Resin composition having polymerizable unsaturated group, curable resin composition, cured product, and article

Abstract

To provide a resin composition capable of giving an insulating material which has a low linear expansion coefficient and is excellent in dielectric characteristics and elongation.SOLUTION: The present disclosure provides a resin composition having a polymerizable unsaturated group which contains an aromatic ester compound (A) and an epoxy resin (B) having a polymerizable unsaturated group. The aromatic ester compound (A) is a compound using an aromatic polycarboxylic acid, an acid halide thereof and / or an esterified product thereof (a1), a monohydroxy aromatic compound (a2), and a polyhydric alcohol compound (a3) as essential reaction raw materials. The polyhydric alcohol compound (a3) has a hydroxyl equivalent of less than 270 g / eq. The epoxy resin (B) having a polymerizable unsaturated group is a resin using an epoxy resin (b1) and an unsaturated monobasic acid (b2) as essential reaction raw materials.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a resin composition having a polymerizable unsaturated group, a curable resin composition, a cured product, and an article. [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] For example, Patent Document 1 discloses a photosensitive resin composition containing an active ester curing agent and a carboxyl group-containing radical polymerizable compound as a material used in an alkali development type photoresist method. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-214057 Summary of the Invention [Problem to be solved by the invention]

[0005] Recently, a new method for forming a solder resist film by inkjet printing has been proposed. This method does not require development, as is required in the alkaline development method, and therefore can reduce the number of steps, time, and consumables. Here, when the viscosity of ink used in the inkjet method decreases, the physical properties required for a solder resist film, such as heat resistance and chemical resistance, tend to deteriorate significantly. Therefore, it is important that the ink used in the inkjet method has low viscosity and does not increase in viscosity. As a material (oligomer) compatible with the inkjet method, epoxy acrylate, which is obtained by partially acrylated epoxy resin and can be cured by ultraviolet light or heat, has been proposed. However, the above-mentioned epoxy acrylate has a hydroxyl group generated by the acrylate conversion of the epoxy resin, which increases the dielectric constant, making it difficult to apply it to high frequency applications when used alone. Furthermore, from the viewpoint of preventing defects such as cracking and peeling, the solder resist film is also required to have excellent adhesion to wiring or substrate, a low coefficient of linear expansion, and flexibility (elongation). Therefore, an object of the present disclosure is to provide a resin composition that can be used to obtain an insulating material having a low linear expansion coefficient and excellent dielectric properties and elongation. Another object of the present disclosure is to provide a curable resin composition containing such a resin composition, a cured product thereof, and an article using such a cured product. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that by using a resin composition containing a specific aromatic ester compound and an epoxy resin having a specific polymerizable unsaturated group, the resulting cured product has a low coefficient of linear expansion and excellent dielectric properties and elongation in a well-balanced manner, and have completed the present invention as described below. The present disclosure provides a resin composition having a polymerizable unsaturated group, which contains an aromatic ester compound (A) and an epoxy resin (B) having 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 less than 270 g / eq; The epoxy resin (B) having a polymerizable unsaturated group is a resin obtained by reacting an epoxy resin (b1) and an unsaturated monobasic acid (b2) as essential reaction raw materials. The present invention relates to a resin composition having a polymerizable unsaturated group, characterized in that: [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a resin composition that can be used to obtain an insulating material having a low linear expansion coefficient and excellent dielectric properties and elongation. Furthermore, according to the present invention, it is possible to provide a curable resin composition containing such a resin composition, a cured product thereof, and an article using such a cured product. DETAILED DESCRIPTION OF THE INVENTION

[0008] 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.

[0009] [Resin composition having a polymerizable unsaturated group] The resin composition having a polymerizable unsaturated group of this embodiment is a resin composition having a polymerizable unsaturated group, which contains an aromatic ester compound (A) (hereinafter also referred to as component (A)) and an epoxy resin (B) having a polymerizable unsaturated group (hereinafter also referred to as component (B)). The aromatic ester compound (A) is a compound obtained by reacting an aromatic polycarboxylic acid, its acid halide and / or its ester (a1), a monohydroxyaromatic compound (a2), and a polyhydric alcohol compound (a3) ​​as essential reaction raw materials. The polyhydric alcohol compound (a3) ​​has a hydroxyl equivalent of less than 270 g / eq. The epoxy resin (B) having a polymerizable unsaturated group is a resin obtained by reacting an epoxy resin (b1) and an unsaturated monobasic acid (b2) as essential reaction raw materials. By using such a resin composition having a polymerizable unsaturated group, it is possible to obtain an insulating material having a low coefficient of linear expansion and excellent dielectric properties and elongation.

[0010] The content of the aromatic ester compound (A) in the total amount (100% by mass) of the resin composition having a polymerizable unsaturated group of the present embodiment is, from the viewpoint of improving the low linear expansion coefficient, dielectric properties, and elongation 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 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less. Furthermore, from the viewpoint of achieving a well-balanced improvement in low linear expansion coefficient, dielectric properties, and elongation, the content of the epoxy resin (B) having a polymerizable unsaturated group in the total amount (100% by mass) of the resin composition having a polymerizable unsaturated group of the present 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.

[0011] In the resin composition having a polymerizable unsaturated group of this embodiment, the mass ratio of the solid content of the aromatic ester compound (A) to the epoxy resin (B) having a polymerizable unsaturated group [(A) / (B)] is preferably in the range of 10 / 90 to 90 / 10 from the viewpoint of achieving a low linear expansion coefficient, dielectric properties, and elongation in a well-balanced manner. From the same viewpoint, the mass ratio is more preferably 10 / 90 or more and more preferably 40 / 60 or less.

[0012] The resin composition having a polymerizable unsaturated group of this embodiment may further contain an optional additional component as an optional component. Furthermore, the resin composition having a polymerizable unsaturated group of this embodiment may be substantially composed of only the component (A), the component (B), and the optional additional component. The resin composition having a polymerizable unsaturated group of this embodiment may be composed of only the component (A) and the component (B). The resin composition having a polymerizable unsaturated group of this embodiment may contain inevitable impurities in addition to the component (A), the component (B), and the optional additional component, as long as the effects of the present disclosure are not impaired. From the viewpoint of achieving a well-balanced improvement in low linear expansion coefficient, dielectric properties, and elongation, the total content of the (A) component and the (B) component in the total amount (100% by mass) of the resin composition having a polymerizable unsaturated group of the present embodiment is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% 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.

[0013] Hereinafter, after explaining the main terms used in this specification, the components contained in the resin composition having a polymerizable unsaturated group of the present embodiment, namely, the aromatic ester compound (A), the epoxy resin (B) having a polymerizable unsaturated group, and the optional additional components, will be described.

[0014] (Terminology explanation) Unless otherwise specified herein, the following terms apply. The "aromatic group" in this specification preferably has an aromatic ring having 3 to 30 carbon atoms. The "aromatic group" in this specification may have a hydrogen atom of the aromatic ring substituted with a substituent, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.

[0015] 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.

[0016] 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."

[0017] 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.

[0018] As used herein, examples of the "aralkyl group" include a benzyl group, a diphenylmethyl group, a biphenyl group, and a naphthylmethyl group.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] In this specification, a "monovalent hydrocarbon group" 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 alkylene group having 1 to 20 carbon atoms.

[0026] 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 alkyl group having 1 to 20 carbon atoms.

[0027] 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.

[0028] 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.

[0029] (Aromatic ester compound (A)) The aromatic ester compound (A) is one of the essential components of the resin composition having 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.

[0030] In this specification, "aromatic polycarboxylic acids, acid halides thereof and / or esters thereof (a1)" may be abbreviated as "aromatic polycarboxylic acids (a1)" hereinafter.

[0031] 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.

[0032] <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).

[0033] 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).

[0034] 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).

[0035] 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.

[0036] The aromatic polycarboxylic acid, its acid halide and / or its ester (a1) is represented by the following general formula (a1): [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).

[0037] 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).

[0038] 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 a3 represents an integer between 2 and 6. a3 is preferably 2. The polyhydric hydroxy aromatic compound (a4) is a compound in which only 2 to 6 hydrogen atoms in the aromatic ring in the aromatic group are substituted with hydroxyl groups, whereas the polyhydric alcohol compound (a3) ​​is a polyhydric alcohol other than the polyhydric hydroxy aromatic compound (a4).

[0039] 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 a4n-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.

[0040] 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.

[0041] 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.

[0042] 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 atoms and hydrogen atoms in the molecule of the polyhydric alcohol compound (a3) ​​(examples of the divalent to hexavalent hydrocarbon group include an alkylene chain or an alkylene ether chain (however, the —CH— group in the alkylene chain or the alkylene ether chain may be substituted with a divalent aromatic group))) and a residue of a polyvalent hydroxy aromatic compound (a4), which is an optional component, are linked together. [ka] (In the above general formula (i), Ar i1 represents a monovalent aromatic group, and Ar i2 represents a divalent aromatic group, and the dashed line in the above general formula (i) represents a bond to another atom.

[0043] 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).

[0044] 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 having excellent low dielectric properties, elongation, and low linear expansion.

[0045] 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.

[0046] 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 Q 2 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] In the above general formula (1), Ar 11is 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).

[0051] 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.

[0052] R in the above general formula (3) 31 is preferably any one of a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, and an aralkyl group, and among these, from the viewpoints of dielectric properties, workability, and flexibility of the obtained cured product, is more preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aralkyl group such as a benzyl group, a diphenylmethyl group, or a naphthylmethyl group, or an arylene group such as a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, or an anthryl group.

[0053] 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.

[0054] p in the above general formula (1) 11is 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.

[0055] 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.

[0056] 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.

[0057] <Reaction raw materials for aromatic ester compound (A)> The reaction raw materials for the aromatic ester compound (A) will be explained below. -Aromatic polycarboxylic acid, its acid halide and / or ester (a1)- In this embodiment, the aromatic polycarboxylic acid, its acid halide and / or ester (a1) (Q of the above general formula (1)) 11 and / or Q 12 The compound (a1) having a partial structure represented by the formula (1) is a carboxylic acid having two or more carboxyl groups or a derivative thereof, specifically a carboxylate, an acid halide, or an ester. The aromatic polycarboxylic acid (a1) and the monohydroxy aromatic compound (a2) described below (Ar in the formula (1)) are 11 and / or Ar 12 and a polyhydric alcohol compound (a3) ​​(a compound having a partial structure represented by A in the above general formula (1)) are used as reaction raw materials, and in the structure of the aromatic ester compound (A), a structural portion having flexibility derived from the polyhydric alcohol compound (a3) ​​(for example, A in the above general formula (1)) and an aromatic ring having high curability at the terminal (for example, Q in the above general formula (1)) are obtained. 11 and / or Q 12 and Ar 11 and / or Ar 12 ) (specifically, a polyaryloxycarbonyl structure) and an ester structure containing both, and therefore have high reactivity.

[0058] 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.

[0059] 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.

[0060] The valence (number) of the carboxyl groups in the aromatic polycarboxylic acids (a1) is preferably from divalent to tetravalent, and more preferably divalent.

[0061] 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.

[0062] Of the above-mentioned examples, from the viewpoints of flexibility of the obtained 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, terephthalic acid chloride, and the like. The aromatic polycarboxylic acids (a1) may be used alone or in combination of two or more.

[0063] -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.

[0064] -Polyhydric alcohol compound (a3)- In this embodiment, the polyhydric alcohol compound (a3) ​​is a compound having at least two hydroxyl groups and belongs to a group of compounds also called polyols. The hydroxyl equivalent of the polyhydric alcohol compound (a3) ​​in this embodiment must be less than 270 g / eq. The hydroxyl equivalent is preferably 31 g / eq or more and less than 270 g / eq, and more preferably 38 g / eq or more and less than 250 g / eq. A hydroxyl equivalent of less than 270 g / eq is excellent in terms of heat resistance of the cured product. The hydroxyl equivalent is a value measured in accordance with JIS K 0070. The valence (number) of the hydroxyl groups in the polyhydric alcohol compound (a3) ​​is preferably from divalent to hexavalent, and more preferably divalent.

[0065] The polyhydric alcohol compound (a3) ​​may or may not contain an aromatic ring. The optional polyhydric hydroxyaromatic 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 hydroxyaromatic compound (a4). The polyhydric alcohol compound (a3) ​​is preferably a compound having two or more hydroxyl groups and a linear or branched alkylene chain (divalent aliphatic hydrocarbon group) or a linear or branched alkylene ether chain (alkyleneoxy group), such as an aliphatic polyol compound (a3-1) or an oxyalkylene group-containing polyol compound (a3-2). The polyhydric alcohol compound (a3) ​​may be used alone or in combination of two or more kinds.

[0066] --Aliphatic polyol compound (a3-1)-- In this embodiment, the aliphatic polyol compound (a3-1) provides a cured product (curable resin composition) that has high flexibility, fracture toughness, and tensile strength, and is excellent in impregnation into substrates and reinforcing fibers. From the viewpoint of ease of control of the molecular weight distribution of the reaction product, the aliphatic polyol compound (a3-1) is preferably a diol compound containing two alcoholic hydroxyl groups, more preferably a linear aliphatic diol compound having 2 to 20 carbon atoms, more preferably a linear aliphatic diol compound having 4 to 18 carbon atoms, and even more preferably a linear aliphatic diol compound having 6 to 16 carbon atoms.

[0067] Examples of the aliphatic polyol compound (a3-1) include linear aliphatic diol compounds such as ethylene glycol (number average molecular weight: 62), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol; propylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-ethylbutane-14-butanediol, and 2,3-dimethyl-1,4-butanediol. Examples of branched chain aliphatic diol compounds include hexanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 3,3-dimethylpentane-1,5-diol, 2,2-diethyl-1,3-propanediol, 3-propylpentane-1,5-diol, 2,2-diethyl-1,4-butanediol, 2,4-diethyl-1,5-pentanediol, 2,2-dipropyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, and 2,5-diethyl-1,6-hexanediol; and tri- or higher functional aliphatic polyol compounds such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol. These aliphatic polyol compounds may be used alone or in combination of two or more.

[0068] --Oxyalkylene group-containing polyol compound (a3-2)-- In the present embodiment, the oxyalkylene group-containing polyol compound (a3-2) is preferably a diol compound having two alcoholic hydroxyl groups, more preferably a diol compound having a hydroxyl group equivalent of 50 to 269 g / eq, and even more preferably a diol compound having a hydroxyl group equivalent of 100 to 250 g / eq, because a cured product (curable resin composition) can be obtained that has high flexibility, fracture toughness, and tensile strength and is excellent in impregnation into substrates and reinforcing fibers. Examples of the oxyalkylene group-containing diol compound (a3-2) include ethylene oxide and propylene oxide adducts of glycols such as diethylene glycol and dipropylene glycol, and ethylene oxide and propylene oxide adducts of polyhydric phenol compounds such as ethylene oxide adducts of bisphenol A. These diol compounds may be used alone or in combination of two or more.

[0069] In this embodiment, the number average molecular weight (Mn) of the polyhydric alcohol compound (a3) ​​is preferably in the range of 62 to 1000, more preferably 62 to 500. A number average molecular weight within the above range is preferable because it improves workability. The number average molecular weight (Mn) of the polyhydric alcohol compound (a3) ​​is either the value published by the manufacturer or a value obtained by measuring by gel permeation chromatography (GPC) under the conditions described below. The polyhydric alcohol compound (a3) ​​may be commercially available, such as diethylene glycol manufactured by Mitsubishi Chemical Corporation and BPA-2 glycol manufactured by Nippon Nyukazai Co., Ltd.

[0070] - 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.

[0071] <Preferred Form of Aromatic Ester Compound (A)> The aromatic ester compound (A) of the present embodiment is represented by the following general formula (1): [ka] [In the above general formula (1), each A independently represents a linear or branched alkylene group, or a linear or branched alkylene ether group, Q 11 and Q 12 each independently represents a divalent aromatic group, Ar 11 and Ar 12 are each independently represented by the following general formula (2) or (3): [ka] [In the above general formula (2) and general formula (3), * represents Ar in the above general formula (1)] 11 or Ar 12 represents the bond to the oxygen atom that bonds to R 21 and R 31each independently represents a halogen atom, an alkyl group, an alkenyl group (such as an allyl group), an alkoxy group, an aryl group, or an aralkyl group; k 21 represents an integer from 0 to 7, and k 31 represents an integer of 0 to 5. p 11 represents an average number of repetitions of 0.01 or more.]

[0072] 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.

[0073] A more preferred example of the aromatic ester compound (A) of the present embodiment is represented by the above general formula (1), in which each A independently represents a linear or branched alkylene group (an alkylene group having 1 to 30 carbon atoms) or a linear or branched alkylene ether group (an alkylene ether group having 1 to 30 carbon atoms), and Q 11 and Q 12 each independently represents a 1,3-phenylene group or a 1,4-phenylene group; p 11 represents the average number of repetitions between 0.01 and 10, Ar 11 and Ar 12 each independently represents a structure represented by the 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 (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.] is preferably represented by.

[0074] 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.

[0075] <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).

[0076] 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).

[0077] In the resin composition having a polymerizable unsaturated group of this embodiment, by using an aromatic ester compound (A), a cured product having a low dielectric loss tangent and excellent linear expansion and elongation can be obtained, which is a preferred embodiment. The reason for this is not necessarily clear, but the aromatic ester compound (A) is preferably an aryloxycarbonyl group (for example, a partial structure represented by the general formula (i) above, more specifically, Q in the general formula (1) above). 11 and / or Q 12 and Ar 11 and / or Ar 12 Because the aromatic ester compound (a3) ​​contains an ester structure having the structure (a3) ​​at its terminal, it exhibits high reactivity with epoxy groups contained in the component (B) described below or a curing agent (e.g., an epoxy resin). This high reactivity can prevent or suppress, for example, the generation of hydroxyl groups resulting from the ring-opening of the epoxy group, which is a preferred embodiment. Furthermore, by using a polyhydric alcohol compound (a3) ​​having a flexible segment structure (e.g., A in the above general formula (1)), an alkylene chain (e.g., a divalent aliphatic hydrocarbon group) or an alkylene ether chain (oxyalkylene group) derived from the polyhydric alcohol compound (a3) ​​can be introduced into the structure of the resulting aromatic ester compound (A). This can impart flexibility to a cured product obtained using the aromatic ester compound (A). Furthermore, the introduction of a structure with low polarity results in excellent low dielectric properties, which is a preferred embodiment.

[0078] 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.

[0079] <Characteristics of aromatic ester compound (A)> When the total number of aromatic ester groups contained in the aromatic ester compound (A) is taken as the number of functional groups of the aromatic ester compound (A), the functional group equivalent of the aromatic ester compound (A) in this embodiment is preferably in the range of 160 to 1500 g / eq, more preferably in the range of 180 to 1200 g / eq, and even more preferably in the range of 200 to 660 g / eq, since this gives a cured product with excellent curability and a low dielectric constant and dielectric dissipation factor (low dielectric properties). The aromatic ester compound (A) of this embodiment preferably has a number average molecular weight (Mn) of 320 to 6000. A number average molecular weight (Mn) of 320 or more is preferable because it provides an excellent dielectric loss tangent. On the other hand, a number average molecular weight (Mn) of 6000 or less is preferable because it provides excellent moldability. From the same viewpoint, the number average molecular weight (Mn) of the aromatic ester compound (A) is more preferably 360 or more, even more preferably 400 or more, and more preferably 5600 or less, even more preferably 5200 or less. 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. 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) and adhesion to copper foil and the like due to a low linear expansion coefficient, 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, which use the curable resin composition.

[0080] <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.

[0081] 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.

[0082] 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.

[0083] 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 excellent solvent solubility, higher curability, or a well-balanced improvement in low linear expansion coefficient, dielectric properties, and elongation, 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.

[0084] 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').

[0085] 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).

[0086] 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. In the second reaction step, the same solvent as that used in the first reaction step can be used.

[0087] 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.

[0088] 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).

[0089] (Epoxy resin (B) having a polymerizable unsaturated group) The epoxy resin (B) having a polymerizable unsaturated group is one of the essential components of the resin composition having a polymerizable unsaturated group of this embodiment. The epoxy resin (B) having a polymerizable unsaturated group is a resin obtained from an epoxy resin (b1) and an unsaturated monobasic acid (b2) as essential reaction raw materials. Typically, the epoxy resin (B) having a polymerizable unsaturated group can be obtained by reacting the epoxy group of the epoxy resin (b1) with the acid group of the unsaturated monobasic acid (b2).

[0090] The epoxy resin (B) having a polymerizable unsaturated group preferably has an epoxy group and a (meth)acryloyl group. In this case, better elongation, linear expansion coefficient, and dielectric properties can be achieved. This can be achieved, for example, by appropriately adjusting the relative amounts of the epoxy resin (b1) and the unsaturated monobasic acid (b2) used so that the epoxy groups of the epoxy resin (b1) remain after the reaction.

[0091] The acid value of the epoxy resin (B) having a polymerizable unsaturated group can be, for example, 50 mgKOH / g or less, 30 mgKOH / g or less, 10 mgKOH / g or less, 5 mgKOH / g or less, or 1 mgKOH / g or less, where the acid value is a value measured by the neutralization titration method of JIS K 0070.

[0092] The reaction raw materials for the epoxy resin (B) having a polymerizable unsaturated group will be described below. <Epoxy resin (b1)> The specific structure of the epoxy resin (b1) is not particularly limited as long as it has a plurality of epoxy groups in the resin and is capable of reacting with the unsaturated monobasic acid (b2). Examples of the epoxy resin (b1) include bisphenol-type epoxy resins, biphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether epoxy resins, naphthalene-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, oxazolidone-type epoxy resins, and hydrogenated versions of these. Among these, as the epoxy resin (b1), from the viewpoint of improving elongation, linear expansion coefficient, and dielectric properties in a balanced manner, bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, biphenol-type epoxy resins, hydrogenated biphenol-type epoxy resins, naphthalene-type epoxy resins, and dihydroxybenzene-type epoxy resins are preferred, and bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, and naphthalene-type epoxy resins are more preferred. These epoxy resins (b1) may be used alone or in combination of two or more.

[0093] Examples of bisphenol type epoxy resins include bisphenol A type epoxy resins, bisphenol AP type epoxy resins, bisphenol B type epoxy resins, bisphenol BP type epoxy resins, bisphenol E type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins.

[0094] Examples of hydrogenated bisphenol epoxy resins include hydrogenated bisphenol A epoxy resins, hydrogenated bisphenol B epoxy resins, hydrogenated bisphenol E epoxy resins, hydrogenated bisphenol F epoxy resins, and hydrogenated bisphenol S epoxy resins.

[0095] Examples of biphenol type epoxy resins include 4,4'-biphenol type epoxy resins, 2,2'-biphenol type epoxy resins, tetramethyl-4,4'-biphenol type epoxy resins, and tetramethyl-2,2'-biphenol type epoxy resins.

[0096] Examples of hydrogenated biphenol type epoxy resins include hydrogenated 4,4'-biphenol type epoxy resins, hydrogenated 2,2'-biphenol type epoxy resins, hydrogenated tetramethyl-4,4'-biphenol type epoxy resins, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resins.

[0097] When the epoxy resin (b1) is any one of a bisphenol-type epoxy resin, a hydrogenated bisphenol-type epoxy resin, a biphenol-type epoxy resin, a hydrogenated biphenol-type epoxy resin, and a dihydroxybenzene-type epoxy resin, the epoxy equivalent of the epoxy resin (b1) is preferably in the range of 110 to 400 g / eq, from the viewpoint of obtaining a resin composition having a polymerizable unsaturated group that is excellent in heat resistance and dielectric properties.

[0098] <Unsaturated monobasic acid (b2)> The unsaturated monobasic acid (b2) refers to a compound having an acid group and a polymerizable unsaturated bond in one molecule. In this specification, the term "polymerizable unsaturated bond" refers to an unsaturated bond that can be radically polymerized. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Examples of the unsaturated monobasic acid (b2) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid, and their esters, acid halides, acid anhydrides, etc. Examples of the unsaturated monobasic acid (b2) include those 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 represents a hydrogen atom or a methyl group.] can also be used.

[0099] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain.

[0100] 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 each independently represents an alkylene group having 1 to 10 carbon atoms; q 51 represents an integer of 1 to 5.] is an example of a (poly)ester chain.

[0101] 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.

[0102] 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 q 61 represents an integer of 1 to 5.] is an example of a (poly)carbonate chain.

[0103] The molecular weight of the compound represented by the general formula (4) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400. These unsaturated monobasic acids (b2) may be used alone or in combination of two or more.

[0104] The amount of unsaturated monobasic acid (b2) used when obtaining epoxy resin (B) having a polymerizable unsaturated group is preferably in the range of 0.2 to 0.8 mol per mol of epoxy resin (b1), from the viewpoint that the obtained epoxy resin (B) having a polymerizable unsaturated group has an epoxy group and a (meth)acryloyl group and thus improves elongation, linear expansion coefficient, and dielectric properties in a balanced manner.

[0105] The molar ratio of acid groups in the unsaturated monobasic acid (b2) to 1 mole of epoxy groups in the epoxy resin (b1) is preferably in the range of 0.2 to 0.8. In this case, the resulting epoxy resin (B) having a polymerizable unsaturated group contains an epoxy group and a (meth)acryloyl group, and the elongation, linear expansion coefficient, and dielectric properties can be improved in a balanced manner.

[0106] The epoxy resin (B) having a polymerizable unsaturated group may be produced by any method without any particular limitation. For example, the epoxy resin (b1) and the unsaturated monobasic acid (b2) may be reacted all at once as reaction raw materials, or may be reacted sequentially as reaction raw materials. In particular, because the reaction can be easily controlled, the epoxy resin (b1) and the unsaturated monobasic acid (b2) are reacted in the presence of a basic catalyst at a temperature of 80 to 140°C, and then an acidic compound is added and mixed at a temperature of 50 to 100°C to deactivate the basic catalyst.

[0107] 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. Examples of suitable ammonium salts include 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. Alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides can also be used. These basic catalysts may be used alone or in combination of two or more.

[0108] The amount of the basic catalyst used is preferably in the range of 0.01 to 0.5 parts by mass, more preferably in the range of 0.01 to 0.4 parts by mass, per 100 parts by mass of the epoxy resin (b1) and the unsaturated monobasic acid (b2) in total, from the viewpoint of obtaining a resin composition having a polymerizable unsaturated group with a low linear expansion coefficient, excellent elongation, and dielectric properties.

[0109] The reaction between the epoxy resin (b1) and the unsaturated monobasic acid (b2) can also be carried out in an organic solvent, if necessary. Examples of organic solvents include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; 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; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; glycol ether solvents such as alkylene glycol monoalkyl ethers, dialkylene glycol monoalkyl ethers, and dialkylene glycol monoalkyl ether acetates; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents may be used alone or in combination. The amount of 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.

[0110] Examples of the acidic compound include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid; etc. These acidic compounds may be used alone or in combination of two or more.

[0111] In the reaction of the epoxy resin (b1) with the unsaturated monobasic acid (b2) in the presence of a basic catalyst, instead of the method of deactivating the basic catalyst with an acidic compound after the reaction, a method of separating and removing the basic catalyst may be used. The above are the essential components contained in the resin composition having a polymerizable unsaturated group of this embodiment.

[0112] (Optional addition ingredient) Furthermore, the resin composition having a polymerizable unsaturated group of the present embodiment may contain various known additives such as an ultraviolet stabilizer and a storage stabilizer in addition to the above-mentioned compounds or resins.

[0113] The method for producing the resin composition having 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.

[0114] [Curable resin composition] The curable resin composition of this embodiment is characterized by containing at least the resin composition having 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 epoxy resin (B) having a polymerizable unsaturated group described above, and a photopolymerization initiator. The photopolymerization initiator may be used alone or in combination of two or more.

[0115] (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.

[0116] 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.

[0117] 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).

[0118] 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 epoxy resin (B) having a polymerizable unsaturated group.

[0119] ((Meth)acrylate Monomer) Furthermore, the curable resin composition of the present embodiment preferably further contains a (meth)acrylate monomer ((meth)acrylate compound) in addition to the aromatic ester compound (A) and the epoxy resin (B) having a polymerizable unsaturated group, which can improve the low linear expansion coefficient, dielectric properties, and elongation in a well-balanced manner.

[0120] Specific examples of the (meth)acrylate monomer include aliphatic mono(meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl mono(meth)acrylate; glycerol mono(meth)acrylate compounds such as glycerol mono(meth)acrylate, glycerol mono(meth)acrylate, and glycerol mono(meth)acrylate; and glycerol mono(meth)acrylate compounds such as glycerol mono(meth)acrylate, glycerol mono(meth)acrylate, and glycerol mono(meth)acrylate. Heterocyclic mono(meth)acrylate compounds such as diethyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzyl benzyl (meth)acrylate, phenylphenoxyethyl (meth)acrylate Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as acrylates: (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene 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 above-mentioned various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; ethylene glycol di(meth)acrylate aliphatic di(meth)acrylate compounds such as methyl acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate; alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate;Aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; polyoxyalkylene-modified di(meth)acrylate 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 above-mentioned various di(meth)acrylate compounds; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; (poly)oxyalkylene chains in which a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned aliphatic tri(meth)acrylate compounds Examples of suitable poly(meth)acrylate compounds include alkylene-modified tri(meth)acrylate compounds; lactone-modified tri(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; tetrafunctional or higher aliphatic poly(meth)acrylate compounds such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; tetrafunctional or higher (poly)oxyalkylene-modified poly(meth)acrylate 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 aliphatic poly(meth)acrylate compounds; and tetrafunctional or higher lactone-modified poly(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compounds. The (meth)acrylate monomers may be used alone or in combination of two or more.

[0121] The content of the (meth)acrylate monomer is preferably 10 parts by mass or more and 500 parts by mass or less per 100 parts by mass of the total of the aromatic ester compound (A) and the epoxy resin (B) having a polymerizable unsaturated group.

[0122] (Other various additives) The curable resin composition of the present embodiment may contain appropriate amounts of various additives, such as other curing agents, curing accelerators, organic solvents, flame retardants, fillers, pigments, antifoaming agents, viscosity modifiers, leveling agents, storage stabilizers, etc., as needed, within the scope of the purpose. However, it is preferable that the curable resin composition of the present embodiment does not contain an organic solvent.

[0123] <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.

[0124] 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.

[0125] 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 resulting cured product will have better dielectric properties, which is preferable, while if the epoxy equivalent of the epoxy resin is 400 g / eq or less, the resulting cured product will have a good balance of low linear expansion coefficient, dielectric properties, and elongation, which is preferable.

[0126] The softening point of the epoxy resin is preferably 20 to 200°C, more preferably 40 to 150°C, from the viewpoint of achieving a low linear expansion coefficient, dielectric properties, and elongation in a well-balanced manner. The softening point of the epoxy resin is preferably 20°C or higher, since it can also have fast curing properties. On the other hand, the softening point of the epoxy resin is preferably 200°C or lower, since it has excellent moldability.

[0127] With regard to the amount of epoxy resin used, when the ester group in the aromatic ester compound (A) is considered to be the functional group, the functional group equivalent ratio of the aromatic ester compound (A) to the amount of epoxy resin used (aromatic ester compound (A) / epoxy resin) is preferably 0.2 to 2, more preferably 0.4 to 1.5. A functional group equivalent ratio of 0.2 or more is preferred because the resulting cured product can have a lower dielectric tangent and higher flexibility. If the functional group equivalent ratio exceeds 2, heat resistance and curability decrease, so it is preferable to use within the above range.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] With regard to the amount of other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents) used, when the ester groups in the aromatic ester compound (A) are considered functional groups, the functional group equivalent ratio (aromatic ester compound (A) / other curing agents) to the amount of the 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. If the functional group equivalent ratio exceeds 2, heat resistance and curability decrease, so it is preferable to use within the above range.

[0132] <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.

[0133] 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.

[0134] 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).

[0135] 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.

[0136] 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.

[0137] 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.

[0138] Of the above-mentioned curing accelerators, it is preferable to use 2-ethyl-4-methylimidazole and N,N-dimethyl-4-aminopyridine (DMAP).

[0139] 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 sufficiently maintained. From the same viewpoint, the content of the curing accelerator is more preferably 0.1 part by mass or more, and more preferably 3 parts by mass or less, relative to 100 parts by mass of the combined total of the (A) and (B) components.

[0140] <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. 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. 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.

[0141] 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.

[0142] 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).

[0143] <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.

[0144] The organic filler is not particularly limited, but examples thereof include polyamide particles. The inorganic filler is not particularly limited, but may include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black, etc. Among these, silica is preferably used. In this case, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. may be used as the silica.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] [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 that is excellent in low dielectric properties, elongation, and low linear expansion.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] [Goods] The article of the present embodiment is characterized by having a coating film made of the above-described cured product. In such an article of the present embodiment, the coating film can function as an insulating material that is excellent in low dielectric properties, elongation, and low linear expansion.

[0154] The article of this embodiment is typically a printed wiring board or a substrate for a semiconductor package, having a solder resist film (the coating film) formed in appropriate positions on the surface layer. [Example]

[0155] 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. In the examples, the instruments and conditions used to measure various properties are as follows:

[0156] . (GPC measurement) Measurements were performed using the following measuring equipment and under the following conditions to obtain GPC charts for the diphenyl isophthalate derivatives, aromatic ester compounds, and epoxy resins having polymerizable unsaturated groups 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, aromatic ester compounds (A), and epoxy resins having polymerizable unsaturated groups (B)) were produced, based on the decrease and disappearance of the raw material peaks. Measurement equipment: 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 "F-80" manufactured by Tosoh Corporation Tosoh Corporation "F-128" Sample: A tetrahydrofuran solution (50 μl) containing 1.0 mass % of the diphenyl isophthalate derivatives obtained in the Synthesis Examples and Examples, the aromatic ester compound (A), and the epoxy resin (B) having a polymerizable unsaturated group, calculated as a solid content, was filtered through a microfilter and used.

[0157] (Tensile test measurement) Manufacturer: Shimadzu Corporation Measuring equipment: Precision universal testing machine Autograph AG-IS Measurement conditions: temperature 23℃, humidity 50%, distance between gauge lines 20mm, distance between fulcrums 20mm, test speed 10mm / min Sample size: 10 x 80 mm

[0158] (Cavity resonance method (measurement of dielectric constant and dielectric loss tangent)) Manufacturer:Agilent Technologies Measurement equipment: 4291B RF Impedance Material Analyzer, 16453A Frequency condition: 1GHz

[0159] (Synthesis Example 1): Synthesis of diphenyl isophthalate derivative (a'-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 808.0 parts by mass of isophthalic acid chloride (4.0 moles of acid chloride groups) as component (a1) and 4140.0 parts by mass of toluene. The system was then purged with nitrogen under reduced pressure and dissolved. Next, 864.0 parts by mass (8.0 moles) of o-cresol (a2) was charged and the system was purged with nitrogen and dissolved. Then, 2.07 parts by mass of tetrabutylammonium bromide was dissolved. While purging with nitrogen gas, the system was controlled to 60°C or below, and 1648.0 parts by mass of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1 hour. After the reaction was completed, the mixture was allowed to stand for separation, and the aqueous layer was removed. Water was then added to the toluene layer containing the dissolved reactant, and the mixture was stirred and mixed for approximately 15 minutes. The mixture was then allowed to stand for separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water and toluene were removed by decanting, and a crystalline compound (intermediate product (a')), a diphenyl isophthalate derivative (a'-1), was obtained.

[0160] (Synthesis Example 2): Synthesis of diphenyl isophthalate derivative (a'-2) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 142.1 parts by mass of isophthalic acid chloride (0.7 moles of acid chloride groups) as component (a1) and 954.0 parts by mass of toluene. The system was then purged with nitrogen under reduced pressure and dissolved. Next, 188.0 parts by mass (1.4 moles) of phenol (a2) was charged and the system was purged with nitrogen under reduced pressure and dissolved. Then, 0.33 parts by mass of tetrabutylammonium bromide was dissolved. While purging with nitrogen gas, the system was controlled to below 60°C, and 288.4 parts by mass of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1 hour. After the reaction was completed, the mixture was allowed to stand for separation, and the aqueous layer was removed. Water was then added to the toluene layer containing the dissolved reactant, and the mixture was stirred and mixed for approximately 15 minutes. The mixture was then allowed to stand for separation, and the aqueous layer was removed. This procedure was repeated until the pH of the aqueous layer reached 7. Thereafter, water and toluene were removed by decanting, and a crystalline compound (intermediate product (a')), a diphenyl isophthalate derivative (a'-2), was obtained.

[0161] (Synthesis Example 3): Synthesis of diphenyl isophthalate derivative (a'-3) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 142.1 parts by mass of isophthalic acid chloride (0.7 moles of acid chloride groups) as component (a1) and 903.0 parts by mass of toluene. The system was then purged with nitrogen under reduced pressure and dissolved. Next, 210.0 parts by mass (1.4 moles) of p-tert-butylphenol (PTBP) as component (a2) was charged and the system was purged with nitrogen under reduced pressure and dissolved. Then, 0.45 parts by mass of tetrabutylammonium bromide was dissolved. While purging with nitrogen gas, the system was controlled to 60°C or below, and 288.4 parts by mass of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued under these conditions for 1 hour. After the reaction was completed, the mixture was allowed to stand for separation, and the aqueous layer was removed. Water was then added to the toluene layer containing the dissolved reactant, and the mixture was stirred and mixed for approximately 15 minutes. The mixture was then allowed to stand for separation, and the aqueous layer was removed. This procedure was repeated until the pH of the aqueous layer reached 7. Water and toluene were then removed by decanting, yielding a crystalline compound (intermediate product (a')), a diphenyl isophthalate derivative (a'-3).

[0162] (Synthesis Example 4): Synthesis of aromatic ester compound (A-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 30.0 g of 1,9-nonanediol (hydroxyl group equivalent: 80 g / eq) as component (a3), 129.68 g of the isophthalic acid diphenyl derivative (a'-1) obtained in Synthesis Example 1, and 0.80 g of 1,8-diazabicyclo[5,4,0]-undecene-7 (hereinafter abbreviated as "DBU"), and the temperature was raised to 190°C, followed by stirring until the reaction was complete. The completion of the reaction was confirmed by GPC. Then, o-cresol was removed by vacuum distillation to obtain aromatic ester compound (A-1). The functional group equivalent and average repeat number p of the obtained aromatic ester compound (A-1) were measured. 11 (See formula (1.1) below) are 319 g / eq and p 11 =1. [ka] The average repeating number p in the aromatic ester compound (A-1) of the above formula (1.1) 11 was calculated from the feed ratio based on the following formula. (The average repeat number p in the obtained aromatic ester (A) 11 ) = (number of moles of hydroxyl groups in polyhydric alcohol compound (a3)) / [(number of moles of aromatic ester groups in intermediate product (a') used as raw material) - (number of moles of hydroxyl groups in polyhydric alcohol compound (a3)]

[0163] (Synthesis Example 5): Synthesis of aromatic ester compound (A-2) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 30.0 parts by mass of 1,9-nonanediol (hydroxyl group equivalent: 80 g / eq) as component (a3), 119.18 parts by mass of the isophthalic acid diphenyl derivative (a'-2) obtained in Synthesis Example 2, and 0.75 parts by mass of DBU. The system was purged with nitrogen under reduced pressure, and then heated to 190°C and stirred until the reaction was complete. The completion of the reaction was confirmed by GPC. Thereafter, phenol was removed by distillation under reduced pressure to obtain aromatic ester compound (A-2). The functional group equivalent and average repeat number p of the obtained aromatic ester compound (A-2) were 11 From the feed ratio, 306g / eq and p 11 =1.

[0164] (Synthesis Example 6): Synthesis of aromatic ester compound (A-3) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 8.5 parts by mass of 1,9-nonanediol (hydroxyl group equivalent: 80 g / eq) as component (a3), 45.67 parts by mass of the isophthalic acid diphenyl derivative (a'-3) obtained in Synthesis Example 3, and 0.27 parts by mass of DBU. The system was then purged with nitrogen under reduced pressure, and the temperature was raised to 190°C, followed by stirring until the reaction was complete. The completion of the reaction was confirmed by GPC. PTBP was then removed by distillation under reduced pressure to obtain aromatic ester compound (A-3). The functional group equivalent and average repeat number p of the obtained aromatic ester compound (A-3) were measured. 11 From the feed ratio, 363g / eq and p 11 =1.

[0165] (Synthesis Example 7): Synthesis of aromatic ester compound (A-4) The same procedure as in Example 1 was carried out to obtain an aromatic ester compound (A-4), except that in Example 1, 1,9-nonanediol as component (a3) ​​was replaced with 30.0 parts by mass of 1,6-hexanediol (hydroxyl group equivalent: 59 g / eq), the amount of isophthalic acid diphenyl derivative (a'-1) was changed from 129.68 parts by mass to 175.86 parts by mass, and DBU was changed from 0.80 parts by mass to 1.03 parts by mass. The functional group equivalent and average repeat number p of the obtained aromatic ester compound (A-4) were11 From the feed ratio, 299g / eq and p 11 =1.

[0166] (Synthesis Example 8): Synthesis of aromatic ester compound (A-5) The same procedure as in Example 1 was carried out to obtain an aromatic ester compound (A-5), except that in Example 1, 1,9-nonanediol as component (a3) ​​was replaced with 40.0 parts by mass of 1,12-dodecanediol (hydroxyl group equivalent: 101 g / eq), the amount of isophthalic acid diphenyl derivative (a'-1) was changed from 129.68 parts by mass to 136.95 parts by mass, and DBU was changed from 0.80 parts by mass to 0.88 parts by mass. The functional group equivalent weight and average repeat number p of the obtained aromatic ester compound (A-5) were 11 From the feed ratio, 342g / eq and p 11 =1.

[0167] (Synthesis Example 9: Production of epoxy resin (B-1) having polymerizable unsaturated groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 346 parts by mass of bisphenol A epoxy resin (epoxy resin (b1)) (DIC Corporation, "EPICLON 850CRP," epoxy equivalent 173 g / eq; hereafter abbreviated as "bisphenol A epoxy resin (1)"), and 0.21 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.21 parts by mass of methoquinone as a thermal polymerization inhibitor were added. Then, 72 parts by mass of acrylic acid (unsaturated monobasic acid (b2)) and 0.21 parts by mass of triphenylphosphine were added. The esterification reaction was carried out at 100 °C for 10 hours while blowing air into the mixture. After confirming that the acid value was 1 mg KOH / g or less, 0.21 parts by mass of oxalic acid was added and the mixture was stirred at 70 °C for 3 hours to obtain an epoxy resin (epoxy acrylate resin) (B-1) having polymerizable unsaturated groups. The epoxy equivalent of this epoxy acrylate resin (B-1) was 450 g / eq. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the bisphenol A epoxy resin (1) was 0.5.

[0168] (Synthesis Example 10: Production of epoxy resin (B-2) having polymerizable unsaturated groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 346 parts by weight of bisphenol A epoxy resin (1) as the epoxy resin (b1), 0.18 parts by weight of dibutylhydroxytoluene as an antioxidant, and 0.18 parts by weight of methoquinone as a thermal polymerization inhibitor. Then, 22 parts by weight of acrylic acid as the unsaturated monobasic acid (b2) and 0.18 parts by weight of triphenylphosphine were added, and the esterification reaction was carried out at 100 °C for 5 hours while blowing air into the mixture. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.18 parts by weight of oxalic acid was added, and the mixture was stirred at 70 °C for 3 hours to obtain an epoxy resin (epoxy acrylate resin) (B-2) having polymerizable unsaturated groups. The epoxy equivalent of this epoxy acrylate resin (B-2) was 241 g / eq. The ratio of moles of acid groups in the acrylic acid to 1 mole of epoxy groups in the bisphenol A epoxy resin (1) was 0.15.

[0169] (Synthesis Example 11: Production of epoxy resin (B-3) having polymerizable unsaturated groups) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 346 parts by weight of bisphenol A epoxy resin (1) as the epoxy resin (b1), 0.19 parts by weight of dibutylhydroxytoluene as an antioxidant, and 0.19 parts by weight of methoquinone as a thermal polymerization inhibitor. Then, 43 parts by weight of acrylic acid as the unsaturated monobasic acid (b2) and 0.19 parts by weight of triphenylphosphine were added, and the esterification reaction was carried out at 100 °C for 8 hours while blowing air into the mixture. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.19 parts by weight of oxalic acid was added, and the mixture was stirred at 70 °C for 3 hours to obtain an epoxy resin (epoxy acrylate resin) (B-3) having polymerizable unsaturated groups. The epoxy equivalent of this epoxy acrylate resin (B-3) was 301 g / eq. The ratio of moles of acid groups in the acrylic acid to 1 mole of epoxy groups in the bisphenol A epoxy resin (1) was 0.3.

[0170] (Synthesis Example 12: Production of epoxy resin (B-4) having polymerizable unsaturated group) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 346 parts by weight of bisphenol A epoxy resin (1) as the epoxy resin (b1), 0.22 parts by weight of dibutylhydroxytoluene as an antioxidant, and 0.22 parts by weight of methoquinone as a thermal polymerization inhibitor. Then, 101 parts by weight of acrylic acid as the unsaturated monobasic acid (b2) and 0.44 parts by weight of triphenylphosphine were added, and the esterification reaction was carried out at 100 °C for 10 hours while blowing air into the mixture. Next, after confirming that the acid value was 1 mg KOH / g or less, 0.22 parts by weight of oxalic acid was added, and the mixture was stirred at 70 °C for 3 hours to obtain an epoxy resin (epoxy acrylate resin) (B-4) having polymerizable unsaturated groups. The epoxy equivalent of this epoxy acrylate resin (B-4) was 785 g / eq. The ratio of moles of acid groups in the acrylic acid to 1 mole of epoxy groups in the bisphenol A epoxy resin (1) was 0.7.

[0171] (Synthesis Example 13: Production of epoxy resin (B-5) having polymerizable unsaturated group) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 346 parts by weight of bisphenol A epoxy resin (1) as the epoxy resin (b1), 0.23 parts by weight of dibutylhydroxytoluene as an antioxidant, and 0.23 parts by weight of methoquinone as a thermal polymerization inhibitor. Then, 122 parts by weight of acrylic acid as the unsaturated monobasic acid (b2) and 0.46 parts by weight of triphenylphosphine were added, and the esterification reaction was carried out at 100 °C for 20 hours while blowing air into the mixture. After confirming that the acid value was 1 mg KOH / g or less, 0.23 parts by weight of oxalic acid was added and the mixture was stirred at 70 °C for 3 hours to obtain an epoxy resin (epoxy acrylate resin) (B-5) having polymerizable unsaturated groups. The epoxy equivalent of this epoxy acrylate resin (B-5) was 1603 g / eq. The ratio of moles of acid groups in acrylic acid to 1 mole of epoxy groups in bisphenol A epoxy resin (1) was 0.85.

[0172] (Synthesis Example 14: Production of epoxy resin (B-6) having polymerizable unsaturated group) A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 282 parts by mass of a naphthalene-type epoxy resin (epoxy resin (b1)) (DIC Corporation, "EPICLON 4032D," epoxy equivalent 141 g / eq; hereafter abbreviated as "naphthalene-type epoxy resin (1)"), and 0.18 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.18 parts by mass of methoquinone as a thermal polymerization inhibitor were added. Then, 72 parts by mass of acrylic acid (unsaturated monobasic acid (b2)) and 0.18 parts by mass of triphenylphosphine were added. The esterification reaction was carried out at 100 °C for 10 hours while blowing air into the mixture. After confirming that the acid value was 1 mg KOH / g or less, 0.18 parts by mass of oxalic acid was added and the mixture was stirred at 70 °C for 3 hours to obtain an epoxy resin (epoxy acrylate resin) (B-6) having polymerizable unsaturated groups. The epoxy equivalent of this epoxy acrylate resin (B-6) was 388 g / eq. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the naphthalene-type epoxy resin (1) was 0.50.

[0173] (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 mass (0.5 mol) of diglycidyl ether of 1,6-hexanediol (manufactured by DIC Corporation: product name: SR-16HL, epoxy equivalent: 127 g / eq) and 228 parts by mass (1.0 mol) of bisphenol A (hydroxyl equivalent: 114 g / eq). The mixture was heated to 140°C over 30 minutes. Next, 1.8 parts by mass 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 mixture was then allowed to react 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.

[0174] (Comparative Synthesis Example 2): Synthesis of aromatic ester compound (C-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 300 parts by 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 vacuum dehydration to remove the MIBK, yielding an aromatic ester compound (C-1). The functional group equivalent of the resulting aromatic ester (C-1) was 404 g / eq based on the charge ratio.

[0175] (Example 1: Preparation of curable resin composition (1)) 20 parts by mass of the aromatic ester compound (A-1) obtained in Synthesis Example 4, 80 parts by mass of the epoxy resin (B-1) having a polymerizable unsaturated group obtained in Synthesis Example 9, 2 parts by mass of a photopolymerization initiator ("Omnirad 907" manufactured by IGM Resins), 1.6 parts by mass of 2-ethyl-4-methylimidazole, and 0.4 parts by mass of 4-dimethylaminopyridine were mixed to obtain a curable resin composition (1).

[0176] (Examples 2 to 15: Preparation of curable resin compositions (2) to (15)) Curable resin compositions (2) to (15) were obtained using the blending ratios shown in Table 1 in the same manner as in Example 1.

[0177] (Comparative Example 1: Preparation of curable resin composition (C1)) 20 parts by mass of the aromatic ester compound (C-1) obtained in Comparative Synthesis Example 2, 80 parts by mass of the epoxy resin (B-1) having a polymerizable unsaturated group obtained in Synthesis Example 9, 2 parts by mass of a photopolymerization initiator ("Omnirad 907" manufactured by IGM Resins), 1.6 parts by mass of 2-ethyl-4-methylimidazole, and 0.4 parts by mass of 4-dimethylaminopyridine were mixed to obtain a curable resin composition (C1).

[0178] The following evaluations were carried out using the curable resin compositions (1) to (15), (C1) and (C2) obtained in the above examples and comparative examples.

[0179] [Method for measuring linear expansion coefficient] The curable resin compositions (1) to (15), (C1) and (C2) obtained in the above Examples and Comparative Examples were applied to an electrodeposited copper foil "F2-WS" manufactured by Furukawa Sangyo Kaisha, Ltd. using an applicator to a thickness of 50 μm, and dried at 80° C. for 30 minutes. Next, the dried coating film was irradiated with 10 kJ / m 2 of a metal halide lamp. 2 After irradiating the laminate with ultraviolet light, the coating was cured at 160°C for 1 hour. The resulting laminate was cut into a 20mm x 5mm size specimen. The specimen was subjected to thermomechanical analysis in tension mode under a nitrogen atmosphere using a thermomechanical analyzer (TMA: "TMA-60" manufactured by Shimadzu Corporation) under the following measurement conditions: Measurement conditions Measurement load: 6mN Heating rate: 10°C / min twice Measurement temperature range: 1st time: 0℃ to 220℃, 2nd time: -60℃ to 240℃ The measurement under the above conditions was carried out twice for the same sample, and the average linear expansion coefficient in the temperature range of 40°C to 60°C in the second measurement was evaluated as the linear expansion coefficient.

[0180] [Method for measuring elongation] The elongation was measured based on a tensile test. Specifically, the curable resin compositions obtained in the examples and comparative examples were applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Kaisha, Ltd.) using a 50 μm applicator, and the curable resin compositions were applied to a copper foil using a metal halide lamp at 10 kJ / m 2 After irradiating the specimen with ultraviolet light, it was heated at 160°C for 1 hour. The cured product was peeled off from the copper foil to obtain Test Piece 1 (cured product). Test Piece 1 (cured product) was then cut into a size of 10 mm x 80 mm, and a tensile test was performed on Test Piece 1 using a precision universal testing machine, Autograph "AG-IS," manufactured by Shimadzu Corporation, under the following measurement conditions. The elongation (%) until the test piece broke was measured. Measurement conditions: temperature 23℃, humidity 50%, distance between gauge lines 20mm, distance between fulcrums 20mm, tensile speed 10mm / min

[0181] [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.

[0182] [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 2After 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.

[0183] Table 1 shows the compositions and evaluation results of the curable resin compositions (1) to (15) obtained in Examples 1 to 15 and the curable resin composition (C1) obtained in Comparative Example 1.

[0184] [Table 1]

[0185] From the results in Table 1, it can be seen that the resin compositions of the examples have a lower linear expansion coefficient than the comparative examples, and are well balanced in terms of dielectric properties and elongation. [Industrial Applicability]

[0186] The present disclosure aims to provide a resin composition that can be used to obtain an insulating material having a low linear expansion coefficient and excellent dielectric properties and elongation. The present invention also provides a curable resin composition containing the resin composition, a cured product thereof, and an article using the cured product.

Claims

1. A resin composition having a polymerizable unsaturated group, comprising an aromatic ester compound (A) and an epoxy resin (B) having a polymerizable unsaturated group, the aromatic ester compound (A) is a compound obtained by reacting an aromatic polycarboxylic acid, an acid halide thereof and / or an ester thereof (a1), a monohydroxyaromatic compound (a2), and a polyhydric alcohol compound (a3) ​​as essential reaction raw materials; the polyhydric alcohol compound (a3) ​​is a linear aliphatic diol compound having 6 to 16 carbon atoms, the hydroxyl group equivalent of the polyhydric alcohol compound (a3) ​​is less than 270 g / eq; the epoxy resin (B) having a polymerizable unsaturated group is a resin containing an epoxy resin (b1) and an unsaturated monobasic acid (b2) as essential reaction raw materials, and is a resin having an epoxy group and a (meth)acryloyl group; A resin composition having 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 a polymerizable unsaturated group according to claim 1 , wherein the formula (I) is an average repeat number of 0.01 or more.

3. Ar in the general formula (1) １１ and Ar １２ are each independently represented by the following general formula (2) or (3): 【Chemistry 2】 [In the above general formula (2) and general formula (3), * represents Ar in the above general formula (1)] １１ or Ar １２ represents the bond to the oxygen atom that bonds to R ２１ and R ３１ each independently represents a halogen atom, an alkyl group, an 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 a polymerizable unsaturated group according to claim 2,

4. The resin composition having a polymerizable unsaturated group according to any one of claims 1 to 3, wherein the number of moles of acid groups in the unsaturated monobasic acid (b2) relative to 1 mole of epoxy groups in the epoxy resin (b1) is in the range of 0.25 to 0.

75.

5. 5. The resin composition having a polymerizable unsaturated group according to claim 1, wherein a mass ratio of solid contents of the aromatic ester compound (A) to the epoxy resin (B) having a polymerizable unsaturated group, [(A) / (B)], is in the range of 10 / 90 to 90 / 10.

6. A curable resin composition comprising the resin composition having a polymerizable unsaturated group according to any one of claims 1 to 5 and a photopolymerization initiator.

7. The curable resin composition according to claim 6 , further comprising a (meth)acrylate monomer.

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

9. An article having a coating film comprising the cured product according to claim 8.

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