiple metals are present, the total amount of these metals is preferably within the above range.

[0251] Furthermore, as methods for reducing the amount of metal impurities accidentally contained in the resin composition of the present invention, there are methods such as selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention through a filter, lining the interior of an apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions that minimize contamination.

[0252] Regarding the resin composition of the present invention, considering its use as a semiconductor material, the halogen atom content is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the perspective of wiring corrosion resistance. Of these, the halogen atom content in the form of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine atoms and bromine atoms. The total amount of chlorine atoms and bromine atoms, or of chlorine ions and bromide ions, is preferably within the above-mentioned ranges. As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

[0253] Conventional containers can be used as containers for the resin composition of the present invention. Furthermore, to prevent the incorporation of impurities into the raw materials or the resin composition of the present invention, multilayer bottles with six layers of six different resins or bottles with a seven-layer structure of six different resins are also preferably used as containers. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351.

[0254] <Cured Resin Composition> By curing the resin composition of the present invention, a cured product of the resin composition can be obtained. The first aspect of the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. The resin composition is preferably cured by heating, with the heating temperature being more preferably in the range of 120°C to 400°C, further preferably in the range of 140°C to 380°C, and particularly preferably in the range of 170°C to 350°C.

[0255] The cured product of the second aspect of the present invention contains a cyclized resin and a carbonate compound. The cyclized resin is preferably a cyclized resin contained in the resin composition, or a resin whose precursor is modified by heating (for example, a resin cyclized from a precursor of the cyclized resin, a resin in which the polymerizable groups contained in the resin are polymerized with other resins or polymerizable compounds). Preferred aspects of the carbonate compound are the same as those described in the resin composition of the first aspect of the present invention. According to this aspect, the cured product has excellent chemical resistance. As described above, carbonate compounds have high polarity and are therefore difficult to dissolve in organic solvents. Cured materials containing such carbonate compounds are believed to have excellent chemical resistance. In the present invention, the first aspect of the cured product and the second aspect of the cured product are collectively referred to as "cured product". Furthermore, the cured product of the first aspect of the present invention may also contain a carbonate compound.

[0256] From the viewpoint of adhesion to metal, the content of the carbonate compound is preferably 0.001 to 0.100 mass %, more preferably 0.003 to 0.080 mass %, and even more preferably 0.005 to 0.050 mass % relative to the total mass of the cured product of the present invention.

[0257] The form of the cured product of the present invention is not particularly limited and can be selected from various shapes, such as film, rod, sphere, or granular, depending on the intended use. In the present invention, the cured product is preferably in the form of a film. Furthermore, by patterning the resin composition, the shape of the cured product can be selected based on the intended use, such as forming a protective film on a wall surface, forming a through hole for electrical conduction, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation. The cured product (a film formed from the cured product) preferably has a thickness of 0.5 μm or greater and 150 μm or less. The shrinkage of the resin composition of the present invention during curing is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, shrinkage refers to the percentage change in volume of the resin composition before and after curing and can be calculated using the following formula. Shrinkage [%] = 100 - (volume after hardening ÷ volume before hardening) × 100

[0258] <Characteristics of Cured Resin Composition> The cured product of the resin composition of the present invention preferably has an imidization reaction rate of 70% or greater, more preferably 80% or greater, and even more preferably 90% or greater. A cured product having an imidization reaction rate of 70% or greater is sometimes said to have excellent mechanical properties. The cured product of the resin composition of the present invention preferably has an elongation at break of 30% or more, more preferably 40% or more, and even more preferably 50% or more. The cured product of the resin composition of the present invention preferably has a glass transition temperature (Tg) of 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.

[0259] <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. Mixing can be performed by mixing with a stirring blade, mixing with a ball mill, mixing by rotating the pot itself, or the like. The temperature during mixing is preferably 10-30°C, more preferably 15-25°C.

[0260] Furthermore, to remove foreign matter such as dust and particulates from the resin composition of the present invention, filtration using a filter is preferably performed. The filter pore size can be, for example, 5 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferably used. The filter can be pre-cleaned with an organic solvent. During the filtration step, multiple filters can be connected in series or in parallel. When using multiple filters, filters of different pore sizes or materials can be combined. For example, a 1 μm HDPE filter can be connected in series as the first stage, and a 0.2 μm HDPE filter can be connected in series as the second stage. Furthermore, various materials can be filtered multiple times. When filtration is performed multiple times, a cycle filtration process can be employed. Furthermore, filtration can be performed after pressurization. When filtration is performed under pressure, the pressure may be, for example, 0.01 MPa to 1.0 MPa, preferably 0.03 MPa to 0.9 MPa, more preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa. In addition to filtration using a filter, impurity removal using an adsorbent can also be performed. Filter filtration and impurity removal using an adsorbent can also be combined. Known adsorbents can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. Furthermore, after filtering with a filter, the resin composition filled in the bottle may be placed under reduced pressure for degassing.

[0261] (Method for producing hardened product) The method for producing the cured product of the present invention preferably includes a film forming step of applying the resin composition on a substrate to form a film. Furthermore, the method for producing a cured product of the present invention preferably includes the film forming step, an exposure step of selectively exposing the film formed in the film forming step, and a development step of developing the film exposed in the exposure step using a developer to form a pattern. The method for producing a cured product of the present invention preferably includes the film forming step, the exposure step, the development step, and at least one of a heating step of heating the pattern obtained in the development step and a post-development exposure step of exposing the pattern obtained in the development step. Furthermore, it is also preferred that the manufacturing method of the present invention includes the above-mentioned film forming step and the step of heating the above-mentioned film. The following describes the details of each step.

[0262] <Film Formation Step> The resin composition of the present invention can be used in a film forming step of forming a film on a substrate. The method for producing the cured product of the present invention preferably includes a film forming step of applying the resin composition on a substrate to form a film.

[0263] 〔Base material〕 The type of substrate can be appropriately selected depending on the intended use. Examples include, but are not particularly limited to, semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; vapor-deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe (e.g., either a substrate formed of metal or a substrate having a metal layer formed by electroplating or vapor deposition); paper; SOG (Spin-On-Glass); TFT (Thin Film Transistor) array substrates; mold substrates; and electrode plates for plasma display panels (PDPs). In the present invention, semiconductor substrates are particularly preferred, with silicon substrates, Cu substrates, and mold substrates being more preferred. Furthermore, a bonding layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like may be provided on the surface of the substrate. The shape of the substrate is not particularly limited and may be circular or rectangular. The size of the substrate is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in diameter, for example, and 100 to 1000 mm in length, preferably 200 to 700 mm in length, for example, of the short side of the substrate is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in diameter, for example, and 200 to 700 mm in length, for example, of the short side of the substrate is, for example, 100 to 1000 mm in length, preferably 200 to 700 mm in length, for example, of the substrate. As the base material, for example, a plate-shaped base material (substrate) is used, preferably a panel-shaped base material (base plate).

[0264] Furthermore, when a film is formed by applying a resin composition to the surface of a resin layer (for example, a layer formed of a cured product) or the surface of a metal layer, the resin layer or the metal layer becomes a base material.

[0265] As a method of applying the resin composition of the present invention to a substrate, coating is preferred.

[0266] Specifically, applicable 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 perspective of film thickness uniformity, spin coating, slit coating, spray coating, or inkjet coating are more preferred, and from the perspective of film thickness uniformity and productivity, spin coating and slit coating are particularly preferred. By adjusting the solid content concentration of the resin composition and coating conditions according to the method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. In the case of spin coating, for example, the coating can be applied at a rotation speed of 500 to 3,500 rpm for approximately 10 seconds to 3 minutes. Furthermore, a method of transferring a coating film formed by applying the coating film to a temporary support in advance by the above-mentioned applying method onto a substrate can also be applied. Regarding the transfer method, the production method described in paragraphs 0023 and 0036 to 0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Application Laid-Open No. 2006-047592 can also be preferably used in the present invention. Furthermore, a step of removing excess film from the ends of the substrate may be performed. Examples of such a step include edge bead washing (EBR) and backwashing. Furthermore, a pre-wetting step may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate before applying the resin composition.

[0267] <Drying Step> The film may be subjected to a step (drying step) of drying the formed film (layer) for removing the solvent after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may also include a drying step of drying the film formed in the film forming step. Furthermore, it is preferred that the drying step be performed after the film forming step and before the exposure step. The film drying temperature in the drying step is preferably 50°C to 150°C, more preferably 70°C to 130°C, and even more preferably 90°C to 110°C. Drying can also be performed under reduced pressure. The drying time can be, for example, 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and even more preferably 2 minutes to 7 minutes.

[0268] <Exposure Step> The film may be subjected to an exposure step for selectively exposing the film. That is, the method for producing a cured product of the present invention may also include an exposure step of selectively exposing the film formed in the film forming step. Selective exposure means exposing a portion of the film. Selective exposure forms exposed areas (exposed portions) and unexposed areas (non-exposed portions) on the film. The exposure dose is not particularly limited as long as it can cure the resin composition of the present invention. For example, the exposure energy at a wavelength of 365 nm is preferably 50 to 10,000 mJ / cm 2 , and more preferably 200 to 8,000 mJ / cm 2 .

[0269] The exposure wavelength can be appropriately set within the range of 190 to 1,000 nm, preferably 240 to 550 nm.

[0270] Regarding the exposure wavelength, if described in relation to the light source, examples include (1) semiconductor lasers (wavelengths of 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), wide (three wavelengths of g, h, and i rays), (4) excimer lasers, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), F2 excimer lasers (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beams, and (7) second harmonics of YAG lasers at 532 nm and third harmonics at 355 nm. Regarding the resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. This allows for particularly high exposure sensitivity. The exposure method is not particularly limited as long as at least a portion of the film formed from the resin composition of the present invention is exposed, and examples thereof include exposure using a photomask and exposure by laser direct imaging.

[0271] <Post-exposure heating step> The film may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably 1 to 12°C / min, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min from the heating start temperature to the maximum heating temperature. In addition, the heating rate can be appropriately changed during heating. The heating method in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, or the like can be used. Furthermore, it is also preferable to carry out the heating in an environment with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.

[0272] <Development Step> The film after exposure may be subjected to a developing step in which a developing solution is used to form a pattern. That is, the method for producing a cured product of the present invention may include a developing step of developing the film exposed in the exposing step using a developer to form a pattern. By performing development, one of the exposed portion and the non-exposed portion of the film is removed, thereby forming a pattern. Here, the development step in which the non-exposed portion of the film is removed is referred to as negative development, and the development step in which the exposed portion of the film is removed is referred to as positive development.

[0273] 〔Developer〕 As the developer used in the development step, an alkaline aqueous solution or a developer containing an organic solvent can be mentioned.

[0274] When the developer is an aqueous alkali solution, examples of the alkaline compound that can be contained in the aqueous alkali solution include inorganic bases, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. TMAH is more preferred. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, and even more preferably 0.3 to 3 mass % based on the total mass of the developer.

[0275] When the developer contains an organic solvent, the compounds described in paragraph 0387 of International Publication No. 2021 / 112189 can be used as the organic solvent. This content is incorporated into this specification. Preferred alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol. Preferred amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

[0276] When the developer contains an organic solvent, one organic solvent may be used alone or in combination of two or more. 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, more preferably containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide, and most preferably containing cyclopentanone.

[0277] 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 greater, more preferably 70% by mass or greater, even more preferably 80% by mass or greater, and particularly preferably 90% by mass or greater. Alternatively, the content may be 100% by mass.

[0278] The developer may also contain other ingredients. Examples of other components include known surfactants and known defoaming agents.

[0279] [Developer Supply Method] The method for supplying the developer is not particularly limited as long as the desired pattern can be formed. Examples include immersing the film-formed substrate in the developer, immersion development using a nozzle to supply the developer to the film formed on the substrate, and continuous supply of the developer. The type of nozzle is not particularly limited, and examples include straight nozzles, shower nozzles, and spray nozzles. From the perspective of developer penetration, non-image area removal, and manufacturing efficiency, a method of supplying developer through a straight nozzle or a method of continuously supplying developer through a spray nozzle is preferred. From the perspective of developer penetration into the image area, a method of supplying developer through a spray nozzle is even better. Alternatively, the steps of continuously supplying developer through a straight nozzle, rotating the substrate and removing the developer from the substrate, continuously supplying developer through a straight nozzle again after spin drying, rotating the substrate and removing the developer from the substrate may be adopted, and this step may be repeated multiple times. In addition, as a method for supplying the developer in the development step, a step of continuously supplying the developer to the substrate, a step of maintaining the developer in a substantially stationary state on the substrate, a step of vibrating the developer on the substrate using ultrasonic waves, etc., and a combination of these steps can be adopted.

[0280] 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 can be preferably 10°C to 45°C, more preferably 18°C ​​to 30°C.

[0281] In the development step, after the treatment with the developer, the pattern may be cleaned (rinsed) with a rinse solution. Alternatively, a method may be employed in which the rinse solution is supplied before the developer in contact with the pattern has completely dried.

[0282] [Rinse solution] When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse liquid. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.

[0283] When the rinse solution contains an organic solvent, examples of the organic solvent include the same organic solvents as exemplified when the developer contains an organic solvent.

[0284] When the rinse liquid contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, with cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME being more preferred, and cyclohexanone and PGMEA being even more preferred.

[0285] When the rinse liquid contains an organic solvent, preferably 50% by mass or more of the rinse liquid is the organic solvent, more preferably 70% by mass or more of the rinse liquid is the organic solvent, and even more preferably 90% by mass or more of the rinse liquid is the organic solvent. Alternatively, 100% by mass of the rinse liquid may be the organic solvent.

[0286] The rinse may also contain other ingredients. Examples of other components include known surfactants and known defoaming agents.

[0287] [How to supply flushing fluid] There are no particular restrictions on the method of supplying the rinsing liquid as long as the desired pattern can be formed. There are methods such as immersing the substrate in the rinsing liquid, supplying the rinsing liquid by filling the substrate with the liquid, supplying the rinsing liquid to the substrate by spraying, and continuously supplying the rinsing liquid to the substrate by a straight nozzle. From the perspectives of rinse liquid penetration, removal of non-image areas, and manufacturing efficiency, the rinse liquid can be supplied using a shower nozzle, straight nozzle, or spray nozzle. Continuous supply using a spray nozzle is preferred, and from the perspective of rinse liquid penetration into the image area, supply using a spray nozzle is even more preferred. The type of nozzle is not particularly limited, and examples include straight nozzles, shower nozzles, and spray nozzles. That is, the rinsing step is preferably a step of supplying or continuously supplying the rinsing liquid to the exposed film through a straight nozzle, and is more preferably a step of supplying the rinsing liquid through a spray nozzle. In addition, as a method for supplying the rinsing liquid in the rinsing step, a step of continuously supplying the rinsing liquid to the substrate, a step of maintaining the rinsing liquid in a roughly static state on the substrate, a step of vibrating the rinsing liquid on the substrate using ultrasound, etc., and a step combining these can be adopted.

[0288] The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly limited, but can be preferably 10°C to 45°C, more preferably 18°C ​​to 30°C.

[0289] <Heating Step> The pattern obtained by the development step (or the pattern after washing in the case where the washing step is performed) can be subjected to a heating step of heating the pattern obtained by the development step. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the development step. Furthermore, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by other methods without performing the development step or a film obtained by the film formation step. In the heating step, the polyimide precursor or other resin is cyclized to become the polyimide or other resin. Furthermore, crosslinking of unreacted crosslinking groups in the specific resin or a crosslinking agent other than the specific resin is also performed. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450° C., more preferably 150 to 350° C., further preferably 150 to 250° C., further preferably 160 to 250° C., and particularly preferably 160 to 230° C.

[0290] The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by heating using the action of the base generated by the base generator.

[0291] Heating in the heating step is preferably performed at a heating rate of 1-12°C / minute from the heating start temperature to the maximum heating temperature. This heating rate is more preferably 2-10°C / minute, and even more preferably 3-10°C / minute. A heating rate of 1°C / minute or higher ensures productivity and prevents excessive volatilization of the acid or solvent. A heating rate of 12°C / minute or lower mitigates residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, the temperature is preferably increased at a rate of 1 to 8°C / second from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0292] The temperature at the start of heating is preferably 20-150°C, more preferably 20-130°C, and even more preferably 25-120°C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the resin composition of the present invention is applied to a substrate and then dried, this refers to the temperature of the dried film (layer). For example, the temperature is preferably raised from a temperature 30-200°C lower than the boiling point of the solvent contained in the resin composition of the present invention.

[0293] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0294] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, further preferably 100°C or higher, and particularly preferably 120°C or higher. The upper limit of the heating temperature is preferably 350° C. or lower, more preferably 250° C. or lower, and further preferably 240° C. or lower.

[0295] Heating can be performed in stages. For example, the temperature can be raised from 25°C to 120°C at a rate of 3°C / minute, held at 120°C for 60 minutes, then raised from 120°C to 180°C at a rate of 2°C / minute, and held at 180°C for 120 minutes. Furthermore, as described in U.S. Patent No. 9,159,547, it is also preferable to perform the treatment while irradiating with ultraviolet light. This pretreatment step can improve film properties. The pretreatment step can be performed in a short time, from about 10 seconds to 2 hours, preferably from 15 seconds to 30 minutes. Pretreatment can be performed in two or more stages. For example, a first stage pretreatment step can be performed at a temperature between 100 and 150°C, followed by a second stage pretreatment step at a temperature between 150 and 200°C. Furthermore, the heating may be followed by cooling, and the cooling rate at this time is preferably 1 to 5°C / min.

[0296] The heating step is preferably performed under a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, from the perspective of preventing decomposition of the specific resin. An oxygen concentration of 50 ppm (volume ratio) or less is preferred, and 20 ppm (volume ratio) or less is even more preferred. The heating method in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.

[0297] <Post-Development Exposure Step> The pattern obtained by the development step (the pattern after the rinse step in the case of the rinse step) can also be used in the post-development exposure step for exposing the pattern after the development step instead of the above-mentioned heating step or in addition to the above-mentioned heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step for exposing the pattern obtained by the development step. 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. In the post-development exposure step, for example, a cyclization reaction of a polyimide precursor or the like can be promoted by sensitization of a photobase generator, or a detachment reaction of an acid-degradable group can be promoted by sensitization 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, and it is preferred that the entire pattern is exposed. The exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ / cm 2 , more preferably 100 to 15,000 mJ / cm 2 , calculated as exposure energy at a wavelength to which the photosensitive compound has sensitivity. The post-development exposure step can be performed, for example, using the light source used in the above-mentioned exposure step, preferably using broadband light.

[0298] <Metal Layer Formation Step> The pattern obtained by the development step (preferably the pattern provided for at least one of the heating step and the post-development exposure step) can also be provided for the 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 a pattern obtained by the development step (preferably a pattern provided for at least one of the heating step and the post-development exposure step).

[0299] The metal layer is not particularly limited and existing metal types 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.

[0300] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese Patent Application Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, U.S. Patent No. 7,888,181B2, and U.S. Patent No. 9,177,926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations thereof are possible. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electrolytic plating can be used. Preferred electroplating methods include electrolytic plating using copper sulfate or a copper cyanide plating solution.

[0301] The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest portion.

[0302] <Purpose> Examples of the manufacturing method and application fields of the cured product of the present invention include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffering films. Other examples include patterning by etching sealing films, substrate materials (base films or cover layers of flexible printed circuit boards, interlayer insulating films), and insulating films used for actual mounting applications, as described above. For information on these applications, see, for example, "Advanced Functionality and Application Technology of Polyimides," published by Science & Technology Co., Ltd. in April 2008, supervised by Masaaki Kakimoto; "Fundamentals and Development of Polyimide Materials," published by the CMC Technical Library in November 2011; and "Latest Polyimide Fundamentals and Applications," published by the Japan Polyimide / Aromatic Polymer Research Society in August 2010.

[0303] Furthermore, the method for producing the cured product of the present invention or the cured product of the present invention can also be used in the production of offset printing plates, screen printing plates, and other printing plates, in the use of molded parts, and in the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

[0304] (Laminate and method for manufacturing the same) The laminated system of the present invention refers to a structure having a plurality of layers formed of the cured product of the present invention. The laminate of the present invention is a laminate comprising two or more layers formed of a cured product, and may be a laminate comprising three or more layers. Among the two or more layers formed of the cured product contained in the laminate, at least one is a layer formed of the cured product of the present invention. From the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product accompanying such shrinkage, it is also preferred that all the layers formed of the cured product contained in the laminate be layers formed of the cured product of the present invention.

[0305] That is, the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention a plurality of times.

[0306] The laminate of the present invention preferably comprises two or more layers formed of a cured product, and preferably comprises a metal layer between any of the layers formed of the cured product. The metal layer is preferably formed by the metal layer forming step. That is, the method for manufacturing a laminate of the present invention preferably includes a metal layer forming step of forming a metal layer on a layer formed from the cured product between the multiple steps of manufacturing the cured product. The preferred embodiment of the metal layer forming step is as described above. As the laminate, for example, a laminate having a layer structure in which at least three layers, namely, a layer formed of a first cured material, a metal layer, and a layer formed of a second cured material, are laminated in this order can be preferably mentioned. It is preferred that both the layer formed from the first cured product and the layer formed from the second cured product be layers formed from the cured product of the present invention. The resin composition of the present invention used to form the layer formed from the first cured product and the resin composition of the present invention used to form the layer formed from the second cured product may have the same composition or different compositions. The metal layer in the laminate of the present invention can be preferably used as metal wiring such as a redistribution layer.

[0307] <Layering Step> The method for manufacturing the laminate of the present invention preferably includes a lamination step. The lamination step is a series of steps comprising repeating at least one of the following steps: (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step, and post-development exposure step, on the surface of the pattern (resin layer) or metal layer. However, an embodiment may also be employed in which at least one of the following steps: (a) film formation step, (d) heating step, and post-development exposure step is repeated. Furthermore, after at least one of the following steps: (d) heating step and post-development exposure step, (e) metal layer formation step may be included. The lamination step may also include the aforementioned drying step, etc., as appropriate.

[0308] When a further layering step is performed after the buildup step, a surface activation step may be performed after the exposure step, the heating step, or the metal layer formation step. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be discussed later.

[0309] The above lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times. For example, a structure of resin layer having 2 or more layers and 20 or less layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferably a structure of 2 or more layers and 9 or less layers. The composition, shape, film thickness, etc. of the above-mentioned layers can be the same or different.

[0310] In the present invention, it is particularly preferred to form a cured product (resin layer) of the resin composition after providing a metal layer so as to cover the metal layer. Specifically, examples include an embodiment in which (a) a film forming step, (b) an exposure step, (c) a development step, (d) a heating step, and at least one of a post-development exposure step, and (e) a metal layer forming step are sequentially repeated, or an embodiment in which (a) a film forming step, (d) a heating step, and at least one of a post-development exposure step, and (e) a metal layer forming step are sequentially repeated. By alternately performing the steps of laminating the resin composition layer (resin layer) of the present invention and the step of forming the metal layer, the resin composition layer (resin layer) of the present invention and the metal layer can be alternately laminated.

[0311] (Surface activation treatment step) The method for producing the laminate of the present invention preferably includes a surface activation step of performing surface activation treatment on at least a portion of the metal layer and the resin composition layer. The surface activation treatment step is usually performed after the metal layer forming step, but the metal layer forming step can also be performed after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step), after the resin composition layer is subjected to the surface activation treatment step. The surface activation treatment can be performed only on at least a portion of the metal layer, only on at least a portion of the exposed resin composition layer, or on at least a portion of both the metal layer and the exposed resin composition layer. The surface activation treatment is preferably performed on at least a portion of the metal layer, preferably on a portion or the entire area of ​​the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer, the adhesion between the metal layer and the resin composition layer (film) disposed thereon can be improved. Furthermore, it is preferred to perform a surface activation treatment on a portion or all of the exposed resin composition layer (resin layer). By performing a surface activation treatment on the surface of the resin composition layer, adhesion to a metal layer or resin layer disposed on the surface of the activated layer can be improved. In particular, when the resin composition layer is being cured, such as during negative-tone development, it is less susceptible to damage from the surface treatment, thus facilitating improved adhesion. The surface activation treatment can be performed, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189, the contents of which are incorporated herein.

[0312] (Semiconductor device and manufacturing method thereof) The present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention. The present invention also discloses a method for producing the cured product of the present invention or a method for producing a semiconductor device including the method for producing the laminate of the present invention. As a specific example of a semiconductor device in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Application Laid-Open No. 2016-027357, the contents of which are incorporated into this specification.

[0313] (Compound) The compound of the present invention is represented by the following formula (X). [Chemical Formula 39] In formula (X), R1 and R2 each independently represent a monovalent organic group, R1 and R2 may be bonded to form a ring structure, L1 represents a divalent linking group, X represents a hydroxyl group or a carboxyl group, Cy represents a ring structure, and R3 represents a structure containing a group having two or more ethylenically unsaturated bonds. Preferred aspects of the compound of the present invention are the same as preferred aspects of the above-mentioned third specific compound. [Example]

[0314] The present invention is further described in detail below using examples. The materials, amounts, ratios, treatment contents, and steps described in the following examples may be modified 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 by mass.

[0315] <Method for producing a cyclized resin precursor> [Synthesis Example 1: Synthesis of a Cyclized Resin Precursor (Resin 1)] 23.48g of 4,4'-oxydiphthalic dianhydride (ODPA) and 22.27g of diphthalic dianhydride (BPDA) were placed in a separable flask, along with 39.69g of 2-hydroxyethyl methacrylate (HEMA) and 136.83g of tetrahydrofuran. The mixture was stirred at room temperature (25°C). While stirring, 24.66g of pyridine was added to obtain a reaction mixture. After the heat generated by the reaction subsided, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours. Next, under ice cooling, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of tetrahydrofuran was added to the reaction mixture over 40 minutes while stirring. Subsequently, a solution of 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.73 g of tetrahydrofuran was added over 60 minutes while stirring. After stirring at room temperature for another 2 hours, 7.17 g of ethanol was added and stirred for 1 hour, followed by the addition of 136.83 g of tetrahydrofuran. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. The resulting reaction solution was added to 716.21 g of ethanol, forming a precipitate containing a crude polymer. The resulting crude polymer was filtered and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer. The resulting precipitate was filtered and vacuum-dried to obtain 80.3 g of powdered Resin 1. The molecular weight of Resin 1 was measured by gel permeation chromatography (standard polystyrene conversion) and the weight-average molecular weight (Mw) was 20,000. The structure of Resin 1 is estimated to be represented by the following formula (P-1).

[0316] [Synthesis Example 2: Synthesis of a Cyclized Resin Precursor (Resin 2)] 21.2 g of 4,4'-oxydiphthalic anhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 4 hours to synthesize the diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -10°C, and while maintaining the temperature at -10±5°C, 17.0 g of sulfinyl chloride was added over 60 minutes. After dilution with 50 mL of N-methylpyrrolidone, a solution of 12.6 g of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at -10±5°C over 60 minutes. The mixture was then stirred at room temperature for 2 hours. Then, 10.0 g of ethanol was added and stirred at room temperature for 1 hour. Next, 6000 g of water was added to precipitate the polyimide precursor. The precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was filtered and dissolved in 500 g of tetrahydrofuran. 6000 g of water (a poor solvent) was added to the resulting solution to precipitate the polyimide precursor. The precipitate (water-polyimide precursor mixture) was stirred for 15 minutes. The stirred precipitate (solid polyimide precursor) was filtered again and dried at 45°C under reduced pressure for 3 days. After dissolving 46.6 g of the dried powder in 419.6 g of tetrahydrofuran, 2.3 g of triethylamine was added and the mixture was stirred at room temperature for 35 minutes. Then, 3000 g of ethanol was added and the precipitate was collected by filtration. The resulting precipitate was dissolved in 281.8 g of tetrahydrofuran. 17.1 g of water and 46.6 g of ion exchange resin UP6040 (AmberTec) were added to the mixture and stirred for 4 hours. The ion exchange resin was then removed by filtration, and the resulting polymer solution was added to 5,600 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 45.1 g of Resin 2. The structure of Resin 2 is estimated to be represented by the following formula (P-2). The molecular weight of Resin 2 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight-average molecular weight (Mw) was 20,000. Furthermore, by appropriately adjusting the equivalent weight of 4,4'-diaminodiphenyl ether, Resin 2 with Mw of 5,000, Resin 2 with Mw of 10,000, and Resin 2 with Mw of 30,000 were synthesized.

[0317] [Synthesis Examples 3-6: Synthesis of Cyclized Resin Precursors (Resins 3-6)] Resins 3 to 6 having structures represented by any one of the following formulas (P-3) to (P-6) were synthesized by the same method as in Synthesis Example 2 except that the compounds used were appropriately changed. The Mw of resin 3 was 20,000, the Mw of resin 4 was 20,000, the Mw of resin 5 was 20,000, and the Mw of resin 6 was 20,000.

[0318] [Chemical Formula 40] [Chemical Formula 41]

[0319] <Examples and Comparative Examples> In each example, the components listed in the following table were mixed to obtain each resin composition. In the comparative example, the components listed in the following table were mixed to obtain a comparative composition. Specifically, the content (blending amount) of each component described in the table except the solvent is the amount (parts by mass) described in the column of "parts by mass" in each column of the table. The solvent content (blending amount) was adjusted so that the solid content concentration of the composition would be the value (mass %) indicated in the "Solid Content Concentration" column in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvent would be the ratio indicated in the "Ratio" column in the table. The obtained resin composition and the comparative composition were pressure-filtered using a polytetrafluoroethylene filter having a pore width of 0.8 μm. In the tables, “-” indicates that the composition does not contain the corresponding component.

[0320] [Table 1] Example Comparative Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 composition resin type Resin 1 Resin 1 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 Mass price 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 specific compound kinds M-1 MR-1 M-1 M-2 M-3 M-4 M-5 M-6 M-7 M-8 M-9 M-10 M-11 M-12 M-13 M-14 parts by mass 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 polymerizable compounds type MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 parts by mass 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Photoinitiator Type I-2 I-2 I-1 I-1​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ — — — — parts by mass — — — — — — — — — — — — — — — — Polymerization inhibitors type B-2 B-2 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-2 C-2 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migrate inhibitors type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type E-1 E-1 - - - - - - - - - - - - - - parts by mass 2.4 2.4 - - - - - - - - - - - - - - type E-2 E-2 - - - - - - - - - - - - - - parts by mass 0.9 0.9 - - - - - - - - - - - - - - solvent type NMP NMP GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 45 45 40 40 40 40 40 40 40 40 40 40 40 40 40 40 type EL EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid component concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 process order Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M M M M M M developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 evaluate Elongation at break B D B C A A C C B B A B B A A C Chemical resistance B D B A B C C C C A C B B C C B Copper substrate adhesion A C A A B A B B B A B A A A A B

[0321] [Table 2] Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 16 17 18 19 20 twenty one twenty two twenty three twenty four 25 26 27 28 29 30 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 3 Resin 4 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 Specific compounds type M-15 M-16 M-17 M-6 M-1 / M-2 M-1 / M-6 M-1 / MR-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 3 3 3 3 1.5 / 1.5 1.5 / 1.5 1.5 / 1.5 6 1 0.5 3 3 3 3 3 polymerizable compounds type MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 — — — MX-1 MX-1 MX-1 MX-1 MX-1 parts by mass 3 3 3 3 3 3 3 — — — 3 3 3 3 3 Photopolymerization initiator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Base generator type — — — A-1 — — — — — — A-1 A-2 A-3 — — parts by mass — — — 2 — — — — — — 2 2 2 — — Polymerization inhibitors type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migrate inhibitors type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 kinds DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid component concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 process order Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M M M M M developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 evaluate Elongation at break B C B A B B C A C C B A A B B Chemical resistance A C C B A B A C B C A C C B B Copper substrate adhesion A B B A A B B A B B A A B A A

[0322] [Table 3] Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 composition resin type Resin 5 Resin 6 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 / Resin 3 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 30,000 10000 5000 20000 20000 20000 / 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 25 45 17 / 17 35 35 35 35 35 35 35 Specific compounds type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 polymerizable compounds type MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 parts by mass 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Photopolymerization initiator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-2 I-3 I-1 / I-2 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 0.5 3 2 2 0.6 / 0.6 1.1 1.1 Base generator type — — — — — — — — — — — — — — — parts by mass — — — — — — — — — — — — — — — Polymerization inhibitors type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.05 0.5 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 migrate inhibitors type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - type - - - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - - - solvent type GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL GBL ratio 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 type DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 program Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 405 365 365 365 Exposure conditions M M M M M M M M M M M D M M M developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 evaluate Elongation at break B B C A A B B B A C B B B B A Chemical resistance B B B A A B B B C A B A B B C Copper substrate adhesion A A B A A A A A A A A A A A A

[0323] [Table 4] Example Example Example Example Example Example Example Example Example Example Example Example Example Example Example 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 35 35 Specific compounds type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 polymerizable compounds type MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 parts by mass 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 Photoinitiator Type I-1 I-1 I-1 I-1 I-1 I-1 I-1 [[ID=四十二]] I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Parts by mass 1.1 1.1 1.1 1.1 1.1 At 1.1 1.1 1.1 1.1 1.1 1.1 1.1 鹼產生劑 1.1 1.1 Base generator Type — — — — — — — — — — — — — — — parts by mass — — — — — — — — — — — — — — — Polymerization inhibitors type B-2 B-3 B-4 B-1 / B-2 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.05 / 0.05 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 C-1 C-2 C-3 C-1 / C-2 C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 0.5 3 1 1 0.5 / 0.5 1 1 1 1 1 1 migrate inhibitors type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-2 D-3 D-4 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 additive type - - - - - - - - - - - - E-3 E-4 E-5 parts by mass - - - - - - - - - - - - 2 2 2 type - - - - - - - - - - - - - - - parts by mass - - - - - - - <00039​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ DMSO DMSO DMSO ratio 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 42 42 program Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M M M M M developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions burden burden burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 180 180 180 180 180 180 180 180 180 180 180 180 180 180 180 evaluate Elongation at break B B B B B B B B B B B B B B B Chemical resistance B B B B B B B B B B B B A A A Copper substrate adhesion A A A A A A A A A A A A A A A

[0324] [Table 5] Example Example Example Example Example Example Example Example Example Example Example Example Example 61 62 63 64 65 66 67 68 69 70 71 72 73 composition resin type Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Resin 2 Mw 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 20000 parts by mass 35 35 35 35 35 35 35 35 35 35 35 35 35 Specific compounds type M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 M-1 parts by mass 3 3 3 3 3 3 3 3 3 3 3 3 3 polymerizable compounds type MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 MX-1 parts by mass 3 3 3 3 3 3 3 3 3 3 3 3 3 Photopolymerization initiator type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 parts by mass 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Base generator type — — — — — — — — — — — — — parts by mass — — — — — — — — — — — — — Polymerization inhibitors type B-1 B-1 B-1 B-1 B-1 B-1 - B-1 B-1 B-1 B-1 B-1 B-1 parts by mass 0.1 0.1 0.1 0.1 0.1 0.1 - 0.1 0.1 0.1 0.1 0.1 0.1 Silane coupling agent type C-1 C-1 C-1 C-1 C-1 - - C-1 C-1 C-1 C-1 C-1 C-1 parts by mass 1 1 1 1 1 - - 1 1 1 1 1 1 migrate inhibitors type D-1 D-1 D-1 D-1 - - - D-1 D-1 D-1 D-1 D-1 D-1 parts by mass 0.2 0.2 0.2 0.2 - - - 0.2 0.2 0.2 0.2 0.2 0.2 additive type E-6 - - - - - - - - - - - - parts by mass 0.1 - - - - - - - - - - - - type - - - - - - - - - - - - - parts by mass - - - - - - - - - - - - - Solvent Type GBL GBL GBL NMP GBL GBL GBL GBL GBL GBL GBL <00°4520> GBL GBL Ratio 40 30 10 <0°4526> 20 40 40 40 40 40 40 40 ạ0 40 Type DMSO DMSO DMSO EL DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO DMSO Ratio 10 It should be noted that there may be some inaccuracies in the above translation due to the lack of clear context for some symbols and abbreviations. If possible, it is recommended to provide more detailed information for a more accurate translation. 20 40 35 10 10 10 10 10 10 10 10 10 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 42 42 program Film thickness (μm) 20 20 20 20 20 20 20 30 10 20 20 20 20 Exposure wavelength (nm) 365 365 365 365 365 365 365 365 365 365 365 365 365 Exposure conditions M M M M M M M M M M M M M developer Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Cyclopentanone Development conditions burden burden burden burden burden burden burden burden burden burden burden burden burden Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 200 180 160 IR Hardening time (min) 180 180 180 180 180 180 180 180 180 120 120 120 180 evaluate Elongation at break B B B B B B B C A B C C B Chemical resistance B B B B B B B B B B B C B Copper substrate adhesion A A A A B B B A A A B B A

[0325] The details of each component listed in the table are as follows.

[0326] 〔Resin〕 Resin 1 to Resin 6: Resin 1 to Resin 6 obtained by the above synthesis example

[0327] 〔Specific compounds〕 M-1 to M-17: Compounds of the following structures. M-1 to M-17 correspond to the above-mentioned specific compounds. In this specification, a bond that intersects the side of a ring structure represents a bond to the ring structure that replaces any of the omitted hydrogen atoms in the ring structure. In addition, MR-1 used in Comparative Example 1 is a polymerizable compound. [Chemical Formula 42] [Chemical Formula 43]

[0328] -Synthesis of M-2- In a flask, 22.4 g (198.2 mmol) of cis-2,6-dimethylpiperidine and 187.6 g (0.7 M (mol / L)) of dichloromethane were stirred at 0°C, followed by the dropwise addition of 20.0 g (99.1 mmol) of bromoacetyl bromide. After the addition was complete, the solution was warmed to room temperature and stirred for 2 hours. The reaction solution was then added to 250 mL of water. After stirring for 15 minutes, the organic layer was separated and recovered, then washed twice with 100 mL of water. The organic layer was dried over sodium sulfate, and the solvent was removed by distillation under reduced pressure, yielding 21.6 g of M-2-A as a solid (93% yield). M-2-A was used in the next reaction without further purification. The physical properties of M-2-A are shown below. 1H-NMR (400MHz, DMSO-d6) δ=4.51(bs,1H),4.30-3.91(m,3H),1.84-1.73(m,1H),1.73-1.47(m,4H),1.46-1.39(m,1H),1.39-1.06(m,6H). In a flask, 24.9 g (161.7 mmol) of vanillyl alcohol and 253.0 g (0.5 M) of acetonitrile were stirred at room temperature, followed by the addition of 26.8 g (194.0 mmol) of potassium carbonate. After the addition of 37.9 g (161.7 mmol) of M-2-A, the solution was heated to 75°C and stirred for 6 hours. After air cooling to room temperature, the solid was removed by vacuum filtration, and the filtrate was distilled off under reduced pressure to obtain a crude solid product. After dissolving the product in 500 mL of ethyl acetate, the organic layer was fractionated and washed once with 240 mL of 1N (1 mol / L) aqueous HCl solution, and then three times with 240 mL of water. The organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude oily product. Purification was performed by silica gel column chromatography (hexane / ethyl acetate = 1 / 1 eluent), followed by removal of the solvent under reduced pressure to obtain 26.5 g of solid M-2-B (53% yield). The physical properties of M-2-B are shown below. 1H-NMR(400MHz,DMSO-d6)δ=6.93(d,1H,J=1.2Hz),6.81-6.76(m,2H),5.07(t,1H,J=5.8Hz),4.81(bs,1H),4.65(bs,1H),4.53(bs, 1H),4.41(d,2H,J=5.7Hz),4.13(bs,1H),3.76(s,3H),1.86-1.75(m,1H),1.75-1.48(m,4H),1.47-1.40(m,1H),1.40-1.04(m,6H). In a flask, 12.0 g (39.0 mmol) of M-2-B and 51.7 g (1 M) of dichloromethane were stirred at 0°C, followed by the dropwise addition of 156 mL of a 1 M dichloromethane solution of boron tribromide (156.0 mmol). After the addition, the solution was warmed to room temperature and stirred for 3 hours. The reaction solution was added to 500 mL of water, followed by 47.0 g of methanol, and stirred for 1 hour. 250 g of dichloromethane was added, and the organic layer was recovered by separation and washed twice with 200 mL of water. The organic layer was dried over sodium sulfate, and the solvent was removed by distillation under reduced pressure, yielding 13.6 g of solid M-2-C (98% yield). The physical properties of M-2-C are as follows. 1H-NMR (400MHz, CDCl 3)δ=9.95(s,1H),7.01(d,1H,J=2.2Hz),6.94(d,1H,J=8.2Hz),6.82(dd,1H,J=8.2,2.2Hz),4.75(b,3H,J=7. 6Hz),4.42(s,2H),3.75(bs,1H),1.88-1.77(m,1H),1.77-1.57(m,4H),1.56-1.49(m,1H),1.41-1.15(m,6H). To a flask were added 0.037 mg of TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl), 30.0 g (16.8 mmol) of M-2-C, 6.7 g (16.8 mmol) of M-2-D, and 41.9 g (0.2 M) of acetonitrile. After stirring at room temperature, 3.5 g (25.3 mmol) of potassium carbonate was added. The solution was heated to 60°C and stirred for 6 hours. After air cooling to room temperature, the solids were removed by filtration under reduced pressure, and the filtrate was distilled off under reduced pressure to obtain an oily crude product. After adding and dissolving 200 g of ethyl acetate, the product was separated and washed twice with an aqueous solution of 2.1 g of sodium bicarbonate dissolved in 200 mL of water, and the organic layer was separated and washed once with 200 mL of water. The organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily crude product. Purification was performed by silica gel column chromatography (hexane / ethyl acetate = 2 / 1 eluent, target product: hexane / ethyl acetate = 1 / 1, Rf = 0.38). The solvent was removed by distillation under reduced pressure to obtain 3.7 g of M-2 as an oil (33% yield). The physical properties of M-2 are shown below. 1H-NMR(400MHz,DMSO-d6)δ=9.58(s,1H),6.87(d,1H,J=8.2Hz),6.79(d,1H,J=2.0Hz),6.72(dd, 1H,J=8.2,2.0Hz),6.35(dd,3H,J=17.2,1.4Hz),6.16(dd,3H,J=17.3,10.4Hz),5.97(dd,3H,J=10 .4,1.4Hz),5.05-4.83(m,3H),4.83-4.63(m,1H),4.55(bs,1H),4.23(s,6H),4.18(s,2H),4.03( bs,1H),2.59(s,4H),1.85-1.71(m,1H),1.71-1.48(m,4H),1.48-1.37(m,1H),1.37-1.06(m,6H). [Chemical Formula 44]

[0329] -Synthesis of M-1, M-3~M-17- M-1, M-3 to M-17 were synthesized using the same method as the synthesis of M-2.

[0330] 〔Polymerizable compounds〕 MX-1: Compound with the following structure. The subscript in parentheses indicates the number of repetitions. MR-1: Compound with the following structure [Chemical Formula 45]

[0331] 〔Photopolymerization initiator〕 I-1~I-5: Compounds with the following structures [Chemical Formula 46]

[0332] 〔Base generator〕 A-1~A-3: Compounds with the following structures [Chemical Formula 47]

[0333] [Polymerization inhibitor] B-1~B-4: Compounds with the following structures [Chemical Formula 48]

[0334] 〔Silane coupling agent (metal adhesion improver)〕 C-1 to C-3: Compounds of the following structures. In the following formulas, Et represents an ethyl group. [Chemical Formula 49]

[0335] 〔Migration inhibitor〕 D-1~D-4: Compounds with the following structures [Chemical Formula 50]

[0336] 〔additive〕 ·E-1~E-6: Compounds with the following structures [Chemical Formula 51]

[0337] Solvent NMP: N-methyl-2-pyrrolidone EL: Ethyl lactate DMSO: dimethyl sulfoxide GBL: gamma-butyrolactone

[0338] <Evaluation>

[0339] [Evaluation of elongation at break] The resin compositions or comparative compositions prepared in the examples and comparative examples were applied to silicon wafers by spin coating to form resin layers. The obtained silicon wafer with the resin layer formed thereon was dried on a hot plate at 100° C. for 5 minutes, thereby obtaining a resin composition layer having a uniform thickness as indicated in the “Thickness (μm)” column of the table on the silicon wafer. In the examples where "Negative" is listed in the Development Conditions column in the table, the entire surface of the resin composition layer on the silicon wafer was exposed at an exposure energy of 500 mJ / cm². The exposure wavelength is listed in the "Exposure Wavelength (nm)" column in the table. In the examples where "Positive" is listed in the Development Conditions column in the table, no exposure was performed. In the example where "M" is written in the exposure condition column, exposure was performed using a stepper as the light source. In the case where "D" is written in the exposure condition column, exposure was performed using a direct exposure device (ADTEC DE-6UH III) as a light source. In the examples where a numerical value is listed in the "Curing Temperature (°C)" column, the exposed resin composition layer is heated at a heating rate of 10°C / minute in a nitrogen atmosphere using a hot plate. After reaching the temperature listed in the "Curing Temperature (°C)" column in the table, the temperature is maintained for the "Curing Time (min)" listed in the table. In the examples where "IR" is listed in the "Curing Temperature (°C)" column, the resin film obtained in each example was heated at a rate of 10°C / min in a nitrogen atmosphere using an infrared lamp heating device (RTP-6, manufactured by ADVANCE RIKO, Inc.). After reaching 230°C, the temperature was maintained for the period of "Curing Time (min)" listed in the table. The cured resin composition layer (cured product) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the cured product was peeled from the silicon wafer. The peeled cured product was punched out using a punching machine to produce test specimens with a width of 3 mm and a length of 30 mm. The longitudinal elongation of the resulting test specimens was measured using a tensile testing machine (Tensilon) at a crosshead speed of 300 mm / min, 25°C, and 65% relative humidity (RH) in accordance with JIS-K6251. Five measurements were performed, and the arithmetic mean of the elongation at break (elongation at break) of the test specimens from each of the five measurements was used as the index value. The evaluation was performed according to the following evaluation criteria, and the evaluation results are recorded in the "Elongation at Break" column of the table. It can be said that the larger the index value, the better the film strength of the cured product. -Evaluation Criteria- A: The above index value is above 65%. B: The above index value is greater than 60% and less than 65%. C: The above index value is greater than 55% and less than 60%. D: The above index value is less than 55%.

[0340] 〔Evaluation of chemical resistance〕 In each example or comparative example, the prepared resin composition or comparative composition was applied to a silicon wafer by spin coating. The silicon wafer was dried on a hot plate at 100°C for 5 minutes, forming a uniform layer of the resin composition having the thickness listed in the "Thickness (μm)" column of the table on the silicon wafer. In the example where the development conditions are "Negative" and the exposure conditions are "M," a resin composition layer on a silicon wafer was exposed using a stepper. Without using a photomask, the entire surface of the photosensitive film was exposed to light of the wavelength listed in the "Exposure Wavelength (nm)" section in the table. The exposure dose was 500 mJ / cm². In the case where "Negative" is listed as the development condition and "D" is listed as the exposure condition, exposure was performed using a direct exposure device (ADTEC DE-6UH III). The entire surface of the photosensitive film was exposed to light of the wavelength listed in the "Exposure Wavelength (nm)" section in the table. The exposure dose was 500 mJ / cm². In the case where "positive" is described in the development conditions, no exposure was performed. Next, in the examples where a numerical value is listed in the "Curing Temperature (°C)" column, the resin film (resin composition layer) obtained in each Example or Comparative Example was heated at a heating rate of 10°C / minute using a hot plate in a nitrogen atmosphere. After reaching the temperature listed in the "Curing Temperature (°C)" column, the temperature was maintained for the time listed in the "Curing Time (min)" column to form a cured film. In the examples where "IR" is listed in the "Curing Temperature (°C)" column, the resin film obtained in each example was heated at a rate of 10°C / minute in a nitrogen atmosphere using an infrared lamp heater (RTP-6, manufactured by ADVANCE RIKO, Inc.). After reaching 230°C, this temperature was maintained for the time listed in the "Curing Time (min)" column to form a cured film. The obtained cured film was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated. Chemical: A mixture of dimethylsulfoxide (DMSO) and a 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) at a ratio of 90:10 (mass ratio) Evaluation conditions: The cured film was immersed in the above-mentioned chemical at 75°C for 15 minutes. The film thickness of the cured film before and after immersion was compared, and the dissolution rate (nm / min) was calculated. The obtained dissolution rate values ​​were evaluated according to the following evaluation criteria, and the evaluation results were recorded in the "Chemical Resistance" column. It can be said that the smaller the dissolution rate, the better the chemical resistance. -Evaluation Criteria- A: Dissolution rate is less than 250nm / min. B: The dissolution rate is 250 nm / min or more and less than 500 nm / min. C: The dissolution rate is 500 nm / min or more and less than 750 nm / min. D: The dissolution rate is 750 nm / min or higher.

[0341] [Evaluation of Adhesion to Copper Substrate] The resin composition or comparative composition prepared in each of the Examples and Comparative Examples was applied in a layered form onto a copper substrate by spin coating to form a resin composition layer or comparative composition layer. The resulting copper substrate with the resin composition layer or comparative composition layer formed thereon was dried on a hot plate at 100°C for 5 minutes, forming a uniform resin composition layer or comparative composition layer having the thickness listed in the "Thickness (μm)" column of the table on the copper substrate. The resin composition layer or comparative composition layer on the copper substrate was exposed to light of the exposure wavelength (nm) listed in the "Exposure Wavelength (nm)" column of the table at an exposure energy of 500 mJ / cm² using a photomask with a 100 μm square non-masked area for the examples listed in the "Development Conditions" column of the table, and a photomask with a 100 μm square mask area for the examples listed in the "Development Conditions" column of the table. In the example where "M" is written in the exposure condition column, exposure was performed using a stepper as the light source. In the example where "D" is listed in the exposure condition column, laser direct imaging exposure was performed in a 100 μm square area using a direct exposure device (ADTEC DE-6UH III) as the light source without using a mask. The film was then developed for 60 seconds using the developer described in the table to obtain a 100 μm square resin layer. The "TMAH aqueous solution" in the table refers to a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. In the examples where a numerical value is recorded in the "Curing Temperature" column, the exposed resin composition layer is heated at a heating rate of 10°C / minute in a nitrogen atmosphere using a hot plate. After reaching the temperature recorded in the "Curing Temperature (°C)" column in the table, the temperature is maintained for the time recorded in the "Curing Time (min)" column in the table. In the examples where "IR" is listed in the "Curing Temperature (°C)" column, the resin films obtained in each example were heated at a rate of 10°C / minute in a nitrogen atmosphere using an infrared lamp heating device (RTP-6, manufactured by ADVANCE RIKO, Inc.). After reaching 230°C, the temperature was maintained for the time indicated in the "Curing Time (min)" table. The shear force of a 100μm square resin layer on a copper substrate was measured using an adhesive strength tester (CondorSigma, manufactured by XYZTEC) at 25°C and 65% relative humidity (RH). Evaluation was performed according to the following criteria. The results are reported in the "Copper Substrate Adhesion" column of the table. It can be concluded that the greater the shear force, the better the metal adhesion (copper adhesion) of the cured film. -Evaluation Criteria- A: Shear force is greater than 30gf. B: Shear force is greater than 25 gf and less than 30 gf. C: Shear force is 25 gf or less. Also, 1gf is 0.00980665N.

[0342] The above results show that the cured product formed from the resin composition of the present invention has excellent elongation at break. The comparative composition of Comparative Example 1 does not contain the specific compound. It is found that the resulting cured product of this comparative composition has poor elongation at break.

[0343] <Example 101> The resin composition used in Example 1 was applied in a layered form to the surface of the copper layer of a resin substrate having a copper layer formed on its surface by spin coating. The film was dried at 100°C for 5 minutes to form a 20μm thick photosensitive film. The film was then exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365nm through a mask (a binary mask with a 1:1 line and space pattern and a line width of 10μm). After exposure, the film was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern. Next, the temperature was raised at a rate of 10°C / minute in a nitrogen atmosphere to 230°C, where it was maintained at 230°C for 180 minutes, forming a redistribution interlayer insulating film. This redistribution interlayer insulating film exhibited excellent insulation properties. Furthermore, when a semiconductor device was manufactured using this interlayer insulating film for a redistribution layer, it was confirmed that the device operated without any problems.

Claims

1. A resin composition comprising: a polyimide precursor; an alkali generating agent having a structure for generating an alkali compound by means of at least one of light, heat, acid and alkali, and having two or more polymerizable groups; and a photopolymerization initiator, wherein the alkali compound generated by the aforementioned alkali generating agent does not have polymerizable groups.

2. The resin composition as claimed in claim 1, wherein the aforementioned alkali generating agent contains at least one group selected from the group consisting of amide, carbamate, urea and quaternary ammonium groups.

3. A resin composition comprising: a polyimide precursor; an alkali-generating agent represented by any one of formulas (1-1) to (1-4); and a photopolymerization initiator, wherein the alkali compound generated by the aforementioned alkali-generating agent does not have a polymerizable group, wherein in formula (1-1), R11 and R12 independently represent hydrogen atoms or monovalent organic groups, R11 and R12 can be bonded to form a ring structure, n represents an integer greater than or equal to 1, R13 represents a monovalent organic group, and at least one of the following conditions 1 and 2 is satisfied: Condition 1: n R11 and n R12 have a total of more than 2 polymerizable groups; Condition 2: R13 has a total of more than 2 polymerizable groups. In formula (1-2), R21 to R24 independently represent hydrogen atoms or monovalent organic groups, R21 to R24 have a total of more than 2 polymerizable groups, at least two of R21 to R24 can be bonded to form a ring structure, and A1 represents a relative anion. In formula (1-3), R31 to R33 each independently represent a hydrogen atom or a monovalent organic group, R31 to R33 have a total of more than 2 polymerizable groups, at least 2 of R31 to R33 can bond together to form a ring structure, and A2 represents a relative anion. In formula (1-4), R41, R42, R43 and R44 each independently represent a hydrogen atom or a monovalent organic group, R41 and R42 can bond together to form a ring structure, R43 and R44 can bond together to form a ring structure, and R41 to R44 have a total of more than 2 polymerizable groups.

4. The resin composition as described in any one of claims 1 to 3, wherein the polymerizable group contained in the aforementioned alkali generating agent is an addition polymerizable polymerizable group or a ring-opening polymerizable polymerizable group.

5. The resin composition as described in any one of claims 1 to 3, wherein the polymerizable group contained in the aforementioned alkali generating agent is a group having an ethylene unsaturated bond.

6. The resin composition as described in any one of claims 1 to 3, wherein the polymerizable group contained in the aforementioned alkali generating agent is (meth)acryloxy.

7. The resin composition as described in any one of claims 1 to 3, wherein the aforementioned alkali generating agent is a nonionic compound.

8. A resin composition comprising: a polyimide precursor; a compound represented by the following formula (X); and a photopolymerization initiator, wherein in formula (X), R1 and R2 independently represent monovalent organic groups, R1 and R2 can be bonded to form a ring structure, L1 represents a divalent linker, X represents a hydroxyl or carboxyl group, Cy represents a ring structure, and R3 represents a structure containing a group having two or more vinyl unsaturated bonds.

9. The resin composition as described in any one of claims 1 to 3 and claim 8, wherein the aforementioned polyimide precursor has a polymerizable group.

10. The resin composition described in any one of claims 1 to 3 and claim 8, used to form an interlayer insulating film for a rewiring layer.

11. A hardener formed by hardening a resin composition described in any one of claims 1 to 3 and claim 8.

12. A laminate comprising two or more layers formed of the hardened material described in claim 11, and comprising a metal layer between any of the layers formed of the hardened material.

13. A method for manufacturing a hardened material, comprising a film forming step of applying a resin composition described in any one of claims 1 to 3 and 8 onto a substrate to form a film.

14. The method for manufacturing a hardened material as described in claim 13, comprising an exposure step of selectively exposing the aforementioned film and a development step of developing the aforementioned film using a developer to form a pattern.

15. A method for manufacturing a hardened material as described in claim 13, comprising a heating step of heating the aforementioned film at 50°C to 450°C.

16. A method for manufacturing a laminate, comprising the method for manufacturing a hardened material as described in claim 13.

17. A method for manufacturing a semiconductor device, comprising the method for manufacturing the hardened material as described in claim 13.

18. A semiconductor element comprising the hardened material described in claim 11.

19. A compound represented by the following formula (X), wherein R1 and R2 independently represent monovalent organic groups, R1 and R2 can be bonded to form a ring structure, L1 represents a divalent linker, X represents a hydroxyl or carboxyl group, Cy represents a ring structure, and R3 represents a structure containing a group having two or more vinyl unsaturated bonds.