Resin composition having an acid group and a polymerizable unsaturated group, curable resin composition, cured product, insulating material, and resist member

Abstract

To provide a resin composition having an acid group and a polymerizable unsaturated group which exhibits excellent developability and allows a cured product obtained therefrom to exhibit excellent elongation, low elasticity, heat resistance and low dielectric characteristics, a curable resin composition containing the resin composition, and a cured product, an insulating material and a resist member obtained using the curable resin composition.SOLUTION: The resin composition having an acid group and a polymerizable unsaturated group contains an aromatic ester compound (A) and a resin (B) having an acid group and a polymerizable unsaturated group. The aromatic ester compound (A) is a compound using an aromatic polycarboxylic acid, an acid halide thereof and / or an esterified product thereof (a1), a monohydroxy aromatic compound (a2), and a polyhydric alcohol compound (a3) as essential reaction raw materials. The polyhydric alcohol compound (a3) has a hydroxyl equivalent of less than 270 g / eq.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a resin composition having an acid group and a polymerizable unsaturated group, a curable resin composition containing the resin composition having an acid group and a polymerizable unsaturated group, and a cured product, insulating material, and resist member obtained from the curable resin composition. [Background technology]

[0002] When mounting and soldering electronic components on a printed wiring board, solder resists are widely used as materials for forming coatings that prevent solder from adhering to areas other than the mounted area and that semi-permanently prevent oxidation or corrosion of wiring. In particular, due to environmental considerations, the mainstream technology for forming such solder resist patterns is the alkaline-developable liquid photoresist method, which can accurately form fine patterns. In recent years, to achieve higher density electronic components, printed wiring boards have become increasingly miniaturized (fine), multi-layered, and single-board, and the mounting method has also shifted to surface mount technology (SMT). Consequently, there is growing demand for solder resist films with finer dimensions, higher Tg, higher resolution, higher precision, and higher reliability. Furthermore, as transmission signal speeds increase, the solder resist market is also seeking technology that exhibits low dielectric constant and low dielectric dissipation factor to reduce time delays for use at high frequencies (gigahertz range). Such alkali-developable liquid photoresists widely use reaction products (acid-pendant epoxy acrylates) obtained by reacting a novolac epoxy resin with an unsaturated monocarboxylic acid and then adding a polybasic acid anhydride (see Patent Document 1). However, it is known that epoxy acrylates have a high dielectric constant due to the generation of hydroxyl groups when the epoxy resin is reacted with the unsaturated monocarboxylic acid. For this reason, Patent Document 2, for example, discloses a technology for improving heat resistance, dielectric loss tangent, and water resistance by using a photosensitive resin composition containing an active ester curing agent and a carboxyl group-containing radical polymerizable compound. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 1-54390 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-214057 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the techniques of Patent Documents 1 and 2 do not consider the elongation and low elasticity of the cured product formed from the photosensitive resin composition. Therefore, the present disclosure provides a resin composition having an acid group and a polymerizable unsaturated group, which exhibits excellent developability and can produce a cured product having excellent elongation, good coating film appearance, and low dielectric properties; a curable resin composition containing the resin composition having an acid group and a polymerizable unsaturated group; and a cured product, an insulating material, and a resist member obtained using the curable resin composition. [Means for solving the problem]

[0005] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that by using a composition containing a specific aromatic ester compound and a resin having an acid group and a polymerizable unsaturated group, excellent developability is exhibited, and the resulting cured product exhibits excellent elongation, good coating film appearance, and low dielectric properties, thereby completing the present invention.

[0006] The resin composition having an acid group and a polymerizable unsaturated group of the present disclosure is a resin composition having an acid group and a polymerizable unsaturated group, which contains an aromatic ester compound (A) and a resin (B) having an acid group and a polymerizable unsaturated group, the aromatic ester compound (A) is a compound obtained by reacting an aromatic polycarboxylic acid, an acid halide thereof and / or an ester thereof (a1), a monohydroxyaromatic compound (a2), and a polyhydric alcohol compound (a3) ​​as essential reaction raw materials; The polyhydric alcohol compound (a3) ​​has a hydroxyl group equivalent of less than 270 g / eq. In this embodiment, the aromatic ester compound (A) is represented by the following general formula (1): [ka] [In the above general formula (1), Q 11 and Q 12 each independently represents a group derived from the aromatic polycarboxylic acid, its acid halide and / or its ester (a1), and Ar 11 and Ar 12 each independently represents a group derived from the monohydroxy aromatic compound (a2), each A independently represents a group derived from the polyhydric alcohol compound (a3), p 11 represents an average repeat number of 0.01 or more.] is preferred. In the present embodiment, in the general formula (1), each A independently represents a linear or branched alkylene group, or a linear or branched alkylene ether group, Q 11 and Q 12 each independently represents a divalent aromatic group; 11 represents the average number of repeats greater than or equal to 0.01, Ar 11 and Ar 12 are each independently represented by the following general formula (2) or (3): [ka] [In the above general formula (2) and general formula (3), * represents Ar in the above general formula (1)] 11 or Ar 12 represents the bond to the oxygen atom that bonds to R 21 and R 31each independently represents a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an aralkyl group; k 21 represents an integer of 0 to 7, and k 31 represents an integer of 0 to 5. It is preferable that the structure represented by the formula: [Effects of the Invention]

[0007] According to the present disclosure, it is possible to provide a resin composition having an acid group and a polymerizable unsaturated group, which exhibits excellent developability and is capable of producing a cured product having excellent elongation, a good coating film appearance, and low dielectric properties; a curable resin composition containing the resin composition having an acid group and a polymerizable unsaturated group; and a cured product, an insulating material, and a resist member obtained using the curable resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0008] Below, we will explain in detail the embodiment of the present disclosure (hereinafter referred to as the "present embodiment"), but the present disclosure is not limited to the description below and can be implemented in various modifications within the scope of its gist.

[0009] [Resin Composition Having Acid Group and Polymerizable Unsaturated Group] The present disclosure relates to a resin composition having an acid group and a polymerizable unsaturated group, which comprises an aromatic ester compound (A) (hereinafter also referred to as component (A)) and a resin (B) (hereinafter also referred to as component (B)) having an acid group and a polymerizable unsaturated group. The aromatic ester compound (A) is a compound obtained by reacting an aromatic polycarboxylic acid, its acid halide and / or its ester (a1), a monohydroxyaromatic compound (a2), and a polyhydric alcohol compound (a3) ​​as essential reaction raw materials. The hydroxyl equivalent of the polyhydric alcohol compound (a3) ​​is less than 270 g / eq. This allows the formation of a cured product that exhibits excellent developability, excellent elongation, good coating appearance, and low dielectric properties. Here, "poor developability" means that the contrast between exposed and unexposed areas is insufficient. One of the causes of poor developability is that when a curable resin composition applied to a substrate is dried and then exposed to light, the unexposed areas remain after (alkali) development due to heating or the like associated with drying, resulting in a decrease in contrast. Therefore, in the present invention, as described in the Examples section below, alkaline developability is evaluated using the drying control range (minutes) as an example of an index of developability. The drying control range specifies the range of drying conditions (drying time) under which development defects are unlikely to occur due to coating film drying or the like. Therefore, if development residues are unlikely to occur even if the drying time is extended (= if the drying control range is large), it is considered that excellent developability can be exhibited.

[0010] In the resin composition having an acid group and a polymerizable unsaturated group of the present disclosure, the content of the aromatic ester compound (A) is preferably in the range of 90 to 10 mass% relative to the total amount (100 mass%) of the resin composition having an acid group and a polymerizable unsaturated group, from the viewpoint of achieving a balanced improvement in excellent developability, excellent elongation, good coating appearance, and low dielectric properties. The upper or lower limit of the content of the aromatic ester compound (A) is preferably 10 mass% or more, more preferably 20 mass% or more, and even more preferably 30 mass% or more, and is preferably 90 mass% or less, more preferably 80 mass% or less, and even more preferably 70 mass% or less. In the resin composition having an acid group and a polymerizable unsaturated group of the present disclosure, the content of the resin (B) having an acid group and a polymerizable unsaturated group is preferably in the range of 90 to 10 mass% relative to the total amount (100 mass%) of the resin composition having an acid group and a polymerizable unsaturated group. The upper or lower limit of the content of the resin (B) having an acid group and a polymerizable unsaturated group is preferably 10 mass% or more, more preferably 20 mass% or more, and even more preferably 30 mass% or more, and is preferably 90 mass% or less, more preferably 80 mass% or less, and even more preferably 70 mass% or less.

[0011] In this embodiment, the mass ratio of the solid content of the aromatic ester compound (A) to the resin (B) having an acid group and a polymerizable unsaturated group [(A) / (B)] is preferably in the range of 5 / 95 to 50 / 50 from the viewpoint of achieving a good balance between excellent developability, excellent elongation, good coating appearance, and low dielectric properties. From the same viewpoint, the upper or lower limit of the mass ratio [(A) / (B)] is more preferably 10 / 90 or more, even more preferably 20 / 80 or more, and more preferably 40 / 60 or less.

[0012] The resin composition having an acid group and a polymerizable unsaturated group according to the present embodiment may further contain an optional additive component as an optional component. Furthermore, the resin composition having an acid group and a polymerizable unsaturated group in this embodiment may be substantially composed of only the component (A), the component (B), and any optional additional components, or may be composed of only the component (A) and the component (B). From the viewpoint of achieving a balanced improvement in excellent developability, excellent elongation, good coating film appearance, and low dielectric properties, the total content of the (A) component and the (B) component relative to the total amount (100% by mass) of the resin composition having an acid group and a polymerizable unsaturated group of this embodiment is preferably 40% by mass or more, more preferably 50% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. The phrase "consisting only of the above component (A), component (B), and optional additional components" means that, relative to the total amount (100% by mass) of the resin composition having an acid group and a polymerizable unsaturated group, preferably 80 to 100% by mass, or at least 90 to 95% by mass, is made up of the components (A) and (B), or the components (A), (B), and optional additional components. The resin composition having an acid group and a polymerizable unsaturated group of the present embodiment may contain unavoidable impurities in addition to the component (A), the component (B), and any optional additional components, as long as the effects of the present disclosure are not impaired. Hereinafter, after explaining the main terms used in this specification, the components contained in the resin composition having an acid group and a polymerizable unsaturated group in this embodiment, namely, the aromatic ester compound (A), the resin having an acid group and a polymerizable unsaturated group (B), and optional additional components, will be described.

[0013] (Terminology explanation) Unless otherwise specified herein, the following terms apply. The "aromatic group" in this specification preferably has an aromatic ring having 3 to 30 carbon atoms. The "aromatic group" in this specification may have a hydrogen atom of the aromatic ring substituted with a substituent, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Examples of the aromatic ring include a monocyclic aromatic ring, a fused aromatic ring, and a ring-assembly aromatic ring. Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of the fused aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Examples of the ring-assembly aromatic ring include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. A monovalent aromatic group refers to a group in which one hydrogen atom has been removed from an "aromatic group," a divalent aromatic group refers to a group in which two hydrogen atoms have been removed from an "aromatic group," and a trivalent to hexavalent aromatic group refers to a group in which three to six hydrogen atoms have been removed from an "aromatic group." Examples of the "aryl group" in this specification include a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, an anthryl group, an azulenyl group, an indenyl group, an indanyl group, a tetralinyl group, etc. Furthermore, the "aryl group" may be such that a hydrogen atom of an aromatic ring in the aryl group is substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. As used herein, examples of the "aralkyl group" include a benzyl group, a diphenylmethyl group, a biphenyl group, and a naphthylmethyl group. Examples of the "alkyl group" in this specification include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n-)decyl group, (n-)undecyl group, (n-)dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclononyl group. As used herein, the term "alkenyl group" includes an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a pentynyl group, a hexynyl group, a vinyl group, an allyl group, an isopropenyl group, and the like. As used herein, the term "alkoxy group" includes, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group. As used herein, the term "halogen atom" includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. As used herein, examples of a "straight-chain or branched-chain alkylene group" include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a propylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group. As used herein, examples of the "straight-chain or branched-chain alkylene ether group" include an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxy(1-methylmethylene) group, an oxy(1,1-dimethylmethylene) group, an oxy(1-methylethylene) group, an oxy(1,1-dimethylethylene) group, an oxy(1,2-dimethylethylene) group, an oxybutylene group, an oxy(1-methylpropylene) group, an oxy(2-methylpropylene) group, an oxypentylene group, an oxyhexylene group, an oxyheptylene group, an oxyoctylene group, an oxynonylene group, an oxydecylene group, an oxyundecylene group, and an oxydodecylene group. The "monovalent hydrocarbon group" in this specification refers to an alkyl group (e.g., the alkyl groups described above), and one or more -CH2- in the alkyl group may be substituted with -O- or -S- so that they are not adjacent to each other, or one or more -CH2-CH2- in the alkyl group may be substituted with -CH=CH- so that they are not adjacent to each other. The hydrocarbon group may be linear or branched, and may be an alkyl group having 1 to 20 carbon atoms. The "divalent hydrocarbon group" in this specification refers to an alkylene group (for example, the above-mentioned linear or branched alkylene group), and one or more -CH2- in the alkylene group may be substituted with -O- or -S- so that they are not adjacent to each other, or one or more -CH2-CH2- in the alkylene group may be substituted with -CH=CH- so that they are not adjacent to each other. The hydrocarbon group may be linear or branched and may be an alkylene group having 1 to 20 carbon atoms. The term "trivalent to hexavalent hydrocarbon group" as used herein refers to an alkyl group (e.g., the above-mentioned linear or branched alkyl group) from which two to five hydrogen atoms have been removed at any position, and in which one or more -CH2- groups in the alkyl group may be substituted with -O- or -S- so that they are not adjacent to each other, or one or more -CH2-CH2- groups in the alkyl group may be substituted with -CH=CH- so that they are not adjacent to each other. The hydrocarbon group may be linear or branched and may have 1 to 20 carbon atoms. As used herein, "(meth)acrylate" means acrylate and / or methacrylate. Also, as used herein, "(meth)acryloyl" means acryloyl and / or methacryloyl. Furthermore, as used herein, "(meth)acrylic" means acrylic and / or methacrylic.

[0014] (Aromatic ester compound (A)) The aromatic ester compound (A) is one of the essential components of the resin composition having an acid group and a polymerizable unsaturated group of this embodiment. The aromatic ester compound (A) is obtained from the essential reaction raw materials, which are an aromatic polycarboxylic acid, its acid halide and / or its ester (a1), a monohydroxy aromatic compound (a2), and a polyhydric alcohol compound (a3). The reaction raw materials may further contain a compound (e.g., a polyhydroxy aromatic compound (a4)) that is reactive with the aromatic polycarboxylic acid, its acid halide and / or its ester (a1), or the monohydroxy aromatic compound (a2). That is, the aromatic ester compound (A) of this embodiment may be a compound used as a reaction raw material that contains the aromatic polycarboxylic acid, its acid halide and / or its ester (a1), the monohydroxy aromatic compound (a2), the polyhydric alcohol compound (a3), and the polyhydroxy aromatic compound (a4). In principle, the aromatic ester compound (A) obtained from the reaction raw materials has no or almost no hydroxyl groups in its molecule, but may contain a compound having a hydroxyl group as a by-product of the reaction product within a range that does not impair the effects of the present disclosure.

[0015] In this specification, "aromatic polycarboxylic acids, acid halides thereof and / or esters thereof (a1)" may be abbreviated as "aromatic polycarboxylic acids (a1)" hereinafter. Before describing the reaction raw materials, that is, the aromatic polycarboxylic acid (a1), the monohydroxy aromatic compound (a2), and the polyhydric alcohol compound (a3), the structure and properties of the aromatic ester compound (A) will be described in detail below.

[0016] <Structure of aromatic ester compound (A)> In terms of structure, the aromatic ester compound (A) of the present embodiment can contain a residue of an aromatic polycarboxylic acid, its acid halide and / or its ester (aromatic polycarboxylic acid) (a1), a residue of a monohydroxyaromatic compound (a2), and a residue of a polyhydric alcohol compound (a3). In terms of another structure, the aromatic ester compound (A) of the present embodiment may contain a residue of an aromatic polycarboxylic acid, its acid halide and / or its ester (aromatic polycarboxylic acid) (a1), a residue of a monohydroxy aromatic compound (a2), a residue of a polyhydric alcohol compound (a3), and a residue of a polyhydric hydroxy aromatic compound (a4). Furthermore, the aromatic ester compound (A) of the present embodiment can have a structure in which an ester bond is formed between a carboxylic acid (or an acid halide or an ester thereof) in the aromatic polycarboxylic acid (a1) and a hydroxyl group in the monohydroxyaromatic compound (a2). Similarly, the aromatic ester compound (A) of the present embodiment can have a structure in which an ester bond is formed between a carboxylic acid (or an acid halide thereof, or an ester thereof) in the aromatic polycarboxylic acid (a1) and a hydroxyl group in the polyhydric alcohol compound (a3). Furthermore, the aromatic ester compound (A) of the present embodiment can have a structure in which an ester bond is formed between a carboxylic acid (or an acid halide or an ester thereof) in the aromatic polycarboxylic acid (a1) and a hydroxyl group in the polyhydroxy aromatic compound (a4).

[0017] In this specification, "aromatic polycarboxylic acid, its acid halide, and / or its ester (a1)" refers to a compound having an aromatic group bonded to two or more atomic groups containing a carbonyl group (-C(=O)-X, where X is a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent hydrocarbon group). In this specification, "residue of aromatic polycarboxylic acid, its acid halide, and / or its ester (a1)" refers to a partial structure of aromatic polycarboxylic acid, its acid halide, and / or its ester (a1) that remains in the molecule of aromatic ester compound (A) produced by reaction or polymerization, and is composed of a chemical bond formed by the reaction or polymerization and a group other than the chemical bond derived from aromatic polycarboxylic acid, its acid halide, and / or its ester (a1) In addition, the term "group derived from" in this specification refers to a partial structure other than the structure of the chemical bond involved in the reaction or polymerization in the product compound formed by the reaction or polymerization. Therefore, the term "group derived from the aromatic polycarboxylic acid, its acid halide and / or its ester (a1)" refers to a divalent or higher group obtained by removing an atomic group containing a carbonyl group (-C(=O)-X (X is a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent hydrocarbon group)) from the aromatic polycarboxylic acid, its acid halide and / or its ester (a1), and may be, for example, a divalent or higher aromatic group.

[0018] The aromatic polycarboxylic acid, its acid halide and / or its ester (a1) is represented by the following general formula (a1): [ka] In this case, Qa1 represents a group derived from an aromatic polycarboxylic acid, an acid halide thereof, and / or an ester thereof (a1), X represents a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent hydrocarbon group, n a1 represents an integer of 2 or more and 6 or less, and the dashed line portion represents a residue of an aromatic polycarboxylic acid, an acid halide thereof and / or an ester thereof (a1). In this specification, the term "residue of a monohydroxy aromatic compound (a2)" refers to a monovalent group obtained by removing a hydrogen atom or a hydroxyl group from a monohydroxy aromatic compound (a2). The "monohydroxy aromatic compound (a2)" is a compound represented by the following general formula (a2): [ka] In this case, Ar a2 represents a group derived from the monohydroxy aromatic compound (a2), that is, a monovalent group obtained by removing a hydrogen atom or a hydroxyl group from the monohydroxy aromatic compound (a2), and the dashed line portion represents a residue of the monohydroxy aromatic compound (a2). In this specification, the term "residue of polyhydric alcohol compound (a3)" refers to a divalent or higher polyvalent group obtained by removing two or more hydrogen atoms or hydroxyl groups from polyhydric alcohol compound (a3). The "polyhydric alcohol compound (a3)" is represented by the following general formula (a3): [ka] In this case, A a3 represents a group derived from the polyhydric alcohol compound (a3), and n represents a group obtained by removing a hydrogen atom or a hydroxyl group from the polyhydric alcohol compound (a3). a3 is the base of valence, n a3 represents an integer between 2 and 6. a3 is preferably 2. The polyhydric hydroxy aromatic compound (a4) is a compound in which only 2 to 6 hydrogen atoms in the aromatic ring in the aromatic group are substituted with hydroxyl groups, whereas the polyhydric alcohol compound (a3) ​​is a polyhydric alcohol other than the polyhydric hydroxy aromatic compound (a4). In this specification, the term "residue of polyhydroxy aromatic compound (a4)" refers to a divalent or higher polyvalent group obtained by removing a hydrogen atom or a hydroxyl group from polyhydroxy aromatic compound (a4). The "polyhydroxy aromatic compound (a4)" is represented by the following general formula (a4): [ka] In this case, Ar a4 represents a group derived from the polyhydroxy aromatic compound (a4), and n a4 n hydrogen atoms or hydroxyl groups removed a4 is a polyvalent group with n a4 represents an integer from 2 to 6. a4 is preferably 2. The polyvalent hydroxy aromatic compound (a4) is a compound in which only 2 to 6 hydrogen atoms in the aromatic ring of the aromatic group are substituted with hydroxyl groups.

[0019] The terms "monovalent" and "divalent" used herein simply indicate the number of bonds, and correspond to the number of ester bonds contributed by one molecule of each compound.

[0020] The group derived from the aromatic polycarboxylic acid (a1) in the aromatic ester compound (A) may be divalent to hexavalent. In other words, the aromatic ester compound (A) may have a structure in which 2 to 6 carboxylic acids (or acid halides thereof, or esters thereof) contained in one molecule of the aromatic polycarboxylic acid (a1) contribute to an ester bond. Similarly, the group derived from the polyhydric alcohol compound (a3) ​​in the aromatic ester compound (A) may be divalent to hexavalent. In other words, the aromatic ester compound (A) may have a structure in which 2 to 6 hydroxyl groups contained in one molecule of the polyhydric alcohol compound (a3) ​​contribute to an ester bond.

[0021] More specifically, the aromatic ester compound (A) of the present embodiment has a partial structure represented by the following general formula (i), in which the same or different aromatic rings are linked to each other via an ester bond: It may have a chemical structure in which a residue of a polyhydric alcohol compound (a3) ​​(for example, a divalent to hexavalent hydrocarbon group having at least carbon atoms and hydrogen atoms in the molecule of the polyhydric alcohol compound (a3) ​​(examples of the divalent to hexavalent hydrocarbon group include an alkylene chain or an alkylene ether chain (however, the -CH2- group in the alkylene chain or the alkylene ether chain may be substituted with a divalent aromatic group))) and a residue of an optional polyhydroxy aromatic compound (a4) are linked together. [ka] (In the above general formula (i), Ar i1 represents a monovalent aromatic group, and Ar i2 represents a divalent aromatic group, and the dashed line in the above general formula (i) represents a bond to another atom. The same or different aromatic rings correspond to the aromatic rings in the molecule of the aromatic polycarboxylic acid (a1) or the monohydroxy aromatic compound (a2). More specifically, the monovalent aromatic group Ar i1 corresponds to the aromatic ring in the molecule of the monohydroxy aromatic compound (a2), and is the divalent aromatic group Ar i2 corresponds to the aromatic polycarboxylic acid (a1). The aromatic ring, which is a rigid mesogenic skeleton, and the alkylene chain, which is a flexible segment, coexist with a certain regularity (repeating unit) within the same molecule of the aromatic ester compound (A), so that the resin composition having an acid group and a polymerizable unsaturated group as a whole exhibits excellent developability and can form a cured product that is excellent in elongation, low elasticity, heat resistance, and low dielectric properties.

[0022] The aromatic ester compound (A) of the present embodiment is represented by the following general formula (1): [ka] [In the above general formula (1), Q 11and Q 12 each independently represents a group derived from an aromatic polycarboxylic acid, an acid halide thereof, and / or an ester thereof (a1), and Ar 11 and Ar 12 each independently represents a group derived from a monohydroxy aromatic compound (a2), each A independently represents a group derived from a polyhydric alcohol compound (a3), p 11 is an average repeat number of 0.01 or more. For convenience of explanation, the above-mentioned derived groups are terms that represent the correspondence between the symbols in general formula (1) and each raw material component, and do not represent all structural moieties derived from each reaction raw material that remain in the aromatic ester compound (A) after the reaction.

[0023] Q in the above general formula (1) 11 and Q 12 Preferably, each independently represents a group derived from an aromatic polycarboxylic acid, its acid halide, and / or its ester (a1) (hereinafter also referred to as a group derived from aromatic polycarboxylic acids (a1)). For example, the group derived from aromatic polycarboxylic acids (a1) is preferably a divalent aromatic group, more preferably an unsubstituted divalent aromatic group. Q in the above general formula (1) 11 and Q 12 is preferably a divalent aromatic group. Examples of the divalent aromatic group include groups in which two hydrogen atoms have been removed from the above-mentioned examples of aromatic rings having 3 to 30 carbon atoms. Among these, Q 11 and Q 12 is more preferably any one of a phenylene group, a naphthalenediyl group, and an anthracenediyl group. 11 and Q 12 may be the same as each other or may be different from each other. Among them, Q is the most popular from the viewpoint of industrial availability of raw materials and solubility. 11 and Q 12 is more preferably a phenylene group. A in the above general formula (1) is a group derived from a polyhydric alcohol compound (a3) ​​and may contain at least one bond structure selected from the group consisting of a hydrocarbon bond (divalent to hexavalent hydrocarbon group), a carbonate bond, an ester bond, an ether bond, a urethane bond, and a siloxane bond. The group derived from the polyhydric alcohol compound (a3) ​​preferably has 3 to 17 carbon atoms, more preferably 4 to 17 carbon atoms, and even more preferably 5 to 15 carbon atoms. When the number of carbon atoms of A corresponding to the flexible segment in the general formula (1) is within the above range, the aromatic ester compound (A) has excellent compatibility, which is a preferred embodiment. In addition, the group derived from the polyhydric alcohol compound (a3) ​​is preferably linear or branched, and more preferably linear. Furthermore, the group derived from the polyhydric alcohol compound (a3) ​​is a linear or branched alkylene group, or a linear or branched alkylene ether group, and -CH2- in the alkylene group or alkylene ether group may be substituted with -O- or -S- so that they are not adjacent to each other, or one or more -CH2-CH2- in the alkylene group may be substituted with at least one bond selected from the group consisting of -CH=CH-, a carbonate bond, an ester bond, an ether bond, a urethane bond, and a siloxane bond so that they are not adjacent to each other.

[0024] Ar in the above general formula (1) 11 and Ar 12 each independently represents a group derived from a monohydroxy aromatic compound (a2), and is represented by the following general formula (2) or (3): [ka] [In the above general formula (2) and general formula (3), * represents Ar in the above general formula (1)] 11 or Ar 12 represents the bond to the oxygen atom that bonds to R 21 and R 31each independently represents a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an aralkyl group; k 21 represents an integer of 0 to 7, and k 31 represents an integer of 0 to 5.] is preferably represented by the following.

[0025] In the above general formula (1), Ar 11 and Ar 12 may be the same as each other or may be different from each other. In the above general formula (1), Ar 11 is preferably a group having a structure represented by the above general formula (3). 12 is preferably a group having the structure represented by the above general formula (3).

[0026] R in the above general formula (2) 21 is preferably any one of a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, and an aralkyl group, and among these, from the viewpoints of dielectric properties, workability, and flexibility of the obtained cured product, is more preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aralkyl group such as a benzyl group, a diphenylmethyl group, or a naphthylmethyl group, or an arylene group such as a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, or an anthryl group. R in the above general formula (3) 31 is preferably any one of a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, and an aralkyl group, and among these, from the viewpoints of dielectric properties, workability, and flexibility of the obtained cured product, is more preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aralkyl group such as a benzyl group, a diphenylmethyl group, or a naphthylmethyl group, or an arylene group such as a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, or an anthryl group.

[0027] k in the above general formula (2) 21is preferably an integer of 0 to 7, more preferably an integer of 0 to 5, and from the viewpoint of reactivity or flexibility of the resulting cured product, is even more preferably an integer of 0 to 4. 31 is preferably an integer of 0 to 5, and more preferably an integer of 0 to 4 from the viewpoint of reactivity or flexibility of the resulting cured product.

[0028] p in the above general formula (1) 11 is preferably an average number of repetitions of 0.01 or more, and from the viewpoints of workability and flexibility of the resulting cured product, it is more preferably an average number of repetitions of 0.1 to 5, and even more preferably an average number of repetitions of 0.2 to 5. The average repeat number p of the aromatic ester compound (A) 1 is calculated from the feed ratio using the following formula (1). Formula (1): (average repeat number p in the obtained aromatic ester compound (A) 1 ) = (number of moles of hydroxyl groups in polyhydric alcohol compound (a3)) / [(number of moles of active ester groups in active ester group-containing intermediate product (a') produced from the reaction raw materials) - (number of moles of hydroxyl groups in polyhydric alcohol compound (a3)] The active ester group-containing intermediate product (a') is a reaction product obtained by reacting an aromatic polycarboxylic acid, its acid halide and / or its ester (a1) with a monohydroxy aromatic compound (a2) as reaction raw materials.

[0029] Another embodiment of the aromatic ester compound (A) of the present embodiment is represented by the following general formula (1'): [ka] [In the above general formula (1'), Q 11 , Q 12 and Q 13 each independently represents a group derived from an aromatic polycarboxylic acid, an acid halide thereof, and / or an ester thereof (a1), and Ar 11 and Ar 12each independently represents a group derived from the monohydroxy aromatic compound (a2), and Ar 13 represents a group derived from a polyhydric hydroxy aromatic compound (a4), each A independently represents a group derived from a polyhydric alcohol compound (a3), p 11 is an average repeat number of 0.01 or more.

[0030] <Reaction raw materials for aromatic ester compound (A)> The reaction raw materials for the aromatic ester compound (A) will be explained below. -Aromatic polycarboxylic acid, its acid halide and / or ester (a1)- In this embodiment, the aromatic polycarboxylic acid, its acid halide and / or ester (a1) (Q of the above general formula (1)) 11 and / or Q 12 The compound (a1) having a partial structure represented by the formula (1) is a carboxylic acid having two or more carboxyl groups or a derivative thereof, specifically a carboxylate, an acid halide, or an ester. The aromatic polycarboxylic acid (a1) and the monohydroxy aromatic compound (a2) described below (Ar in the formula (1)) are 11 and / or Ar 12 and a polyhydric alcohol compound (a3) ​​(a compound having a partial structure represented by A in the above general formula (1)) are used as reaction raw materials, and in the structure of the aromatic ester compound (A), a structural portion having flexibility derived from the polyhydric alcohol compound (a3) ​​(for example, A in the above general formula (1)) and an aromatic ring having high curability at the terminal (for example, Q in the above general formula (1)) are obtained. 11 and / or Q 12 and Ar 11 and / or Ar 12 ) (specifically, a polyaryloxycarbonyl structure) and an ester structure containing both, and therefore have high reactivity.

[0031] The aromatic polycarboxylic acid (a1) is typically a compound having at least two carboxyl groups or the like bonded to a substituted or unsubstituted aromatic ring. However, the carboxyl group or the like moiety may be, in addition to a carboxyl group, a halogenated acyl group such as an acyl fluoride group, an acyl chloride group, or an acyl bromide group; an alkyloxycarbonyl group such as a methyloxycarbonyl group, an ethyloxycarbonyl group; or an aryloxycarbonyl group such as a phenyloxycarbonyl group, a naphthyloxycarbonyl group. In other words, when the carboxyl group or the like moiety is a halogenated acyl group, the aromatic polycarboxylic acid (a1) is an acid halide. Similarly, when the carboxyl group or the like moiety is an alkyloxycarbonyl group or an aryloxycarbonyl group, the aromatic polycarboxylic acid (a1) is an esterified product. The aromatic polycarboxylic acids (a1) preferably have a carboxyl group, an acyl halide group, or an aryloxycarbonyl group, more preferably have a carboxyl group or an acyl halide group, and even more preferably have a carboxyl group, an acyl chloride group, or an acyl bromide group. The aromatic ring is not particularly limited, and examples thereof include a monocyclic aromatic ring, a fused aromatic ring, an aromatic ring assembly, an aromatic ring connected by an alkylene chain, etc. From the viewpoints of flexibility of the obtained cured product, ease of industrial availability of raw materials, and workability, the aromatic ring is preferably a monocyclic aromatic ring or a fused aromatic ring.

[0032] The valence (number) of the carboxyl groups in the aromatic polycarboxylic acids (a1) is preferably from divalent to tetravalent, and more preferably divalent.

[0033] Specific examples of the aromatic polycarboxylic acids (a1) include benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, and 2-allylterephthalic acid; benzenetricarboxylic acids such as trimellitic acid and 5-allyltrimellitic acid; naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 3-allylnaphthalene-1,4-dicarboxylic acid, and 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acids such as 2,4,5-pyridinetricarboxylic acid; triazinecarboxylic acids such as 1,3,5-triazine-2,4,6-tricarboxylic acid; and acid halides and esters thereof.

[0034] Of the above-mentioned examples, from the viewpoints of flexibility of the obtained cured product, ease of industrial availability of raw materials, and workability, the aromatic polycarboxylic acids (a1) are preferably benzenedicarboxylic acid, benzenetricarboxylic acid, naphthalenedicarboxylic acid, and acid halides thereof, more preferably isophthalic acid, terephthalic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 1,3,5-benzenetricarboxylic acid, and acid halides thereof, and even more preferably isophthalic acid chloride and terephthalic acid chloride. The aromatic polycarboxylic acids (a1) may be used alone or in combination of two or more.

[0035] -Monohydroxyaromatic compound (a2)- The monohydroxy aromatic compound (a2) is an aromatic compound having one aromatic hydroxyl group. Specific examples of the monohydroxy aromatic compound (a2) include alkylphenols such as phenol, o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,6-xylenol, and tertiary butylphenol; aralkylphenols such as o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, styrenated phenol, and 4-(α-cumyl)phenol; and naphthol compounds such as 1-naphthol and 2-naphthol. Among these, o-cresol and naphthol are preferred as the monohydroxy aromatic compound (a2) from the viewpoint of superior dielectric properties. The monohydroxy aromatic compound (a2) may be used alone or in combination of two or more kinds.

[0036] -Polyhydric alcohol compound (a3)- In this embodiment, the polyhydric alcohol compound (a3) ​​is a compound having at least two hydroxyl groups and belongs to a group of compounds also called polyols. The hydroxyl equivalent of the polyhydric alcohol compound (a3) ​​in this embodiment must be less than 270 g / eq. The hydroxyl equivalent is preferably 31 g / eq or more and less than 270 g / eq, and more preferably 38 g / eq or more and less than 250 g / eq. A hydroxyl equivalent of less than 270 g / eq is excellent in terms of heat resistance of the cured product. The hydroxyl equivalent is a value measured in accordance with JIS K 0070. The valence (number) of the hydroxyl groups in the polyhydric alcohol compound (a3) ​​is preferably from divalent to hexavalent, and more preferably divalent. In this embodiment, in order to set the hydroxyl group equivalent, which represents the number of hydroxyl groups in one molecule of the polyhydric alcohol compound (a3), within a predetermined range, for example, the length of the molecular chain constituting the polyhydric alcohol compound (a3), or the presence or absence of a repeating unit in the molecular chain constituting the polyhydric alcohol compound (a3), or the number of repeating units, etc., can be adjusted.

[0037] The polyhydric alcohol compound (a3) ​​may or may not contain an aromatic ring. The optional polyhydric hydroxy aromatic compound (a4) is a compound in which only two to six hydrogen atoms in the aromatic ring in the aromatic group are substituted with hydroxyl groups, while the polyhydric alcohol compound (a3) ​​contains polyhydric alcohols other than the polyhydric hydroxy aromatic compound (a4). The polyhydric alcohol compound (a3) ​​is preferably a compound having two or more hydroxyl groups and a linear or branched alkylene chain (divalent aliphatic hydrocarbon group) or a linear or branched alkylene ether chain (alkyleneoxy group), and examples thereof include an aliphatic polyol compound (a3-1) and an oxyalkylene group-containing polyol compound (a3-2). The polyhydric alcohol compound (a3) ​​may be used alone or in combination of two or more kinds.

[0038] --Aliphatic polyol compound (a3-1)-- In this embodiment, the aliphatic polyol compound (a3-1) provides a cured product (curable resin composition) that has high flexibility, fracture toughness, and tensile strength, and is excellent in impregnation into substrates and reinforcing fibers. From the viewpoint of ease of control of the molecular weight distribution of the reaction product, the aliphatic polyol compound (a3-1) is preferably a diol compound containing two alcoholic hydroxyl groups, more preferably a linear aliphatic diol compound having 2 to 20 carbon atoms, more preferably a linear aliphatic diol compound having 4 to 18 carbon atoms, and even more preferably a linear aliphatic diol compound having 6 to 16 carbon atoms.

[0039] Examples of the aliphatic polyol compound (a3-1) include linear aliphatic diol compounds such as ethylene glycol (number average molecular weight: 62), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol; propylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-ethylbutane-14-butanediol, and 2,3-dimethyl-1,4-butanediol. Examples of branched chain aliphatic diol compounds include hexanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 3,3-dimethylpentane-1,5-diol, 2,2-diethyl-1,3-propanediol, 3-propylpentane-1,5-diol, 2,2-diethyl-1,4-butanediol, 2,4-diethyl-1,5-pentanediol, 2,2-dipropyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, and 2,5-diethyl-1,6-hexanediol; and tri- or higher functional aliphatic polyol compounds such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol. These aliphatic polyol compounds may be used alone or in combination of two or more.

[0040] --Oxyalkylene group-containing polyol compound (a3-2)-- In the present embodiment, the oxyalkylene group-containing polyol compound (a3-2) is preferably a diol compound having two alcoholic hydroxyl groups, more preferably a diol compound having a hydroxyl group equivalent of 50 to 269 g / eq, and even more preferably a diol compound having a hydroxyl group equivalent of 100 to 250 g / eq, because a cured product (curable resin composition) can be obtained that has high flexibility, fracture toughness, and tensile strength and is excellent in impregnation into substrates and reinforcing fibers. Examples of the oxyalkylene group-containing diol compound (a3-2) include ethylene oxide and propylene oxide adducts of glycols such as diethylene glycol and dipropylene glycol, and ethylene oxide and propylene oxide adducts of polyhydric phenol compounds such as ethylene oxide adducts of bisphenol A. These diol compounds may be used alone or in combination of two or more. In this embodiment, the number average molecular weight (Mn) of the polyhydric alcohol compound (a3) ​​is preferably in the range of 62 to 1000, more preferably 62 to 500. A number average molecular weight within the above range is preferable because it improves workability. The number average molecular weight (Mn) of the polyhydric alcohol compound (a3) ​​is either the value published by the manufacturer or a value obtained by measuring by gel permeation chromatography (GPC) under the conditions described below. The polyhydric alcohol compound (a3) ​​may be commercially available, such as diethylene glycol manufactured by Mitsubishi Chemical Corporation and BPA-2 glycol manufactured by Nippon Nyukazai Co., Ltd.

[0041] In this embodiment, the reaction raw materials may further include a compound that is reactive with the aromatic polycarboxylic acid, its acid halide and / or its ester (a1), or the monohydroxyaromatic compound (a2). The compound reactive with the aromatic polycarboxylic acid, its acid halide, and / or its ester (a1), or the monohydroxy aromatic compound (a2) is preferably a polyhydroxy aromatic compound (a4). Examples of the polyhydroxy aromatic compound (a4) include dihydroxy aromatic compounds, trihydroxy aromatic compounds, tetrahydroxy aromatic compounds, pentahydroxy aromatic compounds, and hexahydroxy aromatic compounds. Examples of the preferred polyhydroxy aromatic compound (a4) include m-dihydroxybenzene, 2,4-toluenediol, 3,5-toluenediol, p-xylene-2,6-diol, m-xylene-4,6-diol, p-dihydroxybenzene, 2,5-toluenediol, and p-xylene-2,5-diol. The polyhydroxy aromatic compound (a4) may be used alone or in combination of two or more kinds.

[0042] <Preferred Form of Aromatic Ester Compound (A)> The aromatic ester compound (A) of the present embodiment is represented by the following general formula (1): [ka] [In the above general formula (1), each A independently represents a linear or branched alkylene group, or a linear or branched alkylene ether group, Q 11 and Q 12 each independently represents a divalent aromatic group, Ar 11 and Ar 12 are each independently represented by the following general formula (2) or (3): [ka] [In the above general formula (2) and general formula (3), * represents Ar in the above general formula (1)] 11 or Ar 12 represents the bond to the oxygen atom that bonds to R 21 and R 31each independently represents a halogen atom, an alkyl group, an alkenyl group (such as an allyl group), an alkoxy group, an aryl group, or an aralkyl group; k 21 represents an integer from 0 to 7, and k 31 represents an integer of 0 to 5. p 11 represents an average number of repetitions of 0.01 or more.] The aromatic ester compound (A) represented by the general formula (1) has a plurality of ester bonds and contains a chain-like alkylene group or alkylene ether group with relatively low polarity, and therefore it is easy to function as a flexible segment, and is useful in that it can give a cured product with excellent flexibility or low dielectric properties. A more preferred example of the aromatic ester compound (A) of the present embodiment is represented by the above general formula (1), in which each A independently represents a linear or branched alkylene group (an alkylene group having 1 to 30 carbon atoms) or a linear or branched alkylene ether group (an alkylene ether group having 1 to 30 carbon atoms), and Q 11 and Q 12 each independently represents a 1,3-phenylene group or a 1,4-phenylene group; p 11 represents the average number of repetitions between 0.01 and 10, Ar 11 and Ar 12 each independently represents a structure represented by the general formula (2) or (3), and * in the general formula (2) and the general formula (3) represents Ar in the general formula (1). 11 or Ar 12 represents the bond to the oxygen atom that bonds to R 21 and R 31 each independently represents a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an aralkyl group; k 21 represents an integer from 0 to 7, and k 31 represents an integer of 0 to 5.] is preferably represented by the following. In the above general formula (1), A is preferably a linear or branched alkylene group or a linear or branched alkylene ether group, more preferably a linear alkylene group or a linear alkylene ether group, and among these, from the viewpoint of thermal decomposition resistance, it is even more preferable that A contains a linear alkylene ether group.

[0043] <Another preferred embodiment of the aromatic ester compound (A)> Another preferred embodiment of the aromatic ester compound (A) of the present embodiment is a reaction product obtained by using an ester compound (a') (also referred to as intermediate product (a')) and a polyhydric alcohol compound (a3) ​​as reaction raw materials (I), and the ester compound (a') may also be a reaction product obtained by using an aromatic polycarboxylic acid, its acid halide and / or its ester (a1) and a monohydroxy aromatic compound (a2) as reaction raw materials (II). The reaction of an aromatic polycarboxylic acid (a1) with a monohydroxy aromatic compound (a2) forms an ester bond to give an ester compound (a'). On the other hand, the reaction of the ester compound (a') with the polyhydric alcohol compound (a3) ​​causes a transesterification reaction to give an aromatic ester compound (A) containing a terminal aromatic ring-containing group (e.g., an aryloxycarbonyl group). Therefore, the aromatic ester compound (A) of the present embodiment is preferably a reaction product obtained by reacting a reaction product of an aromatic polycarboxylic acid (a1) with a monohydroxy aromatic compound (a2) with a polyhydric alcohol compound (a3) ​​(e.g., a compound having two or more hydroxyl groups and a linear or branched alkylene chain or a linear or branched alkylene ether chain).

[0044] In the resin composition having an acid group and a polymerizable unsaturated group of this embodiment, the use of an aromatic ester compound (A) is preferred because it can provide a cured product with a low dielectric loss tangent and excellent heat resistance and moist heat resistance. The reason for this is not entirely clear, but the aromatic ester compound (A) is preferably an aryloxycarbonyl group (for example, the partial structure represented by the general formula (i) above, more specifically, Q in the general formula (1) above). 11 and / or Q 12 and Ar 11 and / or Ar 12 Because the aromatic ester compound (a3) ​​contains an ester structure having the following structure at its terminal, it exhibits high reactivity with epoxy groups contained in the component (B) or epoxy resin, as described below. This high reactivity can prevent or suppress the generation of hydroxyl groups resulting from the ring-opening of the epoxy group, which is a preferred embodiment. Furthermore, by using a polyhydric alcohol compound (a3) ​​having a flexible segment structure (e.g., A in the above general formula (1)), an alkylene chain (e.g., a divalent aliphatic hydrocarbon group) or an alkylene ether chain (oxyalkylene group) derived from the polyhydric alcohol compound (a3) ​​can be introduced into the structure of the resulting aromatic ester compound (A). This can impart flexibility to a cured product obtained using the aromatic ester compound (A), and furthermore, the introduction of a structure with low polarity results in excellent low dielectric properties, which is a preferred embodiment. Furthermore, as described above, the aromatic ester compound (A) does not have, or substantially does not have, hydroxyl groups in its molecule. Therefore, the cured product obtained by the reaction of the aromatic ester compound (A) also does not have, or substantially does not have, hydroxyl groups derived from the aromatic ester compound (A). Such an aromatic ester compound (A) can prevent or suppress the generation of hydroxyl groups during curing. Generally, highly polar hydroxyl groups are known to increase the dielectric loss tangent. However, the use of the aromatic ester compound (A) of this embodiment is useful because it can achieve a low dielectric loss tangent in the cured product. The aromatic ester compound (A) has two or more reactive ester bonds, and therefore the crosslink density of the cured product is increased, and the heat resistance can be improved.

[0045] <Characteristics of aromatic ester compound (A)> When the total number of aromatic ester groups contained in the aromatic ester compound (A) is taken as the number of functional groups of the aromatic ester compound (A), the functional group equivalent of the aromatic ester compound (A) in this embodiment is preferably in the range of 160 to 1500 g / eq, more preferably in the range of 180 to 1200 g / eq, and even more preferably in the range of 200 to 660 g / eq, since this gives a cured product with excellent curability and a low dielectric constant and dielectric dissipation factor (low dielectric properties). The number average molecular weight (Mn) of the aromatic ester compound (A) of this embodiment is preferably 320 to 3000, more preferably 360 to 2400. A number average molecular weight (Mn) of 320 or more is preferable because it provides an excellent dielectric loss tangent. On the other hand, a number average molecular weight (Mn) of 3000 or less is preferable because it provides excellent moldability. The aromatic ester compound (A) of the present embodiment preferably has a softening point of 200°C or lower, and more preferably 180°C or lower, from the viewpoints of ease of handling when prepared as a curable resin composition described later, and an excellent balance between excellent elongation and dielectric properties of the cured product. The aromatic ester compound (A) of the present embodiment has a flexible segment such as an alkylene chain or an alkylene ether chain, and does not have or substantially does not have a hydroxyl group, and therefore has a low polarity structure. The aromatic ester compound (A) can provide a curable resin composition (for example, an epoxy resin composition containing an epoxy resin) that can exhibit excellent flexibility, moisture absorption resistance, adhesion to copper foil or the like due to the flexibility, and low dielectric properties in the obtained cured product, as well as a semiconductor encapsulating material, a semiconductor device, a prepreg, a circuit board, a build-up film, and the like, using the curable resin composition.

[0046] <Synthesis of aromatic ester compound (A)> The synthesis method of the aromatic ester compound (A) is not particularly limited, except that the aromatic polycarboxylic acid (a1), the monohydroxy aromatic compound (a2), and the polyhydric alcohol compound (a3) ​​are reacted as raw materials. However, in the synthesis of the aromatic ester compound (A), (1) a first reaction step in which an aromatic polycarboxylic acid (a1) is reacted with a monohydroxy aromatic compound (a2) to obtain an intermediate product (a'); and (2) a second reaction step in which the intermediate product (a') is reacted with a polyhydric alcohol compound (a3) ​​to obtain an aromatic ester compound (A) as a reaction product; It is preferable to use a method including the following, because the aromatic ester compound (A) can be obtained relatively easily. In this case, in the first reaction step, an ester compound having an ester bond formed therein is obtained as an intermediate product (a'), and in the subsequent second reaction step, an ester exchange reaction occurs to obtain an aromatic ester compound (A) having an aryloxycarbonyl group structure at its terminal.

[0047] The conditions for the first reaction step are not particularly limited, but can be, for example, in the presence of an alkali catalyst, at a temperature of 60°C or less, for a reaction time of 1 to 24 hours. Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. These alkali catalysts may be used alone or in combination of two or more. Among these, sodium hydroxide or potassium hydroxide is preferred as the alkali catalyst because of its high reaction efficiency. The alkali catalyst may be used as a 3 to 30% aqueous solution. In this case, a phase transfer catalyst may be used to improve the reaction efficiency. Examples of the phase transfer catalyst include alkylammonium salts and crown ethers. These phase transfer catalysts may be used alone or in combination of two or more.

[0048] The first reaction step is preferably carried out in an organic solvent, since this makes it easier to control the reaction. Examples of the organic solvent include hydrocarbon solvents such as pentane and hexane, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ether solvents such as diethyl ether and tetrahydrofuran, acetate ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, carbitol solvents such as cellosolve and butyl carbitol, aromatic hydrocarbon solvents such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These organic solvents may be used alone or in combination of two or more.

[0049] The reaction ratio of the aromatic polycarboxylic acid (a1) and the monohydroxy aromatic compound (a2) can be appropriately changed depending on the desired molecular design. However, from the viewpoint of improving excellent developability, good coating appearance, excellent elongation, and low dielectric properties in a balanced manner, the ratio of the monohydroxy aromatic compound (a2) to 1 mole of the aromatic polycarboxylic acid (a1) is preferably in the range of 2.0 to 5.0 moles, more preferably in the range of 2.0 to 4.0 moles, and even more preferably in the range of 2.0 to 3.0 moles.

[0050] After the reaction in the first reaction step is completed, if an aqueous solution is used in the presence of an alkali catalyst, it is preferable to leave the reaction solution to separate and remove the aqueous layer, and then wash the remaining organic layer with water, repeating the water washing until the aqueous layer becomes nearly neutral (about pH 7). This makes it possible to reduce the content of inorganic salts that adversely affect the insulating properties in the resulting intermediate product (a').

[0051] Next, in the second reaction step, the intermediate product (a') obtained in the first reaction step is reacted with a polyhydric alcohol compound (a3). The conditions for the second reaction step are not particularly limited, but for example, the reaction can be carried out at a temperature of 50 to 250°C and with stirring for 1 to 24 hours. In addition, in the second reaction step, the reaction can be promoted by adding an alkali catalyst, particularly an amine catalyst (alkylamines such as triethylamine, arylamines such as triphenylamine, fused amines such as DBU and DBN, and heterocyclic amines such as imidazole and pyridine).

[0052] During the reaction in the second reaction step, an antioxidant may be used to prevent deterioration due to the inclusion of trace amounts of oxygen. Specific examples of the antioxidant include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, "4-[[4,6-bis(octylthio)- Phenol compounds such as 1,3,5-triazin-2-yl]amino]-1,6-di-tert-butylphenol, quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N''-diphenyl-p-phenylenediamine, Ni-propyl-N''-phenyl-p-phenylenediamine, N-(1,3,5-triazin-2-yl)amino-1,6-di-tert-butylphenol, and the like.Amine compounds such as 3-dimethylbutyl)-N''-phenyl-p-phenylenediamine, diphenylamine, 4,4''-dicumyl-diphenylamine, 4,4''-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine with 2,4,4-trimethylpentene, and reaction products of diphenylamine with 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl)methyl]-2,2-dione, 2,2-bis(2,2-dione), ... Thioether compounds such as (decylthio)propionyl]oxy}methyl)-1,3-propanediyl bis[3-(dodecylthio)propionate], ditridecan-1-yl 3,3'-sulfanediyl dipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitrosoaniline, N-nitroso-N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N Nitroso compounds such as n-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, and 2-nitroso-5-methylaminophenol hydrochloride, esters of phosphoric acid and octadecan-1-ol, triphenyl phosphite, and 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, phosphite compounds such as tris(2,4-di-tert-butylphenyl) phosphite, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate Examples of antioxidants include zinc compounds such as zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and distearyl 3,3'-thiodipropionate. These antioxidants can be used alone or in combination. Examples of commercially available antioxidants include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd. In the second reaction step, the same solvent as that used in the first reaction step can be used.

[0053] The reaction ratio of the intermediate product (a') and the polyhydric alcohol compound (a3) ​​can be appropriately changed depending on the desired molecular design. However, from the viewpoint of achieving a balanced improvement in excellent developability, good coating appearance, excellent elongation, and low dielectric properties, the hydroxyl group equivalent of the polyhydric alcohol compound (a3) ​​relative to 1 equivalent of the active ester group of the intermediate product (a') is preferably in the range of 0.01 to 0.9 mol, more preferably in the range of 0.05 to 0.9 mol, and even more preferably in the range of 0.1 to 0.8 mol.

[0054] After the reaction in the second reaction step is completed, it is preferable to carry out atmospheric distillation or reduced pressure distillation (for example, 0.9 to 0.01 atmospheres) to remove excess monohydroxy aromatic compound (a2), thereby increasing the purity of the resulting aromatic ester compound (A).

[0055] (Resin (B) having an acid group and a polymerizable unsaturated group) The resin composition having an acid group and a polymerizable unsaturated group of this embodiment contains a resin (B) having an acid group and a polymerizable unsaturated group as an essential component. Component (B) is not particularly limited as long as it has an acid group and a polymerizable unsaturated group, and a wide variety of resins can be used, with no particular restrictions on the specific structure or molecular weight.

[0056] In this embodiment, examples of the acid group contained in the resin (B) having an acid group and a polymerizable unsaturated group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferred because it exhibits excellent alkaline developability. In this specification, examples of the "polymerizable unsaturated group" include a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, and a vinyl ether group.

[0057] Examples of the resin (B) having an acid group and a polymerizable unsaturated group of the present embodiment include the following [1] to [6]: [1] an epoxy resin (B1) having an acid group and a polymerizable unsaturated group, [2] Urethane resin (B2) having an acid group and a polymerizable unsaturated group [3] an acrylic resin (B3) having an acid group and a polymerizable unsaturated group, [4] Amide-imide resin (B4) having an acid group and a polymerizable unsaturated group, [5] Acrylamide resin (B5) having an acid group and a polymerizable unsaturated group, [6] Ester resin (B6) having an acid group and a polymerizable unsaturated group, The above epoxy resin (B1) to ester resin (B6) will be explained in order below.

[0058] <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> Examples of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group of the present embodiment include an epoxy (meth)acrylate resin having an acid group, which is produced from an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), and a polybasic acid anhydride (b1-3) as essential reaction raw materials; and an epoxy (meth)acrylate resin having an acid group and a urethane bond, which is produced from an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), a polybasic acid anhydride (b1-3), a polyisocyanate compound (b1-4), and a (meth)acrylate compound (b1-5) having a hydroxyl group as reaction raw materials.

[0059] The specific structure of the epoxy resin (b1-1) is not particularly limited as long as it has a plurality of epoxy groups in the resin. Examples of the epoxy resin (b1-1) include bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, biphenol-type epoxy resins, hydrogenated biphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol novolac-type epoxy resins, naphthol novolac-type epoxy resins, naphthol-phenol co-condensed novolac-type epoxy resins, naphthol-cresol co-condensed novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, biphenyl aralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, and oxazolidone-type epoxy resins. These epoxy resins can be used alone or in combination of two or more.

[0060] Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Examples of the hydrogenated bisphenol epoxy resin include hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol B epoxy resin, hydrogenated bisphenol E epoxy resin, hydrogenated bisphenol F epoxy resin, and hydrogenated bisphenol S epoxy resin. Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'-biphenol type epoxy resin. Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin. The epoxy resin (b1-1) can be used alone or in combination of two or more kinds.

[0061] Examples of the unsaturated monobasic acid (b1-2) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Acid halides and esters of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following general formula (4) can also be used. [ka] [In the above general formula (4), X 41 represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain; X 41A hydrogen atom in the structure of Y may be substituted with a halogen atom or an alkoxy group; 41 is a hydrogen atom or a methyl group.

[0062] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain. An example of the (poly)ester chain is a (poly)ester chain represented by the following general formula (5). [ka] [In the above general formula (5), R 51 and R 52 represents an alkylene group having 1 to 10 carbon atoms, and n represents an integer of 1 to 5.

[0063] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. Furthermore, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used. An example of the (poly)carbonate chain is a (poly)carbonate chain represented by the following general formula (6). [ka] [In the above general formula (6), R 61 represents an alkylene group having 1 to 10 carbon atoms, and n 61 represents an integer from 1 to 5.] The molecular weight of the compound represented by formula (4) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400. The unsaturated monobasic acids (b1-2) can be used alone or in combination of two or more kinds.

[0064] Examples of the polybasic acid anhydride (b1-3) include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, acid halides of aliphatic polybasic acid anhydrides, acid halides of alicyclic polybasic acid anhydrides, and acid halides of aromatic polybasic acid anhydrides.

[0065] Examples of the aliphatic polybasic acid anhydrides include anhydrides of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, etc. The aliphatic hydrocarbon group of the aliphatic polybasic acid anhydride may be either linear or branched, and may have an unsaturated bond in the structure. In the present invention, the alicyclic polybasic acid anhydride is one in which the acid anhydride group is bonded to an alicyclic structure, and the presence or absence of aromatic rings in other structural positions is not important. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydrides. Examples of the aromatic polybasic acid anhydrides include anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid. The polybasic acid anhydrides (b1-3) can be used alone or in combination of two or more. Among these, tetrahydrophthalic anhydride, succinic anhydride, and cyclohexanedicarboxylic anhydride are preferred from the viewpoint of achieving a good balance of excellent developability, good coating film appearance, excellent elongation, and low dielectric properties.

[0066] Examples of the polyisocyanate compound (b1-4) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate. aromatic diisocyanate compounds such as methyl methyl ether, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following general formula (7); and isocyanurate-modified products, biuret-modified products, and allophanate-modified products of these. The polyisocyanate compounds (b1-4) can be used alone or in combination of two or more kinds. [ka] [In the above general formula (7), R 72 and R 73 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; R 71 each independently represents an alkyl group having 1 to 4 carbon atoms, k 71 is 0 or an integer of 1 to 3, and n 71 is an integer greater than or equal to 1.]

[0067] Examples of the (meth)acrylate compound (b1-5) having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. In addition, (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds described above, and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds described above, can also be used. Among these, from the viewpoint of achieving a balanced improvement in excellent developability, good coating film appearance, excellent elongation, and low dielectric properties, those having a molecular weight of 1,000 or less are preferred. Furthermore, when the (meth)acrylate compound (b1-5) having a hydroxyl group is an oxyalkylene-modified compound or a lactone-modified compound, it is preferred that the weight-average molecular weight (Mw) is 1,000 or less. The (meth)acrylate compound (b1-5) having a hydroxyl group can be used alone or in combination of two or more kinds.

[0068] The method for producing the epoxy resin (B1) having an acid group and a polymerizable unsaturated group of the present embodiment is not particularly limited, and any method may be used. The production of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary. In this embodiment, the method for producing the epoxy resin (B1) having an acid group and a polymerizable unsaturated group is not particularly limited, as long as it uses an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), and a polybasic acid anhydride (b1-3) as essential reaction raw materials, or an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), a polybasic acid anhydride (b1-3), a polyisocyanate compound (b1-4), and a (meth)acrylate compound (b1-5) having a hydroxyl group as reaction raw materials. For example, the epoxy resin (B1) may be produced by a method in which all of the reaction raw materials are reacted at once, or by a method in which the reaction raw materials are reacted sequentially. Among these, a method in which the epoxy resin (b1-1) is first reacted with the unsaturated monobasic acid (b1-2), and then the polybasic acid anhydride (b1-3) is reacted is preferred because it allows for easy reaction control. The reaction can be carried out, for example, by reacting an epoxy resin (b1-1) with an unsaturated monobasic acid (b1-2) in the presence of a basic catalyst at a temperature of 100 to 150°C, and then adding a polybasic acid anhydride (b1-3) to the reaction system and reacting at a temperature of 80 to 120°C. In this embodiment, the reaction ratio of the epoxy resin (b1-1) and the unsaturated monobasic acid (b1-2) is preferably in the range of 0.9 to 1.1 moles of the unsaturated monobasic acid (b1-2) per mole of epoxy groups in the epoxy resin (b1-1). The reaction ratio of the polybasic acid anhydride (b1-3) is preferably in the range of 0.2 to 1.0 moles per mole of epoxy groups in the epoxy resin (b1-1).

[0069] Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol, cellosolve, methanol, ethanol, propanol, isopropanol, butanol, and cyclohexanol. Examples of suitable organic solvents include alcohol solvents such as ethanol and propylene glycol monomethyl ether; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and methyl carbitol; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more.

[0070] In addition, commercially available organic solvents can also be used. Examples of commercially available organic solvents include "No. 1 Spindle Oil," "No. 3 Solvent," "No. 4 Solvent," "No. 5 Solvent," "No. 6 Solvent," "Naphtesol H," "Alkene 56NT," "AF Solvent No. 4," "AF Solvent No. 5," "AF Solvent No. 6," and "AF Solvent No. 7" manufactured by ENEOS Corporation; "Diadol 13" and "Dialene 168" manufactured by Mitsubishi Chemical Corporation; "F Oxocol" and "F Oxocol 180" manufactured by Nissan Chemical Industries, Ltd.; "Supersol LA35" and "Supersol LA38" manufactured by Idemitsu Kosan Co., Ltd.; and "ExxonMobil Examples include Exxor D80, Exxor D110, Exxor D120, Exxor D130, Exxor D160, Exxor D100K, Exxor D120K, Exxor D130K, Exxor D280, Exxor D300, and Exxor D320 manufactured by Exxor Chemical Co., Ltd. The organic solvents can be used alone or in combination of two or more. In the present embodiment, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, as this improves the reaction efficiency.

[0071] Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, tri quaternary ammonium salts such as octylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octoate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, etc. can also be used. The basic catalysts can be used alone or in combination of two or more. The amount of the basic catalyst added is preferably in the range of 0.001 to 5 parts by mass per 100 parts by mass of the total of the reaction raw materials.

[0072] In the present embodiment, the acid value of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group is preferably in the range of 30 to 150 mgKOH / g, more preferably in the range of 40 to 120 mgKOH / g, because a resin composition having an acid group and a polymerizable unsaturated group capable of forming a cured product having excellent developability, heat resistance, and dielectric properties can be obtained. Note that the acid value of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group in the present disclosure is a value measured by the neutralization titration method of JIS 0070 (1992).

[0073] <Urethane resin having an acid group and a polymerizable unsaturated group (B2)> Examples of the urethane resin (B2) having an acid group and a polymerizable unsaturated group of the present embodiment include a resin obtained by reacting a polyisocyanate compound (b1-4), a hydroxyl group-containing (meth)acrylate compound (b1-5), a carboxyl group-containing polyol compound (b2-1), and, if necessary, a polybasic acid anhydride (b1-3) and a polyol compound (b2-2) other than the carboxyl group-containing polyol compound (b2-1); a resin obtained by reacting a polyisocyanate compound (b1-4) with a hydroxyl group-containing (meth)acrylate compound (b1-5), a carboxyl group-containing polyol compound (b2-1), and, if necessary, a polybasic acid anhydride (b1-3), and a polyol compound (b2-2) other than the carboxyl group-containing polyol compound (b2-1); Examples of the hydroxyl group-containing (meth)acrylate compound (b1-5) include a resin obtained by reacting a hydroxyl group-containing (meth)acrylate compound (b1-5) with a polybasic acid anhydride (b1-3) and a polyol compound (b2-2) other than the carboxyl group-containing polyol compound (b2-1); or a resin obtained by reacting an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), a polybasic acid anhydride (b1-3), a polyisocyanate compound (b1-4) and a hydroxyl group-containing (meth)acrylate compound (b1-5).

[0074] Examples of the carboxyl group-containing polyol compound (b2-1) include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, etc. The carboxyl group-containing polyol compounds can be used alone or in combination of two or more. Examples of polyol compounds (b2-2) other than the carboxyl group-containing polyol compound (b2-1) include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains have been introduced into the molecular structure of the above-mentioned various polyol compounds; and lactone modified compounds in which (poly)lactone structures have been introduced into the molecular structure of the above-mentioned various polyol compounds. The polyol compounds other than the carboxyl group-containing polyol compounds can be used alone or in combination of two or more.

[0075] The method for producing the urethane resin (B2) having an acid group and a polymerizable unsaturated group in this embodiment is not particularly limited, and any method may be used. The production of the urethane resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary. The organic solvent may be the same as the organic solvent described above in the section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group>, and the organic solvent may be used alone or in combination of two or more. The basic catalyst may be the same as the basic catalyst described above in the section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group>, and the basic catalyst may be used alone or in combination of two or more.

[0076] <Acrylic resin having an acid group and a polymerizable unsaturated group (B3)> Examples of the acrylic resin (B3) having an acid group and a polymerizable unsaturated group in this embodiment include a reaction product obtained by polymerizing, as an essential component, a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group, to obtain an acrylic resin intermediate, and then reacting the resulting acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with the functional group, thereby introducing a (meth)acryloyl group; and a resin obtained by reacting a polybasic acid anhydride (b1-3) with the hydroxyl group in the reaction product.

[0077] In this embodiment, the acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and, if necessary, other polymerizable unsaturated group-containing compounds. Examples of such other polymerizable unsaturated group-containing compounds include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. The other polymerizable unsaturated group-containing compounds can be used alone or in combination of two or more kinds.

[0078] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group possessed by the (meth)acrylate compound (α), but the following combinations are preferred from the viewpoint of reactivity. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more kinds.

[0079] The method for producing the acrylic resin (B3) having an acid group and a polymerizable unsaturated group in this embodiment is not particularly limited, and any method may be used. The production of the acrylic resin (B3) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary. As the organic solvent, the same organic solvents as those described in the above section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> can be used, and the organic solvents can be used alone or in combination of two or more. As the basic catalyst, the same basic catalysts as those described in the above section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> can be used, and the basic catalysts can be used alone or in combination of two or more.

[0080] The acid value of the acrylic resin (B3) having an acid group and a polymerizable unsaturated group in this embodiment is preferably in the range of 30 to 150 mgKOH / g, more preferably in the range of 40 to 120 mgKOH / g, because a resin composition having an acid group and a polymerizable unsaturated group that can form a cured product having excellent developability, heat resistance, and dielectric properties can be obtained. Note that the acid value of the acrylic resin (B3) having an acid group and a polymerizable unsaturated group in this disclosure is a value measured by the neutralization titration method of JIS K 0070 (1992).

[0081] <Amide-imide resin having an acid group and a polymerizable unsaturated group (B4)> In this embodiment, the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group may be, for example, a compound obtained by reacting an amide-imide resin (b4-1) having an acid group and / or an acid anhydride group with a (meth)acrylate compound (b1-5) having a hydroxyl group and / or a (meth)acrylate compound having an epoxy group, and, if necessary, with a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having the reactive functional group may or may not have a (meth)acryloyl group. The amide-imide resin (b4-1) having an acid group and / or an acid anhydride group may have either an acid group or an acid anhydride group, or both. From the viewpoint of reactivity and reaction control with the (meth)acrylate compound (1-5) having a hydroxyl group or the epoxy compound having a (meth)acryloyl group, the amide-imide resin (b4-1) preferably has an acid anhydride group, and more preferably has both an acid group and an acid anhydride group. The acid value of the solid content of the amide-imide resin (b4-1) measured under neutral conditions, i.e., conditions under which the acid anhydride group is not ring-opened, is preferably in the range of 60 to 350 mg KOH / g. On the other hand, the acid value measured under conditions under which the acid anhydride group is ring-opened, such as in the presence of water, is preferably in the range of 61 to 360 mg KOH / g.

[0082] Furthermore, the amide-imide resin (b4-1) may contain, as necessary, a polybasic acid as a reaction raw material in addition to the polyisocyanate compound (b1-4) and the polybasic acid anhydride (b1-3). The polybasic acid may be any compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 -dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. Furthermore, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. The above polybasic acids can be used alone or in combination of two or more kinds.

[0083] The (meth)acrylate compound having an epoxy group is not particularly limited in structure as long as it has a (meth)acryloyl group and an epoxy group in its molecular structure, and a wide variety of compounds can be used. Examples include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate, as well as mono(meth)acrylates of diglycidyl ether compounds such as hydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The above (meth)acrylate compounds having an epoxy group can be used alone or in combination of two or more kinds.

[0084] The specific structure or production method of the amide-imide resin (b4-1) having an acid group and / or an acid anhydride group is not particularly limited, and a wide variety of general amide-imide resins can be used. The amide-imide resin (b4-1) of this embodiment is preferably obtained, for example, from a polyisocyanate compound (b1-4) and a polybasic acid anhydride (b1-3) as reaction raw materials. In the present embodiment, the polyisocyanate compound (b1-4) is preferably an alicyclic diisocyanate compound or a modified product thereof, or an aliphatic diisocyanate compound or a modified product thereof, since a resin composition having an acid group and a polymerizable unsaturated group and having high solvent solubility can be obtained, and more preferably an alicyclic diisocyanate or an isocyanurate-modified product thereof, or an aliphatic diisocyanate or an isocyanurate-modified product thereof. In this embodiment, the proportion of the total mass of the alicyclic diisocyanate compound or modified product thereof and the aliphatic diisocyanate compound or modified product thereof in the total mass of the polyisocyanate compound (b1-4) is preferably 70 mass% or more, and more preferably 90 mass% or more. Furthermore, when an alicyclic diisocyanate compound or a modified product thereof is used in combination with an aliphatic diisocyanate compound or a modified product thereof, the mass ratio of the two (alicyclic diisocyanate compound or a modified product thereof / aliphatic diisocyanate compound or a modified product thereof) is preferably in the range of 30 / 70 to 70 / 30.

[0085] The method for producing the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group in this embodiment is not particularly limited, and any method may be used. The production of the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary. As the basic catalyst, the same basic catalysts as those described in the above section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> can be used, and the basic catalysts can be used alone or in combination of two or more. The organic solvent may be the same as the organic solvents described in the above section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group>, and the organic solvents may be used alone or in combination of two or more.

[0086] In this embodiment, the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group can be prepared by using other reaction raw materials in addition to the reaction raw materials of the amide-imide resin (b4-1) having an acid group and / or an acid anhydride group, the hydroxyl-containing (meth)acrylate compound (b1-5) and / or the (meth)acrylate compound (b4-2) having an epoxy group, depending on the desired resin performance, etc. In this case, the proportion of the total mass of the components (b4-1) to (b4-2) in the total mass of the reaction raw materials for the resin (B4) having an acid group and a polymerizable unsaturated group is preferably 80 mass% or more, more preferably 90 mass% or more.

[0087] In this embodiment, the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group may be produced by any method without particular limitation. For example, the amide-imide resin (b4-1) and the reaction raw materials including the hydroxyl group-containing (meth)acrylate compound (b1-5) and / or the epoxy group-containing (meth)acrylate compound (b4-2) may be reacted all at once, or the reaction raw materials may be reacted sequentially. Furthermore, for example, the reaction between the amide-imide resin (b4-1) and the hydroxyl group-containing (meth)acrylate compound (b1-5) may be carried out by heating and stirring at a temperature of about 80 to 140°C in the presence of a suitable basic catalyst. The production of the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and a basic or acidic catalyst may be used, if necessary.

[0088] The basic catalyst may be the same as the acidic catalyst and basic catalyst described in the section above under <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group>, and these may be used alone or in combination of two or more. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Solid acid catalysts having a strong acid such as a sulfonyl group can also be used. These acid catalysts can be used alone or in combination of two or more.

[0089] The acid value of the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group in this embodiment is preferably in the range of 30 to 150 mgKOH / g, more preferably in the range of 40 to 120 mgKOH / g, because a resin composition having an acid group and a polymerizable unsaturated group capable of forming a cured product having excellent developability, heat resistance, and dielectric properties can be obtained. Note that the acid value of the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group in the present disclosure is a value measured by the neutralization titration method of JIS K 0070 (1992).

[0090] <Acrylamide resin having an acid group and a polymerizable unsaturated group (B5)> Examples of the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group of this embodiment include a resin obtained by reacting a phenolic hydroxyl group-containing compound (b5-1), an alkylene carbonate (b5-2a) or an alkylene oxide (b5-2b), an N-alkoxyalkyl (meth)acrylamide compound (b5-3), a polybasic acid anhydride (b1-3), and, if necessary, an unsaturated monobasic acid (b1-2) as reaction raw materials.

[0091] In this embodiment, the phenolic hydroxyl group-containing compound (b5-1) refers to a compound having at least one phenolic hydroxyl group in its molecule. Examples of the phenolic hydroxyl group-containing compound (b5-1) include a compound represented by any one of the following general formulas (8.1) to (8.4), a reaction product obtained by using, as essential reaction raw materials, an aromatic polyhydroxy compound (b5-4) and a compound represented by any one of the following general formulas (9.1) to (9.5), and a novolac-type phenolic resin obtained by using, as reaction raw materials, one or more of the aromatic polyhydroxy compound (b5-4) and other compounds (b5-5) having one phenolic hydroxyl group in their molecules. [ka] (In the above general formulas (8.1) to (8.4), R 81 ~R 84 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; R 85 and R 86 each independently represents a hydrogen atom or a methyl group; j 81 ~j 84 Each independently represents an integer of 0 or 1 or more, preferably 0 or an integer of 1 to 3, and more preferably 0 or 1. 81 ~k 84 each independently represents an integer of 1 or more, preferably 2 or 3. The positions of the substituents on the aromatic rings in the general formulas (8.1) to (8.4) are arbitrary. For example, in the naphthalene ring of the general formula (8.2), they may be substituted with any hydrogen atom on the ring. In the general formula (8.3), they may be substituted with any hydrogen atom on the benzene ring present in one biphenyl molecule. In the general formula (8.4), they may be substituted with any hydrogen atom on the benzene ring present in one aralkyl molecule. When the number of substituents in one molecule is j, 81 ~j 84 and k 81 ~k 84 This indicates that [ka] (In the above general formulas (9.1) to (9.5), h 91 represents 0 or 1, R 91 ~R 96 each independently represents a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group; k 91 ~k 96 each independently represents 0 or an integer of 1 to 4, and Z 91 ~Z 96 each independently represents a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group; Y 91 represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, and n 91 represents an integer from 1 to 4.) The compounds represented by the above general formulas (9.1) to (9.5) can be used alone or in combination of two or more kinds.

[0092] Examples of the aromatic polyhydroxy compound (b5-4) include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, bisphenol, and compounds having one or more substituents on the aromatic nucleus thereof. Examples of the substituent on the aromatic nucleus include monovalent aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl; alkoxy groups such as methoxy, ethoxy, propyloxy, and butoxy; halogen atoms such as fluorine, chlorine, and bromine; phenyl, naphthyl, and anthryl groups, and aryl groups having the aliphatic hydrocarbon group, alkoxy group, or halogen atom substituted on the aromatic nucleus; phenyloxy, naphthyloxy, and aryloxy groups having the aliphatic hydrocarbon group, alkoxy group, or halogen atom substituted on the aromatic nucleus; phenylmethyl, phenylethyl, naphthylmethyl, and naphthylethyl groups, and aralkyl groups having the aliphatic hydrocarbon group, alkoxy group, or halogen atom substituted on the aromatic nucleus. These aromatic polyhydroxy compounds can be used alone or in combination of two or more. Among these, compounds containing no halogen are preferred because they can provide resins having acid groups and polymerizable unsaturated groups with high insulating reliability.

[0093] Examples of the novolac phenolic resin include resins obtained by reacting one or more compounds having one phenolic hydroxyl group in the molecule with an aldehyde compound in the presence of an acid catalyst.

[0094] The above-mentioned other compounds (b5-5) having one phenolic hydroxyl group in the molecule may be any aromatic compound having one hydroxyl group on the aromatic nucleus, such as phenol or a phenol compound having one or more substituents on the phenolic aromatic nucleus, naphthol or a naphthol compound having one or more substituents on the naphthol aromatic nucleus, and anthracenol or anthracenol compound having one or more substituents on the anthracenol aromatic nucleus. Examples of the substituent on the aromatic nucleus include monovalent aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, aryl groups, aryloxy groups, and aralkyl groups, with specific examples being as described above. These compounds having one phenolic hydroxyl group can be used alone or in combination of two or more.

[0095] Examples of the aldehyde compound include formaldehyde; alkyl aldehydes such as acetaldehyde, propyl aldehyde, butyl aldehyde, isobutyl aldehyde, pentyl aldehyde, and hexyl aldehyde; hydroxybenzaldehydes such as salicyl aldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, and 3,4-dihydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde; Examples of the benzaldehyde include aldehydes having both a hydroxy group and an alkoxy group, such as 4-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, and 4-hydroxy-3,5-dimethoxybenzaldehyde; alkoxybenzaldehydes, such as methoxybenzaldehyde and ethoxybenzaldehyde; hydroxynaphthaldehydes, such as 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, and 6-hydroxy-2-naphthaldehyde; and halogenated benzaldehydes, such as brombenzaldehyde.

[0096] Examples of alkylene carbonates (b5-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred from the viewpoint of achieving a good balance of excellent developability, good coating film appearance, excellent elongation, and low dielectric properties. The alkylene carbonates can be used alone or in combination of two or more.

[0097] Examples of the alkylene oxide (b5-2b) include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred from the viewpoint of achieving a good balance of excellent developability, good coating film appearance, excellent elongation, and low dielectric properties. The alkylene oxides can be used alone or in combination of two or more.

[0098] Examples of the N-alkoxyalkyl(meth)acrylamide compound (b5-3) include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. Among these, N-methoxymethyl(meth)acrylamide is preferred from the viewpoint of achieving a balanced improvement in excellent developability, good coating film appearance, excellent elongation, and low dielectric properties. The N-alkoxyalkyl(meth)acrylamide compounds (b5-3) can be used alone or in combination of two or more kinds.

[0099] In the present embodiment, when the N-alkoxyalkyl(meth)acrylamide compound (b5-3) is used as a reaction raw material for the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group, the equivalent ratio of the N-alkoxyalkyl(meth)acrylamide compound (b5-3) to the polybasic acid anhydride (b1-3) [(b5-3) / (b1-3)] is preferably in the range of 0.2 to 7, more preferably in the range of 0.25 to 6.7, from the viewpoint of achieving a balanced improvement in excellent developability, good coating film appearance, excellent elongation, and low dielectric properties.

[0100] In this embodiment, the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group may be produced by any method without particular limitation. For example, the resin may be produced by reacting all of the reactant materials at once, or by sequentially reacting the reactant materials. Among these, a preferred method is one in which the phenolic hydroxyl group-containing compound (b5-1) is first reacted with an alkylene carbonate (b5-2a) or an alkylene oxide (b5-2b) (e.g., in the presence of a basic catalyst at a temperature of 100 to 200°C), followed by reaction with an unsaturated monobasic acid (b1-2) and / or an N-alkoxyalkyl (meth)acrylamide compound (b2-3b) (e.g., in the presence of an acidic catalyst at a temperature of 80 to 140°C), followed by reaction with a polybasic acid anhydride (b1-3) (e.g., reaction at a temperature of 80 to 140°C), because this method makes it easier to control the reaction. The acrylamide resin (B5) having an acid group and a polymerizable unsaturated group in this embodiment is a resin obtained from the above-mentioned reaction raw materials. Examples of the acrylamide resin (B5) include a resin having a resin structure in which the structural moiety (I) represented by the following general formula (10.1) and the structural moiety (II) represented by the following general formula (10.2) are repeated as structural units, and a resin having a resin structure in which the structural moiety (III) represented by the following formula (10.3) and the structural moiety (IV) represented by the following formula (10.4) are repeated as structural units. [ka] [In the above formula (10.1) or (10.2), R b2and R b8 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms; R b3 and R b9 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; n 1 and n 2 each independently represents 1 or 2; R b4 and R b10 each independently represents a methylene group or a structural moiety represented by any one of the following general formulas (11.1) to (11.5), and R b5 and R b6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R b5 and R b6 may be linked to form a saturated or unsaturated ring, R b11 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, and R b12 represents a hydrogen atom or a methyl group, and R b1 and R b7 are each independently the R b3 and the R b9 or the structural moiety (I) represented by formula (10.1) or the structural moiety (II) represented by formula (10.2) is R marked with an *. b4 or R b10 ] [ka] [In the above general formula (10.3) or (10.4), R b2 and R b8 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R b3 and R b9 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; n 3 and n 4 each independently represents 1 or 2; R b4 and R b10each independently represents a methylene group or a structural moiety represented by any one of the following formulas (11.1) to (11.5), and R b5 and R b6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R b5 and R b6 may be linked to form a saturated or unsaturated ring, R b11 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, and R b12 represents a hydrogen atom or a methyl group, and R b1 and R b7 are each independently the R b3 and the R b9 or the structural moiety (III) represented by general formula (10.3) or the structural moiety (IV) represented by general formula (10.4) is R b4 or R b10 ] [ka] [In the above general formulas (11.1) to (11.5), h 91 represents 0 or 1, R 91 ~R 96 each independently represents a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group; n 91 ~n 96 each independently represents 0 or an integer of 1 to 4, and Y 91 represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, and n 91 represents an integer from 1 to 4, and R 111 ~R 116 each independently represents a hydrogen atom or a methyl group, and W represents the following formula (12.1) or (12.2). [ka] [In the above formula (12.1) or (12.2), R 121 and R 124 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R122 and R 123 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R 122 and R 123 may be linked to form a saturated or unsaturated ring, R 125 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, and R 126 represents a hydrogen atom or a methyl group.

[0101] The acid value of the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group in this embodiment is preferably in the range of 30 to 150 mgKOH / g, more preferably in the range of 40 to 120 mgKOH / g, because a resin composition having an acid group and a polymerizable unsaturated group that can form a cured product having excellent developability, heat resistance, and dielectric properties can be obtained. Note that the acid value of the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group in the present disclosure is a value measured based on the neutralization titration method of JIS K 0070 (1992).

[0102] <Ester resin having an acid group and a polymerizable unsaturated group (B6)> Examples of the ester resin (B6) having an acid group and a polymerizable unsaturated group in this embodiment include a resin obtained by reacting a phenolic hydroxyl group-containing compound (b5-1), an alkylene oxide (b5-2b) or an alkylene carbonate (b5-2a), an unsaturated monobasic acid (b1-2), and a polybasic acid anhydride (b1-3).

[0103] As the alkylene oxide (b5-2b), the same alkylene oxides as those exemplified above as the alkylene oxide (b5-2b) can be used. Among these, ethylene oxide or propylene oxide is preferred from the viewpoint of achieving a good balance between excellent developability, good coating film appearance, excellent elongation, and low dielectric properties. The alkylene oxide (b5-2b) can be used alone or in combination of two or more kinds.

[0104] The alkylene carbonate (b5-2a) may be the same as those exemplified above for the alkylene carbonate (b5-2a). Among these, ethylene carbonate or propylene carbonate is preferred from the viewpoint of achieving a good balance of excellent developability, good coating film appearance, excellent elongation, and low dielectric properties. The alkylene carbonates (b5-2a) can be used alone or in combination of two or more kinds.

[0105] The method for producing the ester resin (B6) having an acid group and a polymerizable unsaturated group of this embodiment is not particularly limited, and any method may be used. The production of the ester resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst or an acidic catalyst, if necessary.

[0106] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more. As the basic catalyst, the same organic solvents as those exemplified above can be used, and the basic catalysts can be used alone or in combination of two or more. As the acidic catalyst, the same organic solvents as those exemplified above can be used, and the acidic catalysts can be used alone or in combination of two or more. The above are the essential components contained in the resin composition having an acid group and a polymerizable unsaturated group in this embodiment.

[0107] (Optional addition ingredient) Furthermore, the resin composition having an acid group and a polymerizable unsaturated group in this embodiment may contain various known additives such as an ultraviolet stabilizer and a storage stabilizer in addition to the above-mentioned compounds or resins.

[0108] The method for producing the resin composition having an acid group and a polymerizable unsaturated group of the present embodiment is not particularly limited, and the composition can be produced by kneading the various components described above using a kneader such as a roll mixer.

[0109] [Curable resin composition] The curable resin composition of this embodiment preferably contains the above-mentioned resin composition having an acid group and a polymerizable unsaturated group, and a photopolymerization initiator. More specifically, a suitable curable resin composition of this embodiment contains the above-mentioned resin composition having an acid group and a polymerizable unsaturated group (essentially containing an aromatic ester compound (A) and an acid group-containing methacrylate (B)), a photopolymerization initiator, and, if necessary, a curing agent, a solvent, other resins, and additives. The curing agent may be an epoxy resin or a curing agent other than the epoxy resin (hereinafter referred to as "other curing agent"). The other resin may be a resin other than the aromatic ester compound (A) and the acid group-containing methacrylate (B). The additive may be a filler, a flame retardant, a curing accelerator, an antioxidant, or an ultraviolet inhibitor.

[0110] In the curable resin composition of the present embodiment, the content of the aromatic ester compound (A) is preferably in the range of 5 to 95 mass %, more preferably in the range of 20 to 80 mass %, based on the solid content of the curable resin composition. In the curable resin composition of the present embodiment, the content of the resin (B) having an acid group and a polymerizable unsaturated group is preferably in the range of 5 to 95 mass %, more preferably in the range of 20 to 80 mass %, of the solid content of the curable resin composition.

[0111] In the curable resin composition of the present embodiment, the content of the resin composition having the acid group and the polymerizable unsaturated group described above is preferably 10 to 95 mass %, and more preferably 20 to 80 mass %, relative to the total amount (100 mass %) of the curable resin composition. In the curable resin composition of the present embodiment, the content of the curing agent is preferably 0 to 50 mass %, and more preferably 5 to 40 mass %, relative to the total amount (100 mass %) of the curable resin composition. In the curable resin composition of the present embodiment, the content of the additive is preferably 0 to 10 mass %, and more preferably 0.1 to 5 mass %, relative to the total amount (100 mass %) of the curable resin composition. Hereinafter, the components that can be contained in the curable resin composition of the present embodiment, namely, the photopolymerization initiator, the curing agent, the solvent, the other resins, and the additives, will be described in detail.

[0112] (Photopolymerization initiator) The photopolymerization initiator can be selected appropriately depending on the type of active energy ray to be irradiated. It may also be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, or a nitrile compound. The photopolymerization initiator is preferably a radical polymerization initiator. Specific examples of such photopolymerization initiators include alkylphenone-based photopolymerization initiators such as 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and intramolecular hydrogen abstraction photopolymerization initiators such as benzophenone compounds. Further, specific examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. Commercially available photopolymerization initiators that can be used in this embodiment include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", and "Omnirad-50". 0," "Omnirad-81" (manufactured by IGM), "Kayacure-DETX," "Kayacure-MBP," "Kayacure-DMBI," "Kayacure-EPA," "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Baicure-10," "Baicure-55" (manufactured by Stauffer Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo), "Sandray 1000" (manufactured by Sandoz), "Deep" (manufactured by Upjohn), "Quantacure-PDO," "Quantacure-ITX," "Quantacure-EPD" (manufactured by Ward-Blenkinsop), and "Runtecure-1104" (manufactured by Runtec).

[0113] The content of the photopolymerization initiator in the curable resin composition of the present embodiment is preferably 0.1 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass in total of the aromatic ester compound (A) and the resin (B) having an acid group and a polymerizable unsaturated group.

[0114] (Other various additives) The curable resin composition of the present embodiment may also contain appropriate amounts of various additives, such as curing agents, curing accelerators, other resins, organic solvents, flame retardants, fillers, pigments, antifoaming agents, viscosity modifiers, leveling agents, and storage stabilizers, as needed, within the scope of the purpose.

[0115] (hardening agent) Examples of the curing agent of the present embodiment include epoxy resins and other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents, etc.), and epoxy resins are preferred.

[0116] <Epoxy resin> The epoxy resin that is a suitable curing agent in this embodiment is not particularly limited, but is preferably, for example, a curable resin that contains two or more epoxy groups in the molecule and can be cured by forming a crosslinked network with the epoxy groups. The epoxy resin of the present embodiment is not particularly limited, but may be a novolac epoxy resin such as a phenol novolac epoxy resin, a cresol novolac epoxy resin, an α-naphthol novolac epoxy resin, a β-naphthol novolac epoxy resin, a bisphenol A novolac epoxy resin, or a biphenyl novolac epoxy resin; aralkyl-type epoxy resins such as phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, and phenol biphenyl aralkyl-type epoxy resins; Bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol AP-type epoxy resin, bisphenol AF-type epoxy resin, bisphenol B-type epoxy resin, bisphenol BP-type epoxy resin, bisphenol C-type epoxy resin, bisphenol E-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, and tetrabromobisphenol A-type epoxy resin; biphenyl-type epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton; Naphthalene-type epoxy resin; Binaphthol-type epoxy resin; Binaphthyl-type epoxy resin; Dicyclopentadiene-type epoxy resins such as dicyclopentadiene phenol-type epoxy resins; glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane-type epoxy resins, triglycidyl-p-aminophenol-type epoxy resins, and diaminodiphenylsulfone-type glycidylamine-type epoxy resins; diglycidyl ester type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resins and hexahydrophthalic anhydride glycidyl ester type epoxy resins; Examples thereof include benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. Among these epoxy resins, so-called glycidyl ether type epoxy resins obtained by epoxidizing a phenol compound are preferred, and among them, novolac type epoxy resins, aralkyl type epoxy resins, and dicyclopentadiene type epoxy resins are more preferred from the viewpoint of dielectric properties. The above-mentioned epoxy resins may be used alone or in combination of two or more.

[0117] The epoxy equivalent of the epoxy resin of this embodiment is preferably 120 to 400 g / eq, and more preferably 150 to 300 g / eq. If the epoxy equivalent of the epoxy resin is 120 g / eq or more, the resulting cured product will have better dielectric properties, which is preferable, while if the epoxy equivalent of the epoxy resin is 400 g / eq or less, the resulting cured product will have an excellent balance between heat resistance and dielectric loss tangent, which is preferable.

[0118] The softening point of the epoxy resin of the present embodiment is preferably 20 to 200°C, more preferably 40 to 150°C, from the viewpoint of achieving a balanced improvement in excellent developability, good coating film appearance, excellent elongation, and low dielectric properties.

[0119] In this embodiment, with respect to the amount of epoxy resin used, when the ester groups in the aromatic ester compound (A) and the acid groups in the resin (B) having an acid group and a polymerizable unsaturated group are taken as (total) functional groups, the functional group equivalent ratio of the amount of epoxy resin used ((aromatic ester compound (A) + resin (B) having an acid group and a polymerizable unsaturated group) / epoxy resin) is preferably 0.2 to 2, more preferably 0.4 to 1.5. A functional group equivalent ratio of 0.2 or more is preferred because the resulting cured product can have a lower dielectric tangent and higher flexibility. If the functional group equivalent ratio exceeds 2, heat resistance and curability decrease, so it is preferable to use within the above range.

[0120] (Other hardeners) The curable resin composition of the present embodiment may contain another curing agent together with or instead of the epoxy resin. Examples of the other curing agent include, but are not limited to, an amine curing agent, an acid anhydride curing agent, and a phenolic resin curing agent. The amine curing agent is not particularly limited, but examples thereof include aliphatic amines such as diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, menthenediamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N-dimethylpiperazine, and triethylenediamine; and aromatic amines such as m-xylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0121] Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, methylbutenyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexene dicarboxylic anhydride.

[0122] Examples of the phenolic resin curing agent include phenol novolac resin, cresol novolac resin, naphthol novolac resin, bisphenol novolac resin, biphenyl novolac resin, dicyclopentadiene-phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, triphenolmethane type resin, tetraphenolethane type resin, and aminotriazine-modified phenolic resin. Any of the other curing agents mentioned above may be used alone or in combination of two or more.

[0123] In this embodiment, with respect to the amount of other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents), when the ester groups in the aromatic ester compound (A) and the acid groups in the resin (B) having an acid group and a polymerizable unsaturated group are taken as the (total) functional groups, the functional group equivalent ratio of the amount of the other curing agents used ((aromatic ester compound (A) + resin (B) having an acid group and a polymerizable unsaturated group)) / other curing agents) is preferably 0.2 to 2, more preferably 0.4 to 1.5. A functional group equivalent ratio of 0.2 or more is preferred because the resulting cured product can have a lower dielectric tangent and higher flexibility. A functional group equivalent ratio of more than 2 reduces heat resistance and curability, so it is preferable to use within the above range.

[0124] <Curing accelerator> The curing accelerator is not particularly limited, but examples thereof include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, urea-based curing accelerators, etc. The above-mentioned curing accelerators may be used alone or in combination of two or more.

[0125] Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tripartylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organic phosphite compounds such as trimethyl phosphite and triethyl phosphite; and phosphonium salts such as ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphinetriphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, butylphenylphosphonium dicyanamide, and tetrabutylphosphonium decanoate.

[0126] Examples of the amine curing accelerator include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5,4,0]-undecene-7 (DBU), and 1,5-diazabicyclo[4,3,0]-nonene-5 (DBN).

[0127] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4 ... Examples of such an alkyl acrylate include ethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, and 2-methylimidazoline.

[0128] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, and 1-phenylbiguanide.

[0129] Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea. Of the above-mentioned curing accelerators, it is preferable to use 2-ethyl-4-methylimidazole and N,N-dimethyl-4-aminopyridine (DMAP).

[0130] The content of the curing accelerator in the curable resin composition of this embodiment can be adjusted as appropriate to obtain the desired curability, but is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the combined total of the (A) and (B) components. A content of 0.01 part by mass or more of the curing accelerator is preferred because it provides excellent curability. On the other hand, a content of 5 parts by mass or less of the curing accelerator is preferred because it provides excellent insulation reliability. From the same viewpoint, the content of the curing accelerator is more preferably 0.1 part by mass or more, and more preferably 3 parts by mass or less, relative to 100 parts by mass of the combined total of the (A) and (B) components.

[0131] (other resins) The curable resin composition of the present embodiment may contain other resins in addition to the epoxy resin or other curing agent, or in place of the epoxy resin or other curing agent. Specific examples of the other resins include, but are not limited to, maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolac resins, cyanate ester resins, styrene-maleic anhydride resins, allyl group-containing resins such as diallyl bisphenol and triallyl isocyanurate, polyphosphate esters, phosphate ester-carbonate copolymers, etc. These other resins may be used alone or in combination of two or more. The content of the other resin in the curable resin composition of the present embodiment is preferably 50 mass % or less of the total.

[0132] (solvent) The curable resin composition of the present embodiment may be prepared without a solvent or may contain a solvent, which has the function of adjusting the viscosity of the curable resin composition. Specific examples of the solvent include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, and 1,2,4-trimethylbenzene; and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more. The content of the solvent in the curable resin composition of this embodiment is preferably 0 to 90 mass %, more preferably 10 to 90 mass %, and even more preferably 20 to 80 mass %, based on the total amount (100 mass %) of the curable resin composition. A solvent content of 10 mass % or more is preferred because of excellent handleability. On the other hand, a solvent content of 90 mass % or less is preferred from the viewpoint of economy.

[0133] (additives) The curable resin composition of the present embodiment may contain additives, such as the curing accelerator, flame retardant, and filler.

[0134] <Flame retardant> The flame retardant of the present embodiment is not particularly limited, but examples thereof include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, and halogen-based flame retardants. The inorganic phosphorus-based flame retardant is not particularly limited, but examples thereof include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphoric acid amides.

[0135] The organic phosphorus flame retardant is not particularly limited, but examples thereof include methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, and stearyl acid phosphate. phosphate esters such as isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, and (2-hydroxyethyl) methacrylate acid phosphate; diphenylphosphines such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and diphenylphosphine oxide; 10-(2,5-dihydroxyphenyl)-10H-9-oxa phosphorus-containing phenols such as 10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphinyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol, and 1,5-cyclooctylenephosphinyl-1,4-phenyldiol; 9,10-dihydro-9-oxa-10-phos cyclic phosphorus compounds such as 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; and compounds obtained by reacting the above-mentioned phosphate esters, diphenylphosphine, or phosphorus-containing phenols with epoxy resins, aldehyde compounds, or phenol compounds. The halogen-based flame retardant is not particularly limited, but examples thereof include brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2-bis(tetrabromophthalimide), 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, tetrabromophthalic acid, etc. The above-mentioned flame retardants may be used alone or in combination of two or more.

[0136] The content of the flame retardant in this embodiment is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the combined total of the (A) and (B) components. A flame retardant content of 0.1 parts by mass or more is preferred because it can provide flame retardancy. On the other hand, a flame retardant content of 50 parts by mass or less is preferred because it can provide flame retardancy while maintaining dielectric properties. From the same viewpoint, the content of the flame retardant is more preferably 1 part by mass or more, and more preferably 30 parts by mass or less, relative to 100 parts by mass of the combined total of the (A) and (B) components.

[0137] (filler) Examples of the filler in this embodiment include organic fillers and inorganic fillers. The organic fillers have functions such as improving elongation and mechanical strength. The inorganic fillers have functions such as reducing the thermal expansion coefficient and imparting flame retardancy. The organic filler is not particularly limited, but examples thereof include polyamide particles. The inorganic filler is not particularly limited, but may include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black, etc. Among these, silica is preferably used. In this case, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. may be used as the silica.

[0138] The filler may be surface-treated as needed. The surface treatment agent that can be used is not particularly limited, but may include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, and the like. Specific examples of the surface treatment agent include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and hexamethyldisilazane. The fillers described above may be used alone or in combination of two or more.

[0139] The content of the filler in this embodiment is preferably 0.5 to 95 parts by mass, and more preferably 5 to 80 parts by mass, relative to 100 parts by mass of the combined amount of the (A) and (B) components. A filler content of 0.5 parts by mass or more is preferred because it allows the filler to fully exert its effects. On the other hand, the content of the filler is preferably 95 parts by mass or less so as not to increase the viscosity of the blend and impair moldability. From the same viewpoint, the content of the filler is more preferably 5 parts by mass or more, and more preferably 80 parts by mass or less, relative to 100 parts by mass of the combined amount of the (A) and (B) components. The method for producing the curable resin composition of the present embodiment is not particularly limited, and the composition can be produced by kneading the various components described above using a kneader such as a roll mixer.

[0140] [Cured product] The cured product in this embodiment is obtained by curing the above-described curable resin composition. Since the aromatic ester compound (A) contained in the curable resin composition itself has a low dielectric loss tangent, the cured product obtained from the curable resin composition also has a low dielectric loss tangent. Furthermore, the obtained cured product can exhibit flexibility, adhesion to metals such as copper foil due to the flexibility, and low dielectric properties, which is a preferred embodiment. The cured product of this embodiment can be obtained by irradiating the curable resin composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the ultraviolet curing reaction.

[0141] In this embodiment, an ultraviolet lamp is generally used as the ultraviolet light source from the viewpoints of practicality and economy, and specific examples include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED. The cumulative light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m2 is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range, since it is possible to prevent or suppress the occurrence of uncured portions. The irradiation of the active energy rays may be carried out in one step, or may be carried out in two or more steps.

[0142] In the present embodiment, as another method for obtaining a cured product by subjecting the curable resin composition to a curing reaction, for example, the heating temperature during heat curing is not particularly limited, but is preferably 100 to 300°C, and the heating time is preferably 1 to 24 hours.

[0143] Examples of applications for the curable resin composition or cured product of this embodiment include printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for buildup boards, insulating materials for circuit boards such as buildup adhesive films, resin casting materials, adhesives, semiconductor encapsulation materials, semiconductor devices, prepregs, conductive pastes, buildup films, buildup substrates, fiber-reinforced composite materials, and molded articles obtained by curing the above-mentioned composite materials. Among these various applications, the curable resin composition of the present invention can be used as an insulating material for so-called electronic component-embedded substrates, in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. Furthermore, among the above, taking advantage of the properties of the cured product, such as excellent flexibility, adhesion, low dielectric properties, and heat resistance, the curable resin composition of the present invention is preferably used for semiconductor encapsulation materials, semiconductor devices, prepregs, flexible wiring boards, circuit boards, buildup films, buildup substrates, multilayer printed wiring boards, fiber-reinforced composite materials, and molded articles obtained by curing the above-mentioned composite materials.

[0144] [Insulating material] The insulating material in this embodiment is made of the curable resin composition described above. Examples of such insulating materials include the interlayer insulating material for build-up substrates, insulating materials for circuit boards such as build-up adhesive films, insulating materials for circuit boards, and insulating materials for substrates with built-in electronic components. For example, a method for producing a build-up substrate from the curable resin composition includes the following three steps. In the first step, the curable resin composition containing an appropriate blend of rubber, filler, etc. is applied to a circuit board with a circuit formed thereon using a spray coating method, curtain coating method, or the like, followed by curing. In the second step, the substrate is subsequently drilled with predetermined through-holes, etc., as needed, treated with a roughening agent, and washed with hot water to form irregularities, followed by plating with a metal such as copper. In the third step, these operations are repeated as desired to alternately build up resin insulating layers and conductor layers with predetermined circuit patterns. It is preferable to drill through-holes after forming the outermost resin insulating layer. The first step can be carried out not only by the above-mentioned solution coating but also by laminating a build-up film that has been coated to a desired thickness and dried in advance. Furthermore, the build-up substrate of the present invention can be produced by forming a roughened surface and omitting the plating process by thermocompressing a copper foil on which a circuit has been formed, the copper foil being prepared by semi-curing the resin composition, at 170 to 250°C.

[0145] [Resist material] The resist member of this embodiment is made of the curable resin composition described above. The resist member can be obtained, for example, by applying the curable resin composition to a substrate, evaporating and drying the organic solvent at a temperature ranging from about 60 to 100°C, exposing the composition to active energy rays through a photomask having a desired pattern formed thereon, developing the unexposed areas with an alkaline aqueous solution, and then heat-curing the composition at a temperature ranging from about 140 to 180°C. The resist member of this embodiment has excellent low dielectric properties and elongation. [Example]

[0146] Examples are given below to explain the present invention in more detail, but the present invention is not limited to the following examples. In the following, "parts" and "%" are based on mass unless otherwise specified. In addition, for GPC measurement, 1 1H-NMR measurement, 13 13C-NMR measurement, and FD-MS spectrum measurement were carried out under the following conditions.

[0147] (Evaluation method) <GPC measurement> Using the following measuring device and measuring conditions, GPC charts of diphenyl isophthalate derivatives, phenolic hydroxyl group-containing resins, and active esters obtained in the following synthesis examples and examples were obtained. From the results of the GPC charts, it was confirmed that the target products (diphenyl isophthalate derivative (a'), aromatic ester compound (A), and resin (B) having an acid group and a polymerizable unsaturated group) were generated from the decrease and disappearance of the raw material peaks. Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation [[ID=1十七]] Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation <F Detector: RI (differential refractometer) Data processing: "GPC workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation Measuring conditions: Column temperature 40 °C Developing solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of the "GPC workstation EcoSEC-WorkStation". (Polystyrene used) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation Sample: A 1.0 mass% solution of diphenyl isophthalate derivative (a') and aromatic ester compound (A) obtained in the following synthesis examples, examples, etc. in tetrahydrofuran, converted to solid content, and filtered through a microfilter (50 μl) was used.

[0148] <FD-MS Spectrum Measurement> The FD-MS spectrum was measured using the following measuring apparatus and measuring conditions. From this result, the mass peak corresponding to the compound with the repeating number p 11 = 1 was confirmed. Measuring apparatus: JMS-T100GC AccuTOF Measuring conditions Measuring range: m / z = 4.00 to 2000.00 Rate of change: 51.2 mA / min Final current value: 45 mA Cathode voltage: -10 kV Recording interval: 0.07 sec

[0149] < 13 <C-NMR Measurement> <000​​​​​​​ Pulse angle: 45° pulse Sample concentration: 30% by mass Accumulation count: 1000 times

[0150] <Tensile test measurement> Manufacturer: Shimadzu Corporation Measuring equipment: Precision universal testing machine Autograph AG-IS Measurement conditions: temperature 23℃, humidity 50%, distance between gauge lines 20mm, distance between fulcrums 20mm, test speed 10mm / min Sample size: 10 x 80 mm

[0151] <Cavity resonance method (measurement of dielectric constant and dielectric loss tangent)> Manufacturer:Agilent Technologies Measurement equipment: 4291B RF Impedance Material Analyzer, 16453A Frequency condition: 1GHz

[0152] <Method for evaluating alkaline developability> The curable resin compositions obtained in each Example and Comparative Example were applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80°C for 130, 140, 150, 160, 170, 180, and 190 minutes, respectively, to prepare samples with different drying times. These were then developed with a 1% aqueous sodium carbonate solution at 30°C for 180 seconds, and the drying time at 80°C of samples that left no residue on the substrate was evaluated as the drying control range (minutes). Note that a longer drying control range (minutes) indicates better alkaline developability.

[0153] <How to evaluate the appearance of the coating> The curable resin compositions obtained in each of the Examples and Comparative Examples were applied to a 125 μm PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd.) using a bar coater (#12) and dried at 80° C. for 5 minutes. Then, the curable resin compositions were applied to a 125 μm PET film (Cosmoshine A4300, manufactured by Toyobo Co., Ltd.) using a high-pressure mercury lamp (irradiation intensity 120 W / cm, cumulative light amount 5 kJ / m). 2 ) to obtain a coating film having a thickness of 10 μm after curing. This coating film was visually evaluated according to the following criteria. ○: No cloudiness ×: Cloudy

[0154] (Synthesis Example 1): Synthesis of diphenyl isophthalate derivative (a'-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 808.0 parts by mass of isophthalic acid chloride (4.0 moles of acid chloride groups) as component (a1) and 4140.0 parts by mass of toluene. The system was then purged with nitrogen under reduced pressure and dissolved. Next, 864.0 parts by mass (8.0 moles) of o-cresol (a2) was charged and the system was purged with nitrogen and dissolved. Then, 2.07 parts by mass of tetrabutylammonium bromide was dissolved. While purging with nitrogen gas, the system was controlled to 60°C or below, and 1648.0 parts by mass of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1 hour. After the reaction was completed, the mixture was allowed to stand for separation, and the aqueous layer was removed. Water was then added to the toluene layer containing the dissolved reactant, and the mixture was stirred and mixed for approximately 15 minutes. The mixture was then allowed to stand for separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water and toluene were removed by decanting, and a crystalline compound (intermediate product (a')), a diphenyl isophthalate derivative (a'-1), was obtained.

[0155] (Synthesis Example 2): Synthesis of diphenyl isophthalate derivative (a'-2) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 142.1 parts by mass of isophthalic acid chloride (0.7 moles of acid chloride groups) as component (a1) and 954.0 parts by mass of toluene. The system was then purged with nitrogen under reduced pressure and dissolved. Next, 188.0 parts by mass (1.4 moles) of phenol (a2) was charged and the system was purged with nitrogen under reduced pressure and dissolved. Then, 0.33 parts by mass of tetrabutylammonium bromide was dissolved. While purging with nitrogen gas, the system was controlled to below 60°C, and 288.4 parts by mass of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1 hour. After the reaction was completed, the mixture was allowed to stand for separation, and the aqueous layer was removed. Water was then added to the toluene layer containing the dissolved reactant, and the mixture was stirred and mixed for approximately 15 minutes. The mixture was then allowed to stand for separation, and the aqueous layer was removed. This procedure was repeated until the pH of the aqueous layer reached 7. Thereafter, water and toluene were removed by decanting, and a crystalline compound (intermediate product (a')), a diphenyl isophthalate derivative (a'-2), was obtained.

[0156] (Synthesis Example 3): Synthesis of diphenyl isophthalate derivative (a'-3) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 142.1 parts by mass of isophthalic acid chloride (0.7 moles of acid chloride groups) as component (a1) and 903.0 parts by mass of toluene. The system was then purged with nitrogen under reduced pressure and dissolved. Next, 210.0 parts by mass (1.4 moles) of p-tert-butylphenol (PTBP) as component (a2) was charged and the system was purged with nitrogen under reduced pressure and dissolved. Then, 0.45 parts by mass of tetrabutylammonium bromide was dissolved. While purging with nitrogen gas, the system was controlled to 60°C or below, and 288.4 parts by mass of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1 hour. After the reaction was completed, the mixture was allowed to stand for separation, and the aqueous layer was removed. Water was then added to the toluene layer containing the dissolved reactant, and the mixture was stirred and mixed for approximately 15 minutes. The mixture was then allowed to stand for separation, and the aqueous layer was removed. This procedure was repeated until the pH of the aqueous layer reached 7. Water and toluene were then removed by decanting, yielding a crystalline compound (intermediate product (a')), a diphenyl isophthalate derivative (a'-3).

[0157] (Synthesis Example 4): Synthesis of aromatic ester compound (A-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 30.0 parts by mass of 1,9-nonanediol (hydroxyl group equivalent: 80 g / eq) as component (a3), 129.68 parts by mass of the isophthalic acid diphenyl derivative (a'-1) obtained in Synthesis Example 1, and 0.80 parts by mass of 1,8-diazabicyclo[5,4,0]-undecene-7 (hereinafter abbreviated as "DBU"), and the mixture was heated to 190°C and stirred until the reaction was completed. The completion of the reaction was confirmed by GPC. Then, o-cresol was removed by vacuum distillation to obtain aromatic ester compound (A-1). The functional group equivalent and average repeat number p of the obtained aromatic ester compound (A-1) were measured. 11 (See formula (1.1) below) are 319 g / eq and p 11 =1. [ka] The average repeating number p in the aromatic ester compound (A-1) of the above formula (1.1) 11 was calculated from the feed ratio based on the following formula. (The average repeat number p in the obtained aromatic ester (A) 11 ) = (number of moles of hydroxyl groups in polyhydric alcohol compound (a3)) / [(number of moles of aromatic ester groups in intermediate product (a') used as raw material) - (number of moles of hydroxyl groups in polyhydric alcohol compound (a3)]

[0158] (Synthesis Example 5): Synthesis of aromatic ester compound (A-2) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 30.0 parts by mass of 1,9-nonanediol (hydroxyl group equivalent: 80 g / eq) as component (a3), 119.18 parts by mass of the isophthalic acid diphenyl derivative (a'-2) obtained in Synthesis Example 2, and 0.75 parts by mass of DBU. The system was purged with nitrogen under reduced pressure, and then heated to 190°C and stirred until the reaction was complete. The completion of the reaction was confirmed by GPC. Thereafter, phenol was removed by distillation under reduced pressure to obtain aromatic ester compound (A-2). The functional group equivalent and average repeat number p of the obtained aromatic ester compound (A-2) were 11 From the feed ratio, 306g / eq and p 11 =1.

[0159] (Synthesis Example 6): Synthesis of aromatic ester compound (A-3) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 8.5 parts by mass of 1,9-nonanediol (hydroxyl group equivalent: 80 g / eq) as component (a3), 45.67 parts by mass of the isophthalic acid diphenyl derivative (a'-3) obtained in Synthesis Example 3, and 0.27 parts by mass of DBU. The system was then purged with nitrogen under reduced pressure, and the temperature was raised to 190°C, followed by stirring until the reaction was complete. The completion of the reaction was confirmed by GPC. PTBP was then removed by distillation under reduced pressure to obtain aromatic ester compound (A-3). The functional group equivalent and average repeat number p of the obtained aromatic ester compound (A-3) were measured. 11 From the feed ratio, 363g / eq and p 11 =1.

[0160] (Synthesis Example 7): Synthesis of aromatic ester compound (A-4) The same procedure as in Example 1 was carried out to obtain an aromatic ester compound (A-4), except that in Example 1, 1,9-nonanediol as component (a3) ​​was replaced with 30.0 parts by mass of 1,6-hexanediol (hydroxyl group equivalent: 59 g / eq), the amount of isophthalic acid diphenyl derivative (a'-1) was changed from 129.68 parts by mass to 175.86 parts by mass, and DBU was changed from 0.80 parts by mass to 1.03 parts by mass. The functional group equivalent and average repeat number p of the obtained aromatic ester compound (A-4) were11 From the feed ratio, 299g / eq and p 11 =1.

[0161] (Synthesis Example 8): Synthesis of aromatic ester compound (A-5) The same procedure as in Example 1 was carried out to obtain an aromatic ester compound (A-5), except that in Example 1, 1,9-nonanediol as component (a3) ​​was replaced with 40.0 parts by mass of 1,12-dodecanediol (hydroxyl group equivalent: 101 g / eq), the amount of isophthalic acid diphenyl derivative (a'-1) was changed from 129.68 parts by mass to 136.95 parts by mass, and DBU was changed from 0.80 parts by mass to 0.88 parts by mass. The functional group equivalent weight and average repeat number p of the obtained aromatic ester compound (A-5) were 11 From the feed ratio, 342g / eq and p 11 =1.

[0162] (Synthesis Example 9): Synthesis of Resin (B-1) Having Acid Groups and Polymerizable Unsaturated Groups A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 123 parts by weight of diethylene glycol monoethyl ether acetate and dissolved in 214 parts by weight of orthocresol novolac epoxy resin "EPICLON N-680" (DIC Corporation, softening point 86°C, epoxy equivalent: 214 g / eq). 0.9 parts by weight of dibutylhydroxytoluene and 0.2 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.4 parts by weight of triphenylphosphine. The mixture was reacted at 120°C for 10 hours while blowing air into it. Next, 72 parts by weight of diethylene glycol monoethyl ether acetate and 76 parts by weight of tetrahydrophthalic anhydride were added and reacted at 110°C for 3 hours to obtain Resin (B-1) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this Resin (B-1) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g. The acid value is a value measured based on the neutralization titration method of JIS K 0070 (1992).

[0163] (Synthesis Example 10): Synthesis of Resin (B-2) Having Acid Groups and Polymerizable Unsaturated Groups A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 499.7 parts by weight of diethylene glycol monomethyl ether acetate, and 244.3 parts by weight of an isocyanurate-modified isophorone diisocyanate (EVONIK "VESTANAT T-1890 / 100", NCO% = 17.2%) and 192.0 parts by weight of trimellitic anhydride were dissolved therein. 1.0 part by weight of dibutylhydroxytoluene was added. The mixture was reacted at 160°C for 6 hours under a nitrogen atmosphere, and the NCO% was confirmed to be 0.1 or less. Next, 0.4 parts by weight of methoquinone was added as a thermal polymerization inhibitor, followed by 147.6 parts by weight of a pentaerythritol polyacrylate mixture (Toagosei Co., Ltd. "Aronix M-306", hydroxyl value: 159.7 mg KOH / g) and 3.5 parts by weight of triphenylphosphine. The mixture was reacted at 110°C for 5 hours while blowing air into it. Then, 165.0 parts by mass of glycidyl methacrylate was added and reacted for 6 hours at 110°C. Next, 110.4 parts by mass of succinic anhydride was added and reacted for 5 hours at 110°C to obtain a resin (B-2) having an acid group and a polymerizable unsaturated group. The acid value of the solid content of the resin (B-2) was 80 mgKOH / g.

[0164] (Comparative Synthesis Example 1): Synthesis of phenolic hydroxyl group-containing resin (c) A flask equipped with a thermometer and stirrer was charged with 127 parts by mass (0.5 mol) of diglycidyl ether of 1,6-hexanediol (manufactured by DIC Corporation, product name: SR-16HL, epoxy equivalent: 127 g / eq) and 228 parts by mass (1.0 mol) of bisphenol A (hydroxyl equivalent: 114 g / eq). The temperature was raised to 140 °C over 30 minutes, and then 1.8 parts by mass of 4% aqueous sodium hydroxide solution was added to the flask. The temperature inside the flask was then raised to 150 °C over 30 minutes and the reaction was continued at 150 °C for 5 hours. A neutralizing amount of sodium phosphate was then added to the flask to obtain phenolic hydroxyl-containing resin (c). A GPC chart (not shown) confirmed the formation of the resin and confirmed that the resulting phenolic hydroxyl-containing resin (c) had a hydroxyl equivalent of 300 g / eq.

[0165] (Comparative Synthesis Example 2): Synthesis of aromatic ester compound (C-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 300 parts by mass of the phenolic hydroxyl-containing resin (c) (hydroxyl equivalent: 300 g / eq) obtained in Comparative Example 1 and 1,212 parts by mass of methyl isobutyl ketone (hereinafter abbreviated as "MIBK"). The system was purged with nitrogen under reduced pressure to dissolve the phenolic hydroxyl-containing resin (c). Next, 140.5 parts by mass (1.0 mol) of benzoyl chloride was charged into the flask. Then, while purging with nitrogen gas, the system was controlled to 60°C or below, and 216 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was continued under the above conditions for 1 hour. After the reaction was completed, the mixture was allowed to stand for separation, and the aqueous layer was removed. Water was then added to the MIBK phase containing the dissolved reactants, and the mixture was stirred and mixed for approximately 10 minutes. The mixture was then allowed to stand for separation, and the aqueous layer was removed. This procedure was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by decanting, and then MIBK was removed by vacuum dehydration to obtain aromatic ester compound (C-1). The functional group equivalent of the obtained aromatic ester compound (C-1) was 404 g / eq based on the charge ratio.

[0166] Examples 1 to 10: Preparation of Resin Compositions Having Acid Groups and Polymerizable Unsaturated Groups and Curable Resin Compositions The aromatic ester compound (A) obtained in the above synthesis example and the resin (B) having an acid group and a polymerizable unsaturated group were mixed in the composition ratio shown in Table 1 to obtain resin compositions (1) to (10) having an acid group and a polymerizable unsaturated group.

[0167] Resin compositions (1) to (10) having an acid group and a polymerizable unsaturated group obtained in Examples 1 to 10 above were mixed with an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), 2-ethyl-4-methylimidazole, and 4-dimethylaminopyridine in the compositional ratios shown in Table 1 to obtain curable resin compositions (1) to (10). Then, the curable resin compositions (1) to (10) were subjected to a tensile test (elongation), and were evaluated for dielectric constant, dielectric loss tangent, and coating appearance according to the procedures described in the "Evaluation Method" section above. The results are shown in Table 1 below.

[0168] Comparative Examples 1 and 2: Preparation of Compositions As in Examples 1 to 10, the components were mixed in the composition ratios shown in Table 1 to obtain compositions (C1) to (C2) of Comparative Examples 1 and 2. The compositions (C1) to (C2) of Comparative Examples 1 and 2 were then subjected to tensile tests (elongation), and evaluated for dielectric constant, dielectric loss tangent, and coating appearance. The results are shown in Table 1 below.

[0169] [Table 1]

[0170] Examples 11 to 20: Preparation of Resin Compositions Having Acid Groups and Polymerizable Unsaturated Groups and Curable Resin Compositions Resin compositions (1) to (10) having an acid group and a polymerizable unsaturated group obtained in Examples 1 to 10 above were mixed with an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), 2-ethyl-4-methylimidazole, dipentaerythritol hexaacrylate, and phthalocyanine green in the compositional ratios shown in Table 2 to obtain curable resin compositions (11) to (20). Then, the alkali developability was evaluated according to the procedure of the evaluation method described in the above (Evaluation Method) column. The results are shown in Table 2 below.

[0171] (Comparative Examples 3-4: Preparation of Composition) As in Examples 11 to 20, the components were mixed in the composition ratios shown in Table 2 to obtain compositions (C3) to (C4) of Comparative Examples 3 and 4. The alkali developability of compositions (C3) to (C4) of Comparative Examples 3 and 4 was then evaluated. The results are shown in Table 2 below.

[0172] [Table 2]

[0173] From the results in Tables 1 and 2, it can be seen that the resin compositions of the examples exhibit superior developability compared to the comparative examples, and that the resulting cured products can exhibit excellent elongation, good coating film appearance, and low dielectric properties. [Industrial Applicability]

[0174] According to the present disclosure, it is possible to provide a resin composition having an acid group and a polymerizable unsaturated group, which exhibits excellent developability and is capable of producing a cured product having excellent elongation, good coating film appearance, and low dielectric properties; a curable resin composition containing the resin composition having an acid group and a polymerizable unsaturated group; and a cured product, insulating material, and resist material obtained using the curable resin composition.

Claims

1. A resin composition having an acid group and a polymerizable unsaturated group, comprising an aromatic ester compound (A) and a resin (B) having an acid group and a polymerizable unsaturated group, the aromatic ester compound (A) is a compound obtained by reacting an aromatic polycarboxylic acid, an acid halide thereof and / or an ester thereof (a1), a monohydroxyaromatic compound (a2), and a polyhydric alcohol compound (a3) ​​as essential reaction raw materials; a mass ratio of the solid content of the aromatic ester compound (A) to the solid content of the resin (B) having an acid group and a polymerizable unsaturated group, [(A) / (B)], is in the range of 5 / 95 to 50 / 50; The resin composition having an acid group and a polymerizable unsaturated group, wherein the polyhydric alcohol compound (a3) ​​has a hydroxyl group equivalent of less than 270 g / eq.

2. The aromatic ester compound (A) is represented by the following general formula (1): 【Chemical 1】 [In the above general formula (1), Q １１ and Q １２ each independently represents a group derived from the aromatic polycarboxylic acid, its acid halide and / or its ester (a1), Ar １１ and Ar １２ each independently represents a group derived from the monohydroxy aromatic compound (a2), each A independently represents a group derived from the polyhydric alcohol compound (a3), p １１ The resin composition having an acid group and a polymerizable unsaturated group according to claim 1 , wherein the formula (I) is an average repeating number of 0.01 or more.

3. Ar in the general formula (1) １１ and Ar １２ are each independently represented by the following general formula (2) or (3): 【Chemistry 2】 [In the above general formula (2) and general formula (3), * represents Ar in the above general formula (1)] １１ or Ar １２ represents the bond to the oxygen atom that bonds to R ２１ and R ３１ each independently represents a halogen atom, an alkyl group, an allyl group, an alkoxy group, an aryl group, or an aralkyl group; k ２１ represents an integer from 0 to 7, and k ３１ represents an integer of 0 to 5. The resin composition having an acid group and a polymerizable unsaturated group according to claim 2, wherein the resin composition is represented by the formula:

4. A curable resin composition comprising the resin composition having an acid group and a polymerizable unsaturated group according to any one of claims 1 to 3, and a photopolymerization initiator.

5. A cured product of the curable resin composition according to claim 4.

6. An insulating material comprising the curable resin composition according to claim 4.

7. A resist member comprising the curable resin composition according to claim 4.

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