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 which has high photosensitivity and allows a cured product obtained therefrom to exhibit excellent elongation, low elasticity, heat resistance and low dielectric characteristics.SOLUTION: A 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 270 g / eq or more.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] When mounting and soldering electronic components on a printed wiring board, solder resists are widely used as insulating materials to prevent solder from adhering to areas other than the mounted area and to form a coating that semi-permanently prevents oxidation or corrosion of wiring. Techniques for forming such solder resist patterns include photoresist methods, which can accurately form fine patterns, and among these, alkali-developable liquid photoresist methods are the mainstream, due to environmental considerations and other factors.

[0003] In addition, in recent years, printed wiring boards have become increasingly miniaturized (fine), multi-layered, and single-board in order to achieve higher density electronic components, 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 delay for use at high frequencies (gigahertz range).

[0004] As such an alkali-developable liquid photoresist, a composition containing a reaction product (acid-pendant epoxy acrylate) obtained by reacting a novolac epoxy resin with an unsaturated monocarboxylic acid and then adding a polybasic acid anhydride is widely used (see Patent Document 1). However, it is known that the dielectric constant of epoxy acrylate increases due to the generation of hydroxyl groups when an epoxy resin is reacted with an unsaturated monocarboxylic acid.

[0005] As a technique that can address this issue, for example, Patent Document 2 discloses that by using a photosensitive resin composition containing an active ester-based curing agent and a carboxyl group-containing radical polymerizable compound, it is possible to improve properties such as dielectric loss tangent while improving heat resistance. [Prior art documents] [Patent documents]

[0006] [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]

[0007] However, Patent Documents 1 and 2 do not consider the elongation and low elasticity of the cured product formed from the composition, and the compositions described in Patent Documents 1 and 2 have room for improvement in these respects.

[0008] Therefore, an object of the present invention is to provide a resin composition that exhibits high photosensitivity and is capable of producing a cured product having excellent elongation, low elasticity, heat resistance, and low dielectric properties. Another object of the present invention is to provide 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. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that a composition containing a specific aromatic ester compound and a resin having a specific acid group and a polymerizable unsaturated group exhibits high photosensitivity, and the resulting cured product exhibits excellent elongation, low elasticity, heat resistance, and low dielectric properties, thereby completing the present invention.

[0010] The resin composition of the present invention 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 hydroxyl group equivalent of the polyhydric alcohol compound (a3) ​​is 270 g / eq or more. It is characterized by:

[0011] 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), and p 11 represents an average repeat number of 0.01 or more.] is preferred.

[0012] 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 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. It is preferable that the structure represented by the formula: [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a resin composition that exhibits high photosensitivity and is capable of producing a cured product having excellent elongation, low elasticity, heat resistance, and low dielectric properties. Furthermore, according to the present invention, it is possible to provide 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. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a GPC chart of the diphenyl isophthalate derivative (a'-1) obtained in an example. DETAILED DESCRIPTION OF THE INVENTION

[0015] The following describes in detail an embodiment of the present invention (sometimes referred to as the "present embodiment"); however, the present invention is not limited to the following description and can be implemented in various modifications within the scope of its gist.

[0016] [Resin Composition Having Acid Group and Polymerizable Unsaturated Group] The resin composition having an acid group and a polymerizable unsaturated group of this embodiment is a resin composition having an acid group and a polymerizable unsaturated group, which contains 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 monohydroxy aromatic compound (a2), and a polyhydric alcohol compound (a3) ​​as essential reaction raw materials. The hydroxyl equivalent of the polyhydric alcohol compound (a3) ​​is 270 g / eq or more. Such a resin composition having an acid group and a polymerizable unsaturated group exhibits high photosensitivity, and is capable of giving a cured product having excellent elongation, low elasticity, heat resistance, and low dielectric properties.

[0017] The content of the aromatic ester compound (A) in the total amount (100% by mass) of the resin composition having an acid group and a polymerizable unsaturated group of the present embodiment is, from the viewpoint of improving photosensitivity, elongation, low elasticity, heat resistance, and low dielectric properties in a balanced manner, preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, and is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less. Furthermore, from the viewpoint of improving photosensitivity, elongation, low modulus, heat resistance, and low dielectric properties in a balanced manner, the content of the resin (B) having an acid group and a polymerizable unsaturated group in the total amount (100% by mass) of the resin composition having an acid group and a polymerizable unsaturated group of this embodiment is preferably 20% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, and is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.

[0018] In the resin composition having an acid group and a polymerizable unsaturated group of this embodiment, the mass ratio [(A) / (B)] of the solid content of the aromatic ester compound (A) to the resin (B) having an acid group and a polymerizable unsaturated group is preferably in the range of 5 / 95 to 50 / 50 from the viewpoint of improving photosensitivity, elongation, low modulus, heat resistance, and low dielectric properties in a balanced manner. From the same viewpoint, the mass ratio [(A) / (B)] is more preferably 10 / 90 or more and more preferably 40 / 60 or less.

[0019] The resin composition having an acid group and a polymerizable unsaturated group of this embodiment may further contain an optional component as an optional component. Furthermore, the resin composition having an acid group and a polymerizable unsaturated group of this embodiment may be substantially composed of only the component (A), the component (B), and the optional component. The resin composition having an acid group and a polymerizable unsaturated group of this embodiment may be composed of only the component (A) and the component (B). The resin composition having an acid group and a polymerizable unsaturated group of this embodiment may contain inevitable impurities in addition to the component (A), the component (B), and the optional component, as long as the effects of the present disclosure are not impaired. From the viewpoint of improving photosensitivity, elongation, low modulus, heat resistance, and low dielectric properties in a balanced manner, the total content of the (A) component and the (B) component in 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.

[0020] 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 of the present 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.

[0021] (Terminology explanation) Unless otherwise specified herein, the following terms apply.

[0022] 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.

[0023] 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.

[0024] 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."

[0025] 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.

[0026] As used herein, examples of the "aralkyl group" include a benzyl group, a diphenylmethyl group, a biphenyl group, and a naphthylmethyl group.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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=CH2- 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.

[0035] 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.

[0036] 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.

[0037] (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 material 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 the molecule, but the aromatic ester compound (A) 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.

[0038] In this specification, "aromatic polycarboxylic acids, acid halides thereof and / or esters thereof (a1)" may be abbreviated as "aromatic polycarboxylic acids (a1)" hereinafter.

[0039] 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.

[0040] <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).

[0041] From the viewpoint of another 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 monohydroxy aromatic compound (a2), a residue of a polyhydric alcohol compound (a3), and a residue of a polyhydric hydroxy aromatic compound (a4).

[0042] 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).

[0043] In this specification, the term "aromatic polycarboxylic acid, its acid halide and / or its ester (a1)" refers to a compound having an aromatic group to which two or more atomic groups containing a carbonyl group (-C(=O)-X (X is a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent hydrocarbon group)) are bonded. In this specification, the term "residue of an aromatic polycarboxylic acid, an acid halide thereof, and / or an ester thereof (a1)" refers to a partial structure of the aromatic polycarboxylic acid, an acid halide thereof, and / or an ester thereof (a1) that remains in the molecule of the 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 derived from the aromatic polycarboxylic acid, an acid halide thereof, and / or an ester thereof (a1) other than the chemical bond. 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.

[0044] The aromatic polycarboxylic acid, its acid halide and / or its ester (a1) is represented by the following general formula (a1):

[0045] [ka] In this case, Q a1 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).

[0046] 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 hydroxy group from the monohydroxy aromatic compound (a2), and the dashed line portion represents a residue of the monohydroxy aromatic compound (a2).

[0047] 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 a3 is the base of valence, n a3represents 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).

[0048] 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-valent group excluding hydrogen atoms or hydroxyl groups, 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.

[0049] 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.

[0050] 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.

[0051] More specifically, the aromatic ester compound (A) of the present embodiment may have a chemical structure in which a partial structure represented by the following general formula (i), in which identical or different aromatic rings are linked together via an ester bond, a residue of a polyhydric alcohol compound (a3) ​​(for example, a divalent to hexavalent hydrocarbon group having at least carbon and hydrogen 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 —CH— group in the alkylene chain or the alkylene ether chain may be substituted with a divalent aromatic group))) and a residue of a polyhydroxy aromatic compound (a4), which is an optional component, are linked together.

[0052] [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.

[0053] 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).

[0054] According to the above, 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), and a cured product can be formed as an insulating material with low dielectric properties and excellent elongation.

[0055] 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 and 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 represents an average repeat number of 0.01 or more.] is preferred. For convenience of explanation, the above-mentioned "group derived from" is a term that indicates the correspondence between the symbols in general formula (1) and each raw material component, and does not indicate all structural moieties derived from each reaction raw material that remain in the aromatic ester compound (A) after the reaction.

[0056] Q in the above general formula (1) 11 and Q 12 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)). The group derived from aromatic polycarboxylic acids (a1) is preferably, for example, 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 1 and Q2 is more preferably any one of a phenylene group, a naphthalenediyl group, and an anthracenediyl group. 11 and Q 12 and may be the same or different from each other. Among them, Q is preferred from the viewpoint of industrial availability of raw materials and solubility. 11 and Q 12 is more preferably a phenylene group.

[0057] A in the above general formula (1) represents 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.

[0058] The group derived from the polyhydric alcohol compound (a3) ​​preferably has 2 to 20 carbon atoms, more preferably 4 to 18 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 residue of the polyhydric alcohol compound (a3) ​​is preferably linear or branched, 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.

[0059] 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 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.

[0060] 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).

[0061] 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.

[0062] R in the above general formula (3) 31is 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.

[0063] k in the above general formula (2) 21 represents an integer of 0 to 7, but from the viewpoint of reactivity or flexibility of the resulting cured product, it is more preferably an integer of 0 to 5, and even more preferably an integer of 0 to 4. Furthermore, k in the above general formula (3) 31 represents an integer of 0 to 5, but is more preferably an integer of 0 to 4 from the viewpoint of reactivity or flexibility of the resulting cured product.

[0064] p in the above general formula (1) 11 is an average number of repetitions of 0.01 or more, and from the viewpoints of workability and flexibility of the resulting cured product, an average number of repetitions of 0.1 to 5 is more preferable, and an average number of repetitions of 0.2 to 5 is even more preferable.

[0065] 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.

[0066] 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 12 each 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.

[0067] <Reaction raw materials for aromatic ester compound (A)> The reaction raw materials for the aromatic ester compound (A) will be explained below.

[0068] -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 12and 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.

[0069] 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.

[0070] 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.

[0071] The valence (number) of the carboxyl groups in the aromatic polycarboxylic acids (a1) is preferably from divalent to tetravalent, and more preferably divalent.

[0072] 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.

[0073] Of the above-mentioned examples, from the viewpoints of flexibility of the resulting cured product, ease of industrial availability of raw materials, and workability, preferred aromatic polycarboxylic acids (a1) are benzenedicarboxylic acid, benzenetricarboxylic acid, naphthalenedicarboxylic acid, and acid halides thereof, more preferred are 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 preferred are isophthalic acid chloride and terephthalic acid chloride. The aromatic polycarboxylic acids (a1) may be used alone or in combination of two or more.

[0074] -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.

[0075] -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 polyhydric alcohol compound (a3) ​​in this embodiment must have a hydroxyl equivalent of 270 g / eq or more. By setting the hydroxyl equivalent to 270 g / eq or more, the properties derived from the polyhydric alcohol compound (a3) ​​are more easily exhibited, and the flexibility of the cured product can be improved. From the same viewpoint, the hydroxyl equivalent of the polyhydric alcohol compound (a3) ​​is preferably 300 g / eq or more. The hydroxyl equivalent of the polyhydric alcohol compound (a3) ​​is not particularly limited, but can be 10,000 g / eq or less. The hydroxyl equivalent is a value measured in accordance with JIS K 0070.

[0076] The valence (number) of the hydroxyl groups in the polyhydric alcohol compound (a3) ​​is preferably from divalent to hexavalent, and more preferably divalent.

[0077] 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 a polyol other than the polyhydric hydroxy aromatic compound (a4). The polyhydric alcohol compound (a3) ​​is preferably a polyol having an aliphatic hydroxyl group. The segment derived from the polyol having an aliphatic hydroxyl group has low polarity and is more flexible, so that the low dielectric properties and flexibility of the resulting aromatic ester compound (A) can be effectively improved. The polyhydric alcohol compound (a3) ​​may be used alone or in combination of two or more kinds.

[0078] Examples of the polyol having an aliphatic hydroxyl group include hydrocarbon polyols (a3-1), polycarbonate polyols (a3-2), polyester polyols (a3-3), polyether polyols (a3-4), polyurethane polyols (a3-5), and polysiloxane polyols (a3-6). Among these, the hydrocarbon polyols (a3-1), polycarbonate polyols (a3-2), polyester polyols (a3-3), polyether polyols (a3-4), and polysiloxane polyols (a3-6) are preferred as the polyol having an aliphatic hydroxyl group from the viewpoints of flexibility and heat resistance.

[0079] --Hydrocarbon polyol (a3-1)-- Examples of the hydrocarbon polyol (a3-1) include hydrocarbon monomer polyols containing hydrocarbon monomers such as ethylene, propylene, butadiene, and styrene as essential constituent monomers; diol compounds synthesized from dimer acids; etc. Among these, from the viewpoint of flexibility, hydrocarbon polyols (a3-1) are preferred, and butadiene polyols containing butadiene monomers as essential constituent monomers are more preferred.

[0080] The hydrocarbon monomer polyol may be copolymerized with other polymerizable monomers. Examples of other polymerizable monomers include aliphatic monoolefin compounds such as butylene, pentene, 2-methyl-1-pentene, hexene, 3-methyl-1-hexene, and 3-methyl-2-hexene; alicyclic monoolefin compounds such as cyclohexene; styrene compounds such as 4-methylstyrene and α-methylstyrene; acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and 2-(dimethylamino)ethyl (meth)acrylate. Examples of the polymerizable monomer include ester compounds, vinyl ester compounds such as vinyl acetate and vinyl propionate, vinyl ether compounds such as vinyl methyl ether and vinyl ethyl ether, vinyl ketone compounds such as vinyl methyl ketone and methyl isopropenyl ketone, ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride, nitrogen-containing compounds such as (meth)acrylonitrile, (meth)acrylamide, vinylpyridine, and vinylpyrrolidone, and halogen-containing compounds such as vinyl chloride, vinylidene chloride, and vinyl fluoride. These other polymerizable monomers may be used alone or in combination of two or more.

[0081] The hydrocarbon monomer polyol may be commercially available, for example, the G series manufactured by Nippon Soda Co., Ltd. ("G-1000" number average molecular weight (Mn) 1400, hydroxyl value 68 to 78 mgKOH / g, "G-2000" number average molecular weight (Mn) 1900, hydroxyl value 35 to 55 mgKOH / g, "G-3000" number average molecular weight (Mn) 3000, hydroxyl value 27 mgKOH / g or more, all hydroxyl-terminated polybutadienes).

[0082] The diol compound synthesized from the dimer acid may be commercially available, for example, Pripol 2033 (hydroxyl value 202 to 212 mgKOH / g) manufactured by Croda Japan.

[0083] The number average molecular weight (Mn) of the hydrocarbon polyol (a3-1) is preferably 500 to 10,000, more preferably 700 to 6,000, and even more preferably 900 to 4,000. When the number average molecular weight is within the above range, the dielectric properties and workability of the resulting aromatic ester compound (A) can be further improved. In this specification, the number average molecular weight (Mn) is the value published by the manufacturer or the value obtained by measurement using gel permeation chromatography (GPC).

[0084] --Polycarbonate polyol (a3-2)-- Examples of the polycarbonate polyol (a3-2) include polyols obtained by adding hydroxyl groups to the terminals of the reaction product of a carbonate ester and / or phosgene with a low-molecular-weight polyol.

[0085] Examples of carbonate esters include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, and diphenyl carbonate.

[0086] From the viewpoint of imparting flexibility, the number of carbon atoms of the low molecular weight polyol is preferably 2 to 20, more preferably 4 to 18. Specific examples of the low molecular weight polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,7-heptanediol, 1,8-octanediol, and the like. hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4'-biphenol, and the like.

[0087] Examples of the polycarbonate polyol (a3-2) include aliphatic polycarbonate polyols and alicyclic polycarbonate polyols (for example, those obtained by reacting cyclohexanedimethanol and its derivatives). Among these, aliphatic polycarbonate polyols are preferred as the polycarbonate polyol (a3-2) from the viewpoint of flexibility.

[0088] The number average molecular weight (Mn) of the polycarbonate polyol (a3-2) is preferably 500 to 5000, more preferably 800 to 3000. When the number average molecular weight is within the above range, the workability of the resulting aromatic ester compound (A) can be further improved.

[0089] The polycarbonate polyol (a3-2) may be commercially available, such as the Kuraray Polyol series "C-2090" and "PHC" manufactured by Kuraray Co., Ltd., and the polycarbonate diol "Duranol" manufactured by Asahi Kasei Corporation.

[0090] --Polyester polyol (a3-3)-- Examples of the polyester polyol (d-3) include polyester polyols obtained by reacting a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, or sebacic acid, or a dialkyl ester thereof, or a mixture thereof, with a glycol such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, or polytetramethylene ether glycol, or a mixture thereof; and polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, polyvalerolactone, or poly(β-methyl-γ-valerolactone).

[0091] The number average molecular weight (Mn) of the polyester polyol (a3-3) is preferably 500 to 5000, more preferably 800 to 3000. When the number average molecular weight is within the above range, the dielectric properties and workability of the resulting aromatic ester compound (A) can be further improved.

[0092] As the polyester polyol (a3-3), commercially available products may be used, such as the Polylite series manufactured by DIC Corporation.

[0093] --Polyether polyol (a3-4)-- Examples of the polyether polyol (a3-4) include polyether polyols obtained by polymerizing an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran using water or a low-molecular-weight polyol such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, or bisphenol A as an initiator.

[0094] The number average molecular weight (Mn) of the polyether polyol (a3-4) is preferably 500 to 5000, more preferably 800 to 3000. When the number average molecular weight is within the above range, the dielectric properties and workability of the resulting aromatic ester compound (A) can be further improved.

[0095] As the polyether polyol (a3-4), commercially available products may be used. Examples of commercially available products include Sannix GP-400, GP-600, GP-1000, GP-1500, GP-3000, GP-4000V, GA-5000S, FA-908, FA-961, FA-921, FA-703, and FA-757 manufactured by Sanyo Chemical Co., Ltd.; Actocol G-28, MN-5000, MN-4000, P-31, and MN-1500 manufactured by Mitsui Chemicals, Inc.; and Excelnol 1030, 4030, 5030, 230, 828, and 837, Preminol 3005, 3010, 3015, 3020, 7001, 7006, and 7012, Preminol S3006 and 3011, and Preminol 7021 (tetrafunctional) manufactured by AGC Corporation.

[0096] --Polyurethane polyol (a3-5)-- Examples of the polyurethane polyol (a3-5) include polyurethane polyols obtained by reacting the various polyols described above with polyisocyanate at an NCO / OH ratio of less than 1. The NCO / OH ratio is more preferably 0.9 or less.

[0097] Examples of the polyisocyanate include aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, and triphenylmethane triisocyanate; aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, and 1,3-(isocyanatomethyl)cyclohexane; polyisocyanate derivatives (modified products) such as biurets of these aromatic or aliphatic polyisocyanates or isocyanurates of these aromatic or aliphatic polyisocyanates; and adducts of these aromatic or aliphatic polyisocyanates modified with trimethylolpropane.

[0098] The number average molecular weight (Mn) of the polyurethane polyol (a3-5) is preferably from 500 to 5000, more preferably from 800 to 3000. When the number average molecular weight is within the above range, the dielectric properties and workability of the resulting aromatic ester compound (A) can be further improved.

[0099] As the polyurethane polyol (a3-5), commercially available products may be used.

[0100] --Polysiloxane polyol (a3-6)-- Examples of the polysiloxane polyol (a3-6) include dimethylpolysiloxane having terminal hydroxyl groups, and methylphenylpolysiloxane having terminal hydroxyl groups.

[0101] The number average molecular weight (Mn) of the polysiloxane polyol (a3-6) is preferably 500 to 5000, more preferably 800 to 3000. When the number average molecular weight is within the above range, the dielectric properties and workability of the resulting aromatic ester compound (A) can be further improved.

[0102] The polysiloxane polyol (a3-6) may be a commercially available product, such as "KF-6000," "KF-6001," "KF-6002," "KF-6003," "X-22-176DX," "X-22-176F," or "X-22-176-GX-A" manufactured by Shin-Etsu Chemical Co., Ltd., or "Silaplane FM-4411," "Silaplane FM-4421," or "Silaplane FM-4425" manufactured by JNC Corporation.

[0103] - Compounds that are reactive with aromatic polycarboxylic acids (a1) or monohydroxy aromatic compounds (a2) - The reaction raw materials for the aromatic ester compound (A) may optionally further contain a compound reactive with the aromatic polycarboxylic acids (a1) or the monohydroxy aromatic compound (a2). Examples of such compounds include polyhydroxy aromatic compounds (a4), such as dihydroxy aromatic compounds, trihydroxy aromatic compounds, tetrahydroxy aromatic compounds, pentahydroxy aromatic compounds, and hexahydroxy aromatic compounds. Preferred polyhydroxy aromatic compounds (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.

[0104] <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 Q12 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 31 each 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.]

[0105] 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.

[0106] 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 (a C1 to C30 alkylene group) or a linear or branched alkylene ether group (a C1 to C30 alkylene ether group), 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 12each independently represents a structure represented by the above general formula (2) or (3), * in the general formula (2) and 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.

[0107] 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.

[0108] <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 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).

[0109] 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).

[0110] 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 elongation, low elasticity, and 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 (A) contains an ester structure having the following structure at its terminal, it exhibits high reactivity with epoxy groups, etc., contained in the component (B) or curing agent described below. This high reactivity can, for example, 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)), it is possible to introduce an alkylene chain (e.g., a divalent aliphatic hydrocarbon group) or an alkylene ether chain (oxyalkylene group) derived from the polyhydric alcohol compound (a3) ​​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 further, the introduction of a structure with low polarity results in excellent low dielectric properties, which is a preferred embodiment.

[0111] 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. In this regard, it is generally known that hydroxyl groups have high polarity and increase the dielectric loss tangent. However, by using the aromatic ester compound (A) of this embodiment, a low dielectric loss tangent can be achieved in the cured product. Furthermore, since the aromatic ester compound (A) has two or more reactive ester bonds, the crosslink density of the cured product can be increased, and the heat resistance can be improved.

[0112] <Characteristics of aromatic ester compound (A)> When the aromatic activated ester group in the aromatic ester compound (A) is used as the functional group, the functional group equivalent of the aromatic ester compound (A) is preferably in the range of 160 to 3000 g / eq. In this case, the curing property is more excellent, and a cured product having a lower dielectric constant and dielectric dissipation factor (low dielectric characteristics) can be obtained. From the same viewpoint, the functional group equivalent of the aromatic ester compound (A) is more preferably 180 g / eq or more, and even more preferably 200 g / eq or more, and more preferably 2800 g / eq or less, and even more preferably 2600 g / eq or less.

[0113] The number average molecular weight (Mn) of the aromatic ester compound (A) is preferably 320 to 6000. When the number average molecular weight (Mn) is 320 or more, the dielectric loss tangent can be made better, and when it is 6000 or less, the moldability can be improved. From the same viewpoint, the number average molecular weight (Mn) of the aromatic ester compound (A) is more preferably 360 or more, and even more preferably 400 or more, and more preferably 5600 or less, and even more preferably 5200 or less.

[0114] From the viewpoints of achieving a better balance between handleability when preparing a curable resin composition described later and the heat resistance and dielectric properties of the cured product, 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.

[0115] 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 (elongation), low elasticity, heat resistance, adhesion to copper foil and the like due to the flexibility, and low dielectric properties in the obtained cured product, as well as semiconductor encapsulating materials, semiconductor devices, prepregs, circuit boards, build-up films, and the like that use the curable resin composition.

[0116] <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 used as raw materials and reacted. 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.

[0117] 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.

[0118] 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.

[0119] 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 photosensitivity, elongation, low modulus, heat resistance, 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.

[0120] 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').

[0121] 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).

[0122] During the reaction in the second reaction step, an antioxidant may be used to prevent deterioration due to contamination with trace amounts of oxygen. Specific examples of antioxidants 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)] phenolic 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;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) thioether compounds such as N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline ... -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, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -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, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds, esters of phosphoric acid and octadecan-1-ol, triphenyl phosphite, 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.

[0123] In the second reaction step, the same solvent as that used in the first reaction step can be used.

[0124] 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 obtaining an aromatic ester compound (A) with better workability and flexibility, the hydroxyl group equivalent of the polyhydric alcohol compound (a3) ​​relative to 1 equivalent of the active ester group in 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.

[0125] 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).

[0126] (Resin (B) having an acid group and a polymerizable unsaturated group) The resin (B) having an acid group and a polymerizable unsaturated group is one of the essential components of the resin composition having an acid group and a polymerizable unsaturated group of this embodiment. The 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.

[0127] 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. Examples of the polymerizable unsaturated group contained in the resin (B) having an acid group and a 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.

[0128] 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.

[0129] <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.

[0130] 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.

[0131] 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.

[0132] 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): [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 41 A 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.] can also be used.

[0133] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain. The (poly)ester chain is, for example, a 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.

[0134] 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. The (poly)carbonate chain may be, for example, a 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 of 1 to 5.] is an example of a (poly)carbonate chain.

[0135] 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.

[0136] The unsaturated monobasic acids (b1-2) may be used singly or in combination of two or more.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] The polybasic acid anhydrides (b1-3) may be used singly or in combination of two or more. Among these, tetrahydrophthalic anhydride, succinic anhydride, and cyclohexanedicarboxylic anhydride are preferred from the viewpoint of more effectively improving photosensitivity, elongation, low modulus, heat resistance, and / or low dielectric properties.

[0142] 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.]

[0143] 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.

[0144] Among these, from the viewpoint of more effectively improving photosensitivity, elongation, low elasticity, heat resistance and / or 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.

[0145] The method for producing the epoxy resin (B1) having an acid group and a polymerizable unsaturated group 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.

[0146] 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 140°C.

[0147] 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).

[0148] 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.

[0149] 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.

[0150] Examples of basic catalysts 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, trioctylmethylammonium chloride, and trioctylmethylammonium chloride. 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.

[0151] 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, from the viewpoints of enabling the resin composition to exhibit higher photosensitivity and enabling the resulting cured product to exhibit superior elongation, low elasticity, heat resistance, and low dielectric properties. Note that, in the present disclosure, the acid value of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group is a value measured by the neutralization titration method of JIS 0070 (1992).

[0152] <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 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); Examples of the resin include a resin obtained by reacting a (meth)acrylate compound (b1-5), 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).

[0153] 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.

[0154] 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.

[0155] The method for producing the urethane resin (B2) having an acid group and a polymerizable unsaturated group 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.

[0156] 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.

[0157] <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.

[0158] 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.

[0159] 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.

[0160] 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 kinds. 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.

[0161] 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, from the viewpoints of enabling the resin composition to exhibit higher photosensitivity and enabling the resulting cured product to exhibit superior elongation, low elasticity, heat resistance, and low dielectric properties. Note that the acid value of the acrylic resin (B3) having an acid group and a polymerizable unsaturated group in the present invention is a value measured by the neutralization titration method of JIS K 0070 (1992).

[0162] <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.

[0163] 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).

[0164] 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.

[0165] 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.

[0166] 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.

[0167] The method for producing the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group 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.

[0168] 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.

[0169] The method for producing the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group is not particularly limited, and any method may be used. 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.

[0170] 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.

[0171] The acid value of the amide-imide resin (B4) 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 high photosensitivity, heat resistance, and dielectric properties is 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).

[0172] <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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] 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 viewpoints of providing a resin composition with higher photosensitivity and of providing a cured product with superior elongation, low elasticity, heat resistance, and low dielectric properties. The alkylene carbonates can be used alone or in combination of two or more.

[0179] Examples of alkylene oxides (b5-2b) include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred from the viewpoints of providing a resin composition with higher photosensitivity and of providing a cured product with superior elongation, low elasticity, heat resistance, and low dielectric properties. The alkylene oxides can be used alone or in combination of two or more.

[0180] 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 viewpoints of providing a resin composition with higher photosensitivity and exhibiting superior elongation, low elasticity, heat resistance, and low dielectric properties in the resulting cured product. The N-alkoxyalkyl(meth)acrylamide compounds (b5-3) can be used alone or in combination of two or more kinds.

[0181] 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 viewpoints of making the resin composition exhibit higher photosensitivity and making the obtained cured product exhibit better elongation, low elasticity, heat resistance, and low dielectric properties.

[0182] 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.

[0183] 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 b2 and 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 b4and R b10 each 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 124each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R 122 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.

[0184] The acid value of the acrylamide resin (B5) 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, from the viewpoints of enabling the resin composition to exhibit higher photosensitivity and enabling the resulting cured product to exhibit better elongation, low elasticity, heat resistance, and low dielectric properties. 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).

[0185] <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 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).

[0186] The alkylene oxide (b5-2b) may be the same as those exemplified above for the alkylene oxide (b5-2b). Among these, ethylene oxide or propylene oxide is preferred, from the viewpoints of providing a resin composition with higher photosensitivity and of providing a cured product with superior elongation, low elasticity, heat resistance, and low dielectric properties. The alkylene oxide (b5-2b) can be used alone or in combination of two or more kinds.

[0187] 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 viewpoints of providing a resin composition with higher photosensitivity and of providing a cured product with superior elongation, low elasticity, heat resistance, and low dielectric properties. The alkylene carbonates (b5-2a) can be used alone or in combination of two or more kinds.

[0188] The method for producing the ester resin (B6) having an acid group and a polymerizable unsaturated group 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.

[0189] 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.

[0190] The above are the essential components contained in the resin composition having an acid group and a polymerizable unsaturated group according to this embodiment.

[0191] (Optional addition ingredient) Furthermore, the resin composition having an acid group and a polymerizable unsaturated group of the present embodiment may contain, in addition to the above-mentioned compounds or resins, various known additives such as an ultraviolet stabilizer and a storage stabilizer.

[0192] 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.

[0193] [Curable resin composition] The curable resin composition of this embodiment is characterized by containing at least the resin composition having an acid group and a polymerizable unsaturated group described above, and a photopolymerization initiator. In other words, the curable resin composition of this embodiment is characterized by containing at least the aromatic ester compound (A) described above, the resin (B) having an acid group and a polymerizable unsaturated group described above, and a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more.

[0194] (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.

[0195] 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.

[0196] Commercially available photopolymerization initiators 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", "Omnirad-500", and "Omnirad-1000". Examples of suitable anti-inflammatory agents include "IGM (Irradiation Group)", "Kayacure-DETX", "Kayacure-MBP", "Kayacure-DMBI", "Kayacure-EPA", and "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", and "Quantacure-EPD" (manufactured by Ward-Blenkinsop), and "Runtecure-1104" (manufactured by Runtec).

[0197] 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.

[0198] (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.

[0199] <Curing agent> Examples of the curing agent include epoxy resins and other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents, etc.), with epoxy resins being preferred.

[0200] The epoxy resin is not particularly limited, but is preferably 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 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.

[0201] The epoxy equivalent of the epoxy resin is preferably 120 to 400 g / eq, more preferably 150 to 300 g / eq. If the epoxy equivalent of the epoxy resin is 120 g / eq or more, the dielectric properties of the resulting cured product will be excellent, and if the epoxy equivalent of the epoxy resin is 400 g / eq or less, the balance between the heat resistance and the dielectric loss tangent of the resulting cured product will be excellent.

[0202] The softening point of the epoxy resin is preferably 20 to 200°C, more preferably 40 to 150°C, from the viewpoints of making the resin composition exhibit higher photosensitivity and making the resulting cured product exhibit better elongation, low elasticity, heat resistance, and low dielectric properties.

[0203] With regard 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 ((aromatic ester compound (A) + resin (B) having an acid group and a polymerizable unsaturated group) / epoxy resin) to the amount of epoxy resin used 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.

[0204] Examples of amine curing agents include, but are not limited to, 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.

[0205] Examples of acid anhydride curing agents 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.

[0206] Examples of phenolic resin curing agents include phenol novolac resin, cresol novolac resin, naphthol novolac resin, bisphenol novolac resin, biphenyl novolac resin, dicyclopentadiene-phenol adduct resin, phenol aralkyl resin, naphthol aralkyl resin, triphenolmethane type resin, tetraphenolethane type resin, and aminotriazine-modified phenol resin. Any of the other curing agents mentioned above may be used alone or in combination of two or more.

[0207] Regarding 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 (total) functional groups, the functional group equivalent ratio ((aromatic ester compound (A) + resin (B) having an acid group and a polymerizable unsaturated group) / other curing agents) to the amount of other curing agents used 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 results in reduced heat resistance and curability, so it is preferable to use within the above range.

[0208] <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.

[0209] 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.

[0210] 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).

[0211] 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.

[0212] 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.

[0213] 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.

[0214] Of the above-mentioned curing accelerators, it is preferable to use 2-ethyl-4-methylimidazole and N,N-dimethyl-4-aminopyridine (DMAP).

[0215] 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 relative to 100 parts by mass of the combined total of the (A) and (B) components. When the content of the curing accelerator is 0.01 part by mass or more, the curability can be more reliably improved. On the other hand, when the content of the curing accelerator is 5 parts by mass or less, the insulation reliability can be maintained sufficiently well. From the same viewpoint, the content of the curing accelerator is more preferably 0.1 part by mass or more, and more preferably 5 parts by mass or less, relative to 100 parts by mass of the combined total of the (A) and (B) components.

[0216] <Other resins> Examples of 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.

[0217] The content of the other resin in the curable resin composition of the present embodiment is preferably 50 mass % or less of the total.

[0218] <Organic solvents> The curable resin composition of the present embodiment may contain an organic solvent or may be solvent-free. The organic solvent has the function of adjusting the viscosity of the curable resin composition, etc.

[0219] Specific examples of organic solvents 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 organic solvents may be used alone or in combination of two or more.

[0220] The content of the organic 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 content of the organic solvent of 10 mass % or more is preferred because of excellent handleability. On the other hand, a content of the solvent of 90 mass % or less is preferred from the viewpoint of economy.

[0221] <Flame retardant> The flame retardant is not particularly limited, but examples thereof include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, halogen-based flame retardants, etc. The above-mentioned flame retardants may be used alone or in combination of two or more.

[0222] 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.

[0223] 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.

[0224] Examples of the halogen-based flame retardant include, but are not limited to, 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, and tetrabromophthalic acid.

[0225] The amount of flame retardant used in the curable resin composition of this embodiment is preferably 0.1 to 50 parts by mass per 100 parts by mass of the combined total of the components (A) and (B). When the content of the flame retardant is 0.1 part by mass or more, flame retardancy can be more reliably imparted. On the other hand, when the content of the flame retardant is 50 parts by mass or less, flame retardancy can be imparted 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, per 100 parts by mass of the combined total of the components (A) and (B).

[0226] <Filler> Examples of fillers include organic fillers and inorganic fillers. Organic fillers have functions such as improving elongation and mechanical strength. Inorganic fillers have functions such as reducing the coefficient of thermal expansion and imparting flame retardancy. The above-mentioned fillers may be used alone or in combination of two or more.

[0227] The organic filler is not particularly limited, but examples thereof include polyamide particles.

[0228] 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.

[0229] 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.

[0230] The amount of filler used in the curable resin composition of this embodiment is preferably 0.5 to 95 parts by mass per 100 parts by mass of the combined amount of the (A) and (B) components. When the filler content is 0.5 parts by mass or more, the effects of the filler can be sufficiently imparted. On the other hand, when the filler content is 95 parts by mass or less, deterioration of moldability due to an increase in the viscosity of the blend can be suppressed. From the same viewpoint, the filler content is more preferably 5 parts by mass or more and more preferably 80 parts by mass or less per 100 parts by mass of the combined amount of the (A) and (B) components.

[0231] 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.

[0232] [Cured product] The cured product of this embodiment is a cured product of the above-described curable resin composition. In other words, the cured product of this embodiment is obtained by irradiating the above-described curable resin composition with active energy rays to cure it. The cured product of this embodiment can function as an insulating material excellent in elongation, low elasticity, heat resistance, and low dielectric properties.

[0233] Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, γ rays, etc. When ultraviolet rays are used as active energy rays, irradiation may be carried out in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out a curing reaction by ultraviolet rays.

[0234] Specific examples of ultraviolet radiation sources include ultraviolet lamps such as low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, and metal halide lamps, as well as sunlight and LEDs. Of these, ultraviolet lamps are generally used from the viewpoints of practicality and economy.

[0235] The cumulative light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range. When the integrated light amount is within the above range, the occurrence of uncured portions can be sufficiently prevented or suppressed. The irradiation of the active energy rays may be carried out in one step or in two or more steps.

[0236] Another method for curing a curable resin composition to obtain a cured product is, for example, heat curing. The heating temperature for heat curing is not particularly limited, but is preferably 100 to 300°C, and the heating time is preferably 1 to 24 hours.

[0237] 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.

[0238] [Insulating material] The insulating material of this embodiment is made of the curable resin composition described above. Preferably, the insulating material of this embodiment is obtained by curing the curable resin composition by irradiating it with active energy rays. The insulating material of this embodiment has excellent elongation, low elasticity, heat resistance, and low dielectric properties.

[0239] Examples of such insulating materials include the above-mentioned 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 above-mentioned curable resin composition includes a method consisting of 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 on which a circuit has been formed using a spray coating method, curtain coating method, or the like, and then cured. In the second step, if necessary, predetermined through-holes or the like are drilled, followed by treatment with a roughening agent and rinsing the surface with hot water to form irregularities, and then 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 a predetermined circuit pattern. It is preferable that the through-holes be drilled after the formation of 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.

[0240] [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 in the range of 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 in the range of about 140 to 180°C. The resist member of this embodiment has excellent low dielectric properties and elongation. [Example]

[0241] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way.

[0242] The GPC was measured under the following conditions.

[0243] (GPC measurement) Measurements were performed using the following measuring equipment and conditions to obtain GPC charts of the diphenyl isophthalate derivatives and aromatic ester compounds obtained in the following synthesis examples and working examples. From the results of the GPC charts, it was confirmed that the target products (diphenyl isophthalate derivatives and aromatic ester compounds) were produced, based on the decrease and disappearance of the raw material peaks. Measuring device: Tosoh Corporation "HLC-8320 GPC" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40°C Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual for the GPC Workstation EcoSEC-WorkStation. (Polystyrene used) Tosoh Corporation "A-500" Tosoh Corporation "A-1000" Tosoh Corporation "A-2500" Tosoh Corporation "A-5000" "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 Tosoh Corporation "F-80" Tosoh Corporation "F-128" Sample: A tetrahydrofuran solution (50 μl) of 1.0 mass % in terms of solid content of the diphenyl isophthalate derivatives and aromatic ester compounds obtained in the synthesis examples and working examples was filtered through a microfilter and used.

[0244] (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 (component (a1)) and 4140.0 parts by mass of toluene. The system was purged with nitrogen under reduced pressure and dissolved. Next, 864.0 parts by mass of o-cresol (component (a2)) was charged and the system was purged with nitrogen and dissolved. Subsequently, 2.07 parts by mass of tetrabutylammonium bromide was dissolved, and 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. Furthermore, water was 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 decantation to obtain a crystalline compound (intermediate product (a')), a diphenyl isophthalate derivative (a'-1). Figure 1 shows the GPC chart of the obtained diphenyl isophthalate derivative (a'-1).

[0245] (Synthesis Example 2): Synthesis of aromatic ester compound (A-1) A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer was charged with 200 parts by mass of polybutadiene having hydroxyl groups at both ends as component (a3) ​​(trade name: G-1000, manufactured by Nippon Soda Co., Ltd., hydroxyl value: 74.2 mg KOH / g, hydroxyl equivalent: 756 g / eq), 91.5 parts by mass of the diphenyl isophthalate derivative (a'-1) as intermediate product (a') obtained in Synthesis Example 1, 0.29 parts by mass of 1,8-diazabicyclo[5,4,0]-undecene-7 (hereinafter abbreviated as "DBU"), 4-[[4,6-bis(octylthio)-1,3,5-triazin-2-yl]amino]-1,6-di-tert-butylphenol (trade name: IRGANOX®, manufactured by BASF Japan Ltd.), and 0.29 parts by mass of 565) was charged, and the system was purged with nitrogen under reduced pressure, then the temperature was raised to 180°C and stirred until the reaction was complete. The completion of the reaction was confirmed by GPC. Thereafter, o-cresol was removed by distillation under reduced pressure to obtain aromatic ester compound (A-1). The functional group equivalent of the obtained aromatic ester compound (A-1) was 995 g / eq based on the charge ratio, and the average repeat number p 11 (see general formula (1) above) was found to be 1 based on the charging ratio. The structure of the obtained aromatic ester compound (A-1) was as shown below. [ka]

[0246] (Synthesis Example 3): Synthesis of aromatic ester compound (A-2) In Synthesis Example 2, IRGANOX 565 was omitted, and 200.0 parts by mass of polycarbonate polyol (Kuraray Co., Ltd., product name: C-2090, hydroxyl value: 56.8 mg KOH / g, hydroxyl equivalent: 988 g / eq) was used instead of G-1000, the amount of isophthalic acid diphenyl derivative (a'-1) obtained in Synthesis Example 1 was changed from 91.5 parts by mass to 70.0 parts by mass, and DBU was changed from 0.29 parts by mass to 0.27 parts by mass, but the same procedure as in Synthesis Example 2 was performed to obtain aromatic ester compound (A-2). The functional group equivalent of this aromatic ester compound (A-2) was 1194 g / eq based on the charging ratio, and the average repeat number p 11(see general formula (1) above) was 1 based on the charging ratio. The structure of the obtained aromatic ester compound (A-2) was a structure that satisfied the general formula (1) above.

[0247] (Synthesis Example 4): Synthesis of aromatic ester compound (A-3) In Synthesis Example 2, IRGANOX 565 was omitted, and instead of G-1000, 50.0 parts by mass of polyester polyol (manufactured by Croda Japan Co., Ltd., trade name: PRIPLAST 1837LQGD, hydroxyl value 110 mg KOH / g, hydroxyl equivalent: 510 g / eq) was used, the amount of diphenyl isophthalate derivative (a'-1) obtained in Synthesis Example 1 was changed from 91.5 parts by mass to 34.0 parts by mass, and DBU was changed from 0.29 parts by mass to 0.084 parts by mass. An aromatic ester compound (A-3) was obtained by the same procedure as in Synthesis Example 2. The functional group equivalent of this aromatic ester compound (A-3) was 748 g / eq based on the charging ratio, and the average repeat number p 11 (see general formula (1) above) was 1 based on the charging ratio. The structure of the obtained aromatic ester compound (A-3) was a structure that satisfied the general formula (1) above.

[0248] (Synthesis Example 5: Production 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).

[0249] (Synthesis Example 6: Production 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 monoethyl 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 as an antioxidant. 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, 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 nonvolatile content of this resin (B-2) having an acid group and a polymerizable unsaturated group was 62% by mass, and the acid value of the solid content was 80 mgKOH / g.

[0250] (Comparative Synthesis Example 1): Synthesis of phenolic hydroxyl group-containing resin (a'-2) A flask equipped with a thermometer and a stirrer was charged with 127 parts by weight of diglycidyl ether of 1,6-hexanediol (manufactured by DIC Corporation, product name: SR-16HL, epoxy equivalent: 127 g / eq) and 228 parts by weight of bisphenol A (hydroxyl equivalent: 114 g / eq), and the temperature was raised to 140 °C over 30 minutes. Next, 1.8 parts by weight of 4% aqueous sodium hydroxide solution was added to the flask, and the temperature inside the flask was raised to 150 °C over 30 minutes. 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 (a'-2). A GPC chart (not shown) confirmed the formation of phenolic hydroxyl-containing resin (a'-2), and the hydroxyl equivalent of resin (a'-2) was confirmed to be 300 g / eq.

[0251] (Comparative Synthesis Example 2): Synthesis of aromatic ester compound (A-4) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 300 parts by weight of the phenolic hydroxyl-containing resin (a'-2) (hydroxyl equivalent: 300 g / eq) obtained in Comparative Synthesis Example 1 and 1,212 parts by weight of methyl isobutyl ketone (hereinafter abbreviated as "MIBK"). The system was purged with nitrogen under reduced pressure to dissolve the phenolic hydroxyl-containing resin (a'-2). Next, 140.5 parts by weight (1.0 mol) of benzoyl chloride was charged to the flask. Then, while purging with nitrogen gas, the system was controlled to 60°C or below, and 216 parts by weight 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. The water was then removed by decanting, followed by removing the MIBK by vacuum dehydration, yielding aromatic ester compound (A-4). The functional group equivalent of the resulting aromatic ester (A-4) was 404 g / eq based on the charge ratio.

[0252] (Example 1: Preparation of curable resin composition (1)) A resin composition (1) having an acid group and a polymerizable unsaturated group was obtained by mixing 15 parts by mass of the aromatic ester compound (A-1) obtained in Synthesis Example 2 with 100 parts by mass (62 parts by mass as solids) of the resin (B-2) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 62% by mass obtained in Synthesis Example 6. 22.7 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 12.2 parts by mass of diethylene glycol monoethyl ether acetate as an organic solvent, 3.9 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), 0.5 parts by mass of 2-ethyl-4-methylimidazole, 7.7 parts by mass of dipentaerythritol hexaacrylate, and 0.5 parts by mass of phthalocyanine green.

[0253] (Examples 2 to 8: Preparation of curable resin compositions (2) to (8)) In the same manner as in Example 1, an aromatic ester compound selected from (A-1) to (A-4) and a resin having an acid group and a polymerizable unsaturated group selected from (B-1) to (B-2) were mixed in the blending ratios shown in Table 1 to obtain resin compositions (2) to (8) having an acid group and a polymerizable unsaturated group, and curable resin compositions (2) to (8).

[0254] (Comparative Example 1: Preparation of curable resin composition (R1)) A curable resin composition (R1) was obtained by mixing 100 parts by mass (65 parts by mass as solids) of the resin (B-1) having an acid group and a polymerizable unsaturated group and having a non-volatile content of 65% by mass obtained in Synthesis Example 5, 25.3 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 13.6 parts by mass of diethylene glycol monoethyl ether acetate as an organic solvent, 3.3 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), 0.5 parts by mass of 2-ethyl-4-methylimidazole, 6.5 parts by mass of dipentaerythritol hexaacrylate, and 0.5 parts by mass of phthalocyanine green.

[0255] (Comparative Example 2: Preparation of curable resin composition (R2)) Resin composition (R1) was obtained by mixing 15 parts by mass of the aromatic ester compound (A-4) obtained in Comparative Synthesis Example 2 with 100 parts by mass (62 parts by mass as solids) of the resin (B-2) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 62% by mass obtained in Synthesis Example 6. This resin composition was then mixed with 22.7 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 12.2 parts by mass of diethylene glycol monoethyl ether acetate as an organic solvent, 3.9 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), 0.5 parts by mass of 2-ethyl-4-methylimidazole, 7.7 parts by mass of dipentaerythritol hexaacrylate, and 0.5 parts by mass of phthalocyanine green to obtain curable resin composition (R2).

[0256] The following evaluations were carried out using the curable resin compositions (1) to (8), (R1) and (R2) obtained in the above examples and comparative examples.

[0257] [Photosensitivity evaluation method] The curable resin composition obtained in each Example and Comparative Example was applied to a glass substrate using an applicator to a film thickness of 50 μm, and then dried at 80° C. for 30 minutes. Then, the composition was irradiated with 5 kJ / m irradiated light using a metal halide lamp via a Kodak Step Tablet No. 2. 2 This was developed for 180 seconds in a 1% by mass aqueous solution of sodium carbonate, and the number of remaining steps was used for evaluation. The greater the number of remaining steps, the higher the photosensitivity.

[0258] Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (8) prepared in Examples 1 to 8 and the curable resin compositions (R1) and (R2) prepared in Comparative Examples 1 and 2.

[0259] [Table 1]

[0260] (Example 9: Preparation of curable resin composition (9)) A resin composition (9) having an acid group and a polymerizable unsaturated group was obtained by mixing 15 parts by mass of the aromatic ester compound (A-1) obtained in Synthesis Example 2 with 100 parts by mass (62 parts by mass as solids) of the resin (B-2) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 62% by mass obtained in Synthesis Example 6. 22.7 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 12.2 parts by mass of diethylene glycol monoethyl ether acetate as an organic solvent, 3.9 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), and 0.3 parts by mass of 4-dimethylaminopyridine.

[0261] (Examples 10 to 16: Preparation of curable resin compositions (10) to (16)) In the same manner as in Example 9, an aromatic ester compound selected from (A-1) to (A-4) and a resin having an acid group and a polymerizable unsaturated group selected from (B-1) to (B-2) were mixed in the blending ratios shown in Table 2 to obtain resin compositions (10) to (16) having an acid group and a polymerizable unsaturated group, and also obtain curable resin compositions (10) to (16).

[0262] (Comparative Example 3: Preparation of curable resin composition (R3)) A curable resin composition (R3) was obtained by mixing 100 parts by mass (65 parts by mass as solids) of the resin (B-1) having an acid group and a polymerizable unsaturated group and having a nonvolatile content of 65% by mass obtained in Synthesis Example 5, 25.3 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 13.6 parts by mass of diethylene glycol monoethyl ether acetate as an organic solvent, and 3.3 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins).

[0263] (Comparative Example 4: Preparation of curable resin composition (R4)) Using the blending ratios shown in Table 2, a curable resin composition (R4) was obtained in the same manner as in Comparative Example 3.

[0264] The curable resin compositions obtained in the above Examples and Comparative Examples were evaluated as follows.

[0265] [Heat resistance evaluation method] The curable resin compositions obtained in each of the Examples and Comparative Examples were applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Kaisha) using an applicator to a thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply the applied curable resin compositions to a copper foil to a thickness of 50 μm. 2 After irradiating the film with ultraviolet light, the film was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the copper foil to obtain a cured product. A 6 mm x 35 mm test piece was cut out from the cured product, and the temperature at which the change in elastic modulus was maximized was evaluated as the glass transition temperature using a viscoelasticity measuring device (DMA: Rheometrics solid viscoelasticity measuring device "RSAII", tensile method: frequency 1 Hz, heating rate 3°C / min). Note that a higher glass transition temperature indicates better heat resistance.

[0266] [Method for measuring elongation] The elongation was measured based on a tensile test. <Preparation of test piece 1> The curable resin compositions obtained in the examples and comparative examples were applied onto copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using a 50 μm applicator, and then heated at 10 kJ / m using a metal halide lamp. 2 After irradiating with ultraviolet light, the product was heated for 1 hour at 160° C. The cured product was peeled off from the copper foil to obtain a test piece 1 (cured product).

[0267] <Tensile test> The test piece 1 was cut into a size of 10 mm × 80 mm, and a tensile test was performed on the test piece 1 under the following measurement conditions using a precision universal testing machine, Autograph "AG-IS," manufactured by Shimadzu Corporation. The elongation (%) until the test piece broke was measured.

[0268] Measurement conditions: temperature 23℃, humidity 50%, distance between gauge lines 20mm, distance between supports 20mm, tensile speed 10mm / min

[0269] [Method for measuring elastic modulus] Using the same test piece 1 (cured product) as above, the elastic modulus was measured at 2 mm / min in accordance with JIS K 7181. A smaller value indicates lower elasticity.

[0270] [Method for measuring dielectric constant] The curable resin composition obtained in each of the Examples and Comparative Examples was applied to a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply 10 kJ / m 2 After irradiating the glass substrate with ultraviolet light, the coating was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The product was then stored for 24 hours in a room at 23°C and 50% humidity to prepare a test piece. The dielectric constant of the test piece at 1 GHz was measured using a network analyzer E8362C manufactured by Agilent Technologies Inc. by the cavity resonance method.

[0271] [Method for measuring dielectric loss tangent] The curable resin composition obtained in each of the Examples and Comparative Examples was applied to a glass substrate using an applicator to a film thickness of 50 μm, and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply 10 kJ / m 2 After irradiating the glass substrate with ultraviolet light, the coating was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The product was then stored in a room at 23°C and 50% humidity for 24 hours to prepare a test specimen. The dielectric loss tangent of the test specimen at 1 GHz was measured using the cavity resonance method with an Agilent Technologies Network Analyzer E8362C.

[0272] Table 2 shows the compositions and evaluation results of the curable resin compositions (9) to (16) obtained in Examples 9 to 16 and the curable resin compositions (R3) and (R4) obtained in Comparative Examples 3 and 4.

[0273] [Table 2]

[0274] From Tables 1 and 2, it can be seen that the resin compositions of the examples exhibit higher photosensitivity than the comparative examples, and the resulting cured products exhibit excellent elongation, low elasticity, heat resistance, and low dielectric properties. [Industrial Applicability]

[0275] According to the present invention, it is possible to provide a resin composition that exhibits high photosensitivity and is capable of producing a cured product having excellent elongation, low elasticity, heat resistance, and low dielectric properties. Furthermore, according to the present invention, it is possible to provide 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.

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; the hydroxyl group equivalent of the polyhydric alcohol compound (a3) ​​is 270 g / eq or more, a mass ratio [(A) / (B)] of solid contents of the aromatic ester compound (A) to the resin (B) having an acid group and a polymerizable unsaturated group is in the range of 5 / 95 to 50 / 50; A resin composition having an acid group and a polymerizable unsaturated group, characterized in that:

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 1 to 2, and the formula (II ...

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 alkenyl group, an alkoxy group, an aryl group, or an aralkyl group; k ２１ represents an integer from 0 to 7, 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,

4. The resin composition having an acid group and a polymerizable unsaturated group according to any one of claims 1 to 3, wherein the polyhydric alcohol compound (a3) ​​is a polyol having an aliphatic hydroxyl group.

5. 5. The resin composition having an acid group and a polymerizable unsaturated group according to claim 4, wherein the polyol having an aliphatic hydroxyl group is at least one selected from the group consisting of hydrocarbon polyols, polycarbonate polyols, polyester polyols, polyether polyols, polyurethane polyols, and polysiloxane polyols.

6. 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 5, and a photopolymerization initiator.

7. A cured product of the curable resin composition according to claim 6.

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

9. A resist member comprising the curable resin composition according to claim 6.

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