Resin composition, curable composition, cured product, insulating material, and resist member

Abstract

To provide a resin composition capable of improving elongation, adhesion and low dielectric characteristics of a cured product obtained therefrom in a well-balanced manner, and to provide a cured product, an insulating material, and a resist member.SOLUTION: The present disclosure is the resin composition containing: a phosphorus-containing active ester which uses an aromatic compound having two or more carboxyl groups and / or an acid halide or esterified product thereof (A), an aromatic monoalcohol (B), a phosphorus-containing polyhydric alcohol compound (C), and an ether bond-containing aliphatic compound (D) as reaction raw materials; and a resin having an acid group and a polymerizable unsaturated group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a resin composition, a curable composition, a cured product, an insulating material, and a resist member. [Background technology]

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

[0003] [Patent Document 1] Patent No. 6094271 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-169021 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the techniques of Patent Documents 1 and 2 do not consider the elongation and adhesion of the cured product formed from the photosensitive resin composition. Therefore, the present disclosure provides a resin composition that can improve elongation, adhesion, and low dielectric properties in a well-balanced manner in the resulting cured product, a curable composition containing the resin composition, and a resin composition, a curable composition, a cured product, an insulating material, and a resist member that are obtained using the curable composition. [Means for solving the problem]

[0005] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that by using a composition containing a specific phosphorus-containing active ester and a resin having an acid group and a polymerizable unsaturated group, it is possible to improve the elongation, adhesion, and low dielectric properties of the resulting cured product in a balanced manner, thereby completing the present invention.

[0006] The resin composition of the present disclosure contains a phosphorus-containing active ester obtained from reaction raw materials including an aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A), an aromatic monoalcohol (B), a phosphorus-containing polyhydric alcohol aromatic compound (C), and an ether bond-containing aliphatic compound (D), and a resin having an acid group and a polymerizable unsaturated group. [Effects of the Invention]

[0007] According to the present disclosure, it is possible to provide a resin composition that has excellent adhesion and that can give a cured product that is excellent in dielectric properties and elongation. Furthermore, according to the present disclosure, it is possible to provide a curable composition containing such a resin composition, a cured product thereof, and an insulating material and a resist material using such a cured product. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a GPC chart of the diphenyl isophthalate derivative (1) obtained in Synthesis Example 1. [Figure 2] 1 is a 1H-NMR chart of the diphenyl isophthalate derivative (1) obtained in Synthesis Example 1. [Figure 3] 1 is an FD-MS spectrum chart of the diphenyl isophthalate derivative (1) obtained in Synthesis Example 1. [Figure 4] 1 is a GPC chart of the phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) obtained in Synthesis Example 2. [Figure 5] 1 is a 13C-NMR chart of the phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) obtained in Synthesis Example 2. [Figure 6] 1 is an FD-MS spectrum chart of the phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) obtained in Synthesis Example 2. [Figure 7] 1 is a GPC chart of the phosphorus-containing active ester (1) obtained in Synthesis Example 3. [Figure 8] 1 is a C-NMR chart of the phosphorus-containing active ester (1) obtained in Synthesis Example 3. [Figure 9] 1 is an FD-MS spectrum chart of the phosphorus-containing active ester (1) obtained in Synthesis Example 3. [Figure 10] 1 is a GPC chart of the phosphorus-containing polyhydric alcohol compound (EC-HCA-HQ) obtained in Synthesis Example 4. [Figure 11] 1 is a GPC chart of the phosphorus-containing active ester (2) obtained in Synthesis Example 5. [Figure 12]1 is a GPC chart of the phosphorus-containing polyhydric alcohol compound (PC-HCA-NQ) obtained in Synthesis Example 6. [Figure 13] 1 is a GPC chart of the phosphorus-containing active ester (3) obtained in Synthesis Example 7. [Figure 14] 1 is a GPC chart of the phosphorus-containing polyhydric alcohol compound (PC-PPQ) obtained in Synthesis Example 8. [Figure 15] 1 is a GPC chart of the phosphorus-containing active ester (4) obtained in Synthesis Example 9. [Figure 16] 1 is a GPC chart of the comparative intermediate (1) obtained in Comparative Synthesis Example 1. [Figure 17] 1 is a GPC chart of the phosphorus atom-containing compound (1) obtained in Comparative Synthesis Example 2. [Figure 18] 1 is a GPC chart of the phosphorus atom-containing ester compound (1) obtained in Comparative Synthesis Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0009] Below, we will explain in detail the embodiment of the present disclosure (hereinafter referred to as the "present embodiment"), but the present disclosure is not limited to the description below and can be implemented in various modifications within the scope of its gist.

[0010] [Resin composition] The present disclosure relates to a resin composition containing a phosphorus-containing active ester and a resin having an acid group and a polymerizable unsaturated group. The phosphorus-containing active ester is a compound obtained by reacting, as essential raw materials, an aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A), an aromatic monoalcohol (B), a phosphorus-containing polyhydric alcohol compound (C), and an ether bond-containing aliphatic compound (D). This makes it possible to form a cured product with a good balance of improved elongation, adhesion, and low dielectric properties.

[0011] In the resin composition of the present disclosure, the content of the phosphorus-containing active ester is preferably in the range of 90 to 10 mass% relative to the total amount (100 mass%) of the resin composition, from the viewpoint of improving elongation, adhesion, and low dielectric properties in a balanced manner. The upper or lower limit of the content of the phosphorus-containing active ester is preferably 10 mass% or more, more preferably 20 mass% or more, and even more preferably 30 mass% or more, and is preferably 90 mass% or less, more preferably 80 mass% or less, and even more preferably 70 mass% or less. In the resin composition of the present disclosure, the content of the resin having an acid group and a polymerizable unsaturated group is preferably in the range of 90 to 10% by mass relative to the total amount (100% by mass) of the resin composition. The upper or lower limit of the content of the resin having an acid group and a polymerizable unsaturated group is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0012] In the resin composition of this embodiment, the mass ratio of the solid content of the phosphorus-containing active ester to the resin having an acid group and a polymerizable unsaturated group [(phosphorus-containing active ester) / (resin having an acid group and a polymerizable unsaturated group)] is preferably in the range of 5 / 95 to 50 / 50 from the viewpoint of improving elongation, adhesion, and low dielectric properties in a balanced manner. From the same viewpoint, the upper or lower limit of the mass ratio [(phosphorus-containing active ester) / (resin having an acid group and a polymerizable unsaturated group)] is more preferably 10 / 90 or more, even more preferably 20 / 80 or more, and more preferably 40 / 60 or less.

[0013] The resin composition in the present embodiment may further contain an optional additive component as an optional component. The resin composition of the present embodiment may be substantially composed of only the phosphorus-containing active ester, the resin having an acid group and a polymerizable unsaturated group, and any additional components.Furthermore, the resin composition of the present embodiment may be composed of only the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group. The total content of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group in the total amount (100% by mass) of the resin composition of this embodiment is preferably 40% by mass or more, more preferably 50% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, from the viewpoint of improving elongation, adhesion, and low dielectric properties in a balanced manner. The above phrase "consisting only of a phosphorus-containing active ester, a resin having an acid group and a polymerizable unsaturated group, and optional additional components" means that, relative to the total amount (100% by mass) of the resin composition, preferably 80 to 100% by mass, or at least 90 to 95% by mass, is the phosphorus-containing active ester, the resin having an acid group and a polymerizable unsaturated group, or is the phosphorus-containing active ester, the resin having an acid group and a polymerizable unsaturated group, and optional additional components. The resin composition of the present embodiment may contain inevitable impurities in addition to the phosphorus-containing active ester, the resin having an acid group and a polymerizable unsaturated group, and any optional added components, as long as the effects of the present disclosure are not impaired. Hereinafter, the main terms used in this specification will be explained, followed by a description of the components contained in the resin composition of this embodiment, namely, the phosphorus-containing active ester, the resin having an acid group and a polymerizable unsaturated group, and the optional added components.

[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, and more preferably has an aromatic ring having 4 to 26 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. The "aromatic group" also includes heteroaromatic groups, and may be substituted with -O-, -S-, or -N= so that -CH2- or -CH= in the "aromatic group" are not adjacent to each other. Examples of the aromatic ring include a monocyclic aromatic ring, a fused aromatic ring, and an assembled 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 assembled aromatic ring include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. In addition, a hydrogen atom of the aromatic ring in the aromatic group may be 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. 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." As used herein, examples of the "aryl group" 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, and a tetralinyl group. The "aryl group" may have a hydrogen atom in an aromatic ring 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. The "arylene group" may be a divalent group obtained by removing any one hydrogen atom from the aforementioned "aryl group." As used herein, examples of the "aralkyl group" include a benzyl group, a diphenylmethyl group, a biphenyl group, and a naphthylmethyl group. A hydrogen atom of an aromatic ring in the aralkyl group may be 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. Examples of the "aralkylene group" include a divalent group obtained by removing any one hydrogen atom from the above-mentioned "aralkyl group." Examples of the "alkyl group" in this specification include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, an (n-)heptyl group, an (n-)octyl group, an (n-)nonyl group, an (n-)decyl group, an (n-)undecyl group, an (n-)dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group. The "alkylene group" includes a divalent group obtained by removing any one hydrogen atom from the "alkyl group". Examples of the "alkenyl group" in this specification include 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, etc. Examples of the "alkenylene group" include a divalent group obtained by removing any one hydrogen atom from the above-mentioned "alkenyl group." As used herein, the term "alkoxy group" includes, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group. As used herein, the term "halogen atom" includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. As used herein, examples of a "straight-chain or branched-chain alkylene group" include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a propylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group. As used herein, examples of the "straight-chain or branched-chain alkylene ether group" include an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxy(1-methylmethylene) group, an oxy(1,1-dimethylmethylene) group, an oxy(1-methylethylene) group, an oxy(1,1-dimethylethylene) group, an oxy(1,2-dimethylethylene) group, an oxybutylene group, an oxy(1-methylpropylene) group, an oxy(2-methylpropylene) group, an oxypentylene group, an oxyhexylene group, an oxyheptylene group, an oxyoctylene group, an oxynonylene group, an oxydecylene group, an oxyundecylene group, and an oxydodecylene group. As used herein, the term "monovalent hydrocarbon group" includes linear, branched, or cyclic saturated hydrocarbons, unsaturated hydrocarbons, or aromatic groups. For example, the "monovalent hydrocarbon group" is a group selected from the group consisting of alkyl groups (e.g., the alkyl groups described above), alkyl groups, alkenyl groups, aryl groups, aralkyl groups, and alkoxy groups, and one or more -CH2- groups in the 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 is preferably a group having 1 to 20 carbon atoms, and may be an alkyl group having 1 to 20 carbon atoms. The term "divalent hydrocarbon group" as used herein includes linear, branched, or cyclic saturated hydrocarbons, unsaturated hydrocarbons, or aromatic groups. For example, it is a group selected from the group consisting of alkylene groups (e.g., the linear or branched alkylene groups described above), alkenylene groups, arylene groups, aralkylene groups, and alkylene ether groups, and one or more -CH2- in the group may be substituted with -O- or -S- so that they are not adjacent to each other, or one or more -CH2-CH2- in the alkylene group may be substituted with -CH=CH- so that they are not adjacent to each other. The hydrocarbon group may be linear or branched, and is preferably a group having 1 to 20 carbon atoms, and may be an alkylene group having 1 to 20 carbon atoms. As used herein, the term "trivalent to hexavalent hydrocarbon group" includes linear, branched, or cyclic saturated hydrocarbons, unsaturated hydrocarbons, and aromatic groups. For example, it refers to a group obtained by removing two to five hydrogen atoms from any one of a group selected from the group consisting of alkyl groups (e.g., the alkyl groups described above), alkyl groups, alkenyl groups, aryl groups, aralkyl groups, and alkoxy groups, and one or more -CH2- in the group obtained by removing the hydrogen atoms 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 have 1 to 20 carbon atoms. As used herein, "(meth)acrylate" means acrylate and / or methacrylate. Also, as used herein, "(meth)acryloyl" means acryloyl and / or methacryloyl. Furthermore, as used herein, "(meth)acrylic" means acrylic and / or methacrylic. As used herein, the term "carbonate compound" refers to an aliphatic hydrocarbon having a carbonate group (-O-(C=O)-O-), and examples thereof include alkylene carbonates having 1 to 5 carbon atoms (such as ethylene carbonate, propylene carbonate, or butylene carbonate).

[0015] (phosphorus-containing active ester) The phosphorus-containing active ester of this embodiment is one of the essential components of the resin composition of this embodiment. The phosphorus-containing active ester is obtained from essential reaction raw materials, which are an aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A), an aromatic monoalcohol (B), a phosphorus-containing polyhydric alcohol compound (C), and an ether bond-containing aliphatic compound (D). If necessary, the reaction raw materials may further contain a compound that is reactive with the aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A), the aromatic monoalcohol (B), the phosphorus-containing polyhydric alcohol compound (C), or the ether bond-containing aliphatic compound (D). In principle, the phosphorus-containing activated ester obtained from the reaction raw materials has no or almost no hydroxyl groups in its molecule, but may contain a compound having a hydroxyl group as a by-product of the reaction product within a range that does not impair the effects of the present disclosure.

[0016] In this specification, "aromatic compounds having two or more carboxyl groups and / or acid halides or esters thereof (A)" may be hereinafter simply referred to as "aromatic polycarboxylic acids (A)." Before describing the reaction raw materials for the phosphorus-containing activated ester, namely, the aromatic polycarboxylic acid (A), the aromatic monoalcohol (B), the phosphorus-containing polyhydric alcohol compound (C), and the ether bond-containing aliphatic compound (D), the structure and properties of the phosphorus-containing activated ester will be described in detail below.

[0017] <Structure of phosphorus-containing activated ester> In terms of chemical structure, the phosphorus-containing activated ester of the present embodiment includes a residue of an aromatic compound having two or more carboxyl groups and / or an acid halide or ester thereof (A), a residue of an aromatic monoalcohol (B), a residue of a phosphorus-containing polyhydric alcohol compound (C), and a residue of an ether bond-containing aliphatic compound (D). More specifically, the phosphorus-containing activated ester of the present embodiment has a structure in which an ester bond derived from a carboxylic acid or an acid halide group thereof in the aromatic polycarboxylic acid (A) and a phenolic hydroxyl group in the aromatic monoalcohol (B) is formed, and an ether bond derived from a hydroxyl group in the phosphorus-containing polyhydric alcohol compound (C) and an ether group in the ether bond-containing aliphatic compound (D) is formed.

[0018] In this specification, "an aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A)" refers to a compound having an aromatic group to which two or more carbonyl-containing atomic groups (-C(=O)-X (X represents a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent hydrocarbon group)) are bonded. In this specification, "a residue of an aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A)" refers to a partial structure of an aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A) that remains in the phosphorus-containing activated ester molecule after reaction or polymerization, and is composed of a chemical bond formed by the reaction or polymerization and a group other than the chemical bond derived from the aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A). Furthermore, in this specification, the term "group derived from" 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 an aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A)" refers to a divalent or higher group obtained by removing an atomic group containing a carbonyl group (-C(=O)-X (X represents a hydrogen atom, a halogen atom, a hydroxyl group, or a monovalent hydrocarbon group) from an aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A), and may be, for example, a divalent or higher aromatic group.

[0019] The aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A) is represented by the following general formula (A): [ka] In this case, Q a1 represents a group derived from an aromatic compound having two or more carboxyl groups and / or an acid halide or ester thereof (A), 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 compound having two or more carboxyl groups and / or its acid halide or ester (A).

[0020] In this specification, the term "residue of aromatic monoalcohol (B)" refers to a monovalent group obtained by removing a hydrogen atom or a hydroxyl group from aromatic monoalcohol (B). "Aromatic monoalcohol (B)" is a monovalent group represented by the following general formula (b1): [ka] In this case, Ar b1 represents a group derived from the aromatic monoalcohol (B), which is a monovalent group obtained by removing a hydrogen atom or a hydroxyl group from the aromatic monoalcohol (B), and the dashed line portion represents a residue of the aromatic monoalcohol (B).

[0021] In this specification, the term "residue of phosphorus-containing polyhydric alcohol compound (C)" refers to a divalent or higher polyvalent group obtained by removing two or more hydrogen atoms or hydroxyl groups from phosphorus-containing polyhydric alcohol compound (C). The "phosphorus-containing polyhydric alcohol compound (C)" is represented by the following general formula (c1): [ka] In this case, A c1 represents a group derived from the phosphorus-containing polyhydric alcohol compound (C), and n is a group obtained by removing a hydrogen atom or a hydroxyl group from the phosphorus-containing polyhydric alcohol compound (C). c1Specifically, it represents a divalent to hexavalent hydrocarbon group containing a phosphorus atom, and n c1 represents an integer between 2 and 6. c1 is preferably 2.

[0022] In this specification, the term "residue of an ether bond-containing aliphatic compound (D)" refers to a divalent or higher group in which one or more ether bonds present in the ether bond-containing aliphatic compound (D) have been cleaved at at least one location, and more specifically refers to a divalent or higher group in which at least one of the two bonds (=ether bonds) connecting at least one oxygen atom in the ether bond-containing aliphatic compound (D) to two carbon atoms bonded to the oxygen atom (either one of which may be a hydrogen atom) has been cleaved. The "ether bond-containing aliphatic compound (D)" is represented by the following general formula (d1): [ka] [In the above general formula (d1), R d1 and R d2 each independently represents a hydrogen atom, an alkyl group, or an alkylene group; R d1 or R d2 When one of R is an alkylene group, the other is also an alkylene group, and R d1 and R d2 may be bonded to each other to form a ring structure, and one or more -CH2- in the alkyl group or alkylene group may be substituted with -O-, -C(=O)-, -C(=O)-O- or -S- so that they are not adjacent to each other.]. The dashed line in the above general formula (d1) represents R d1 and R d2 and R are bonded to each other. d1 and R d2 It represents both the unbound and unbound forms. Examples of the ether bond-containing aliphatic compound (D) include alkylene oxides (e.g., glycidyl ethers) and compounds containing a carbonate group (-O-(C=O)-O-). Specific examples include compounds having an epoxy group such as ethylene oxide, propylene oxide, and butylene oxide; carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate; and alkylene polyols. In addition, in this specification, R d1 and R d2 and (D) together represent a group derived from the ether bond-containing aliphatic compound (D). For example, when the phosphorus-containing activated ester is represented by general formula (1), -R 1 - are each independently -R d1 -R d2 -or-R d2 -R d1 Similarly, -R in general formula (1) 2 - are each independently -R d1 -R d2 -or-R d2 -R d1 -It is possible. When the ether bond-containing aliphatic compound (D) is represented by the above general formula (d1), the group derived from the ether bond-containing aliphatic compound (D) is a group derived from the ether bond-containing aliphatic compound (D) represented by the above general formula (d1) by combining an oxygen atom with R d1 or R d2 and -R d1 -R d2 -or-R d2 -R d1 - is expressed as

[0023] In this specification, the values ​​of "monovalent" or "divalent" indicate the number of bonds, and correspond to the number of ester bonds or ether bonds contributed by one molecule of each compound.

[0024] The group derived from the aromatic polycarboxylic acid (A) in the phosphorus-containing active ester may be divalent to hexavalent. In other words, the phosphorus-containing active ester may have a structure in which the aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A) directly or indirectly contributes to the ester bond. Similarly, the group derived from the phosphorus-containing polyhydric alcohol compound (C) in the phosphorus-containing active ester may be divalent to hexavalent. In other words, the phosphorus-containing active ester may have a structure in which 2 to 6 hydroxyl groups contained in one molecule of the phosphorus-containing polyhydric alcohol compound (C) directly or indirectly contribute to an ester bond.

[0025] <<Preferred form of phosphorus-containing active ester>> More specifically, the phosphorus-containing activated ester 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, and a residue of a phosphorus-containing polyhydric alcohol compound (C) (for example, a divalent to hexavalent hydrocarbon group (alkylene chain, alkyleneoxy chain, aromatic group) having a phosphorus atom and also carbon atoms and hydrogen atoms) and a residue of an ether bond-containing aliphatic compound (D) are linked together: [ka] (In the above general formula (i), Ar b1 represents a group derived from the aromatic monoalcohol (B), for example, a monovalent aromatic group, and Q a1 represents a group derived from an aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A), for example, a divalent aromatic group, and * in the above general formula (i) represents a bond to another atom. The same or different aromatic rings correspond to aromatic rings in the molecule of the aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A) or aromatic monoalcohol (B). 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 phosphorus-containing active ester, so that the resin composition as a whole exhibits flame retardancy and can form a cured product with excellent elongation, adhesion, and low dielectric properties.

[0026] The phosphorus-containing activated ester of this embodiment preferably has a partial structure represented by the following general formula (J-1), a divalent partial structure represented by the following general formula (J-2), a divalent partial structure represented by the following general formula (J-3), a monovalent partial structure represented by the following general formula (J-4), and a monovalent partial structure represented by the following general formula (J-5). A more preferred form of the phosphorus-containing activated ester has a repeating unit composed of the partial structure represented by the following general formula (J-1), the divalent partial structure represented by the following general formula (J-2), and the divalent partial structure represented by the following general formula (J-3), and a partial structure represented by the following general formula (J-4) and / or (J-5) that is chemically bonded to the repeating unit as a terminal portion of the repeating unit. [ka] (In the above general formula (J-1), A represents a divalent to tetravalent group derived from the phosphorus-containing polyhydric alcohol compound (C), and each dashed line is independently absent or a single bond.) [ka] (In the above general formula (J-2), R 1 represents a group derived from the ether bond-containing aliphatic compound (D), and y 1 represents an average number of repetitions greater than or equal to 1.) [ka] (In the above general formula (J-3), R 2 represents a group derived from the ether bond-containing aliphatic compound (D), and Q 2 represents a group derived from an aromatic compound having two or more carboxyl groups and / or an acid halide or ester thereof (A), and z 1is the average number of repetitions greater than or equal to 1, and x 1 indicates an average number of repeats of 0.1 or more.) [ka] (In the above general formula (J-4), Ar 2 represents a group derived from the aromatic monoalcohol (B). [ka] (In the above general formula (J-5), Q 1 represents a group derived from an aromatic compound having two or more carboxyl groups and / or an acid halide or ester thereof (A), and Ar 1 represents a group derived from the aromatic monoalcohol (B). (In this specification, * represents a bond to another atom. However, oxygen atoms are not bonded adjacently (-OO-).) As represented by the above general formula (J-1), A, which is a group derived from the phosphorus-containing polyhydric alcohol compound (C), is preferably a divalent to tetravalent group, and more preferably a divalent or trivalent group. For convenience of explanation, the groups derived from each of the general formulae (J-1) to (J-5) are represented by the general formula (J-1)~(J-5) middle The term "a" represents the correspondence between the symbols and the respective raw material components, but does not represent all of the structural moieties derived from the respective reaction raw materials that remain in the phosphorus-containing activated ester after the reaction. This allows the resulting cured product to have improved elongation, adhesion, and low dielectric properties in a well-balanced manner.

[0027] In the general formula (J-1), A represents a group derived from the phosphorus-containing polyhydric alcohol compound (C) 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. Furthermore, the dashed lines in the general formula (J-1) may each independently be absent or a single bond. Therefore, when both dashed lines are absent, A represents a divalent group; when one of the two dashed lines is absent, A represents a trivalent group; and when both dashed lines are single bonds, A represents a tetravalent group. The group derived from the phosphorus-containing polyhydric alcohol compound (C) preferably has 1 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and even more preferably 6 to 25 carbon atoms.

[0028] The phosphorus in the group derived from the phosphorus-containing polyhydric alcohol compound (C) is not particularly limited by the valence (-3, -1, +1, +3, +5) or the bonding form of the phosphorus, but preferably exists in the form of a pentavalent phosphorus in which an oxo group (=O) is directly bonded to the phosphorus atom, i.e., an oxophosphorus (V) group (≡P(=O)). Therefore, the group derived from the phosphorus-containing polyhydric alcohol compound (C) preferably has an oxophosphorus (V) group (≡P(=O)), and more preferably has three hydrocarbon groups bonded to the phosphorus atom of the oxophosphorus (V) group (≡P(=O)) directly or via oxygen (-O-). Furthermore, examples of the group derived from the phosphorus-containing polyhydric alcohol compound (C) include groups containing phosphorus and a divalent or higher aliphatic hydrocarbon group or a divalent or higher cyclic hydrocarbon group, and preferably have an aromatic group containing divalent or higher phosphorus, more preferably an aromatic group having an oxophosphorus (V) group (≡P(=O)). More specifically, the group derived from the phosphorus-containing polyhydric alcohol compound (C) contains a phosphorus or oxophosphorus (V) group (≡P(=O)) and is a linear or branched alkylene group, a linear or branched alkylene ether group, or a hydrocarbon group having an aromatic ring (an arylene group or an aralkylene group), and -CH- in the alkylene group, alkylene ether group, or hydrocarbon group having an aromatic ring may be substituted with -O- or -S- so that they are not adjacent to each other, or one or more -CH-CH- 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.

[0029] A preferred form of the group derived from the phosphorus-containing polyhydric alcohol compound (C) is a group having an oxophosphorus (V) group (≡P(=O)) and a hydrocarbon group bonded to the oxophosphorus (V) group (≡P(=O)), and a more preferred form is a group having an oxophosphorus (V) group (≡P(=O)) and two to seven cyclic groups (e.g., aromatic rings) bonded to the oxophosphorus (V) group (≡P(=O)). When the cyclic group in the group derived from the phosphorus-containing polyhydric alcohol compound (C) is a condensed polycyclic hydrocarbon, the number of cyclic groups is counted as one aggregate. Therefore, for example, when the condensed polycyclic hydrocarbon is a phenanthrene group, the number of cyclic groups is 1. Furthermore, a ring-assembly hydrocarbon is one in which two or more ring systems are directly connected by a single or double bond, and the number of bonds is one less than the number of ring systems. When the group derived from the phosphorus-containing polyhydric alcohol compound (C) has such a ring-assembly hydrocarbon, each ring system is counted as one. For example, when the ring-assembly hydrocarbon is a terphenyl group, the number of cyclic groups is three.

[0030] A in the above general formula (J-1) represents the following general formula (j): [ka] [In the above general formula (j), M j is (n 1 +1)-valent aromatic group, R 3 and R 4 each independently represents a monovalent hydrocarbon group or a divalent hydrocarbon group, R 3 or R 4 When one of R is a divalent hydrocarbon group, the other is also a divalent hydrocarbon group, and R 3 and R 4 form a ring structure bonded to each other, and n 1 represents an integer of 2 to 4, and * in the above general formula (j) represents a bond bonding to an oxygen atom. In addition, the dashed line portion in the above general formula (j) preferably represents R 3 and R 4 This shows that they may be bonded to each other.

[0031] In the above general formula (j), n 1 represents an integer of preferably 2 or more and 4 or less, more preferably 2 or 3. 1 For example, if is 3, M j is a tetravalent group having three bonds to the oxygen atom. In the general formula (j) above, M j is (n 1 +1)-valent aromatic group, and is selected from a monocyclic aromatic ring, a condensed aromatic ring, and an aromatic ring assembly. 1 +1) hydrogen atoms are removed. For example, M jis one aromatic group selected from the group consisting of benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl, and (n) from the one aromatic group 1 +1) hydrogen atoms have been removed. The one aromatic group may be unsubstituted, or a hydrogen atom of an aromatic ring in the aromatic group may be 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.

[0032] In the general formula (j), the monovalent hydrocarbon group preferably contains a linear, branched, or cyclic saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic group, and is more preferably one type of group selected from the group consisting of alkyl groups, alkenyl groups, aryl groups, aralkyl groups, and alkoxy groups, and one or more -CH2- groups in the selected type of group may be substituted with -O- or -S- so that they are not adjacent to each other. Furthermore, the monovalent hydrocarbon group preferably has 1 to 20 carbon atoms. In the general formula (j), the divalent hydrocarbon group preferably contains a linear, branched, or cyclic saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic group, and is more preferably one type of group selected from the group consisting of alkylene groups, alkenylene groups, arylene groups, aralkylene groups, and alkylene ether groups, and one or more -CH2- groups in the selected type of group may be substituted with -O- or -S- so that they are not adjacent to each other.Furthermore, the divalent hydrocarbon group preferably has 1 to 20 carbon atoms.

[0033] R in the above general formula (J-2) 1R in the above general formula (J-3) preferably represents a group derived from the ether bond-containing aliphatic compound (D). 2 Preferably, R in the general formulae (J-2) and (J-3) represents a group derived from the ether bond-containing aliphatic compound (D). 1 and R 2 Preferably, each independently represents a group derived from the ether bond-containing aliphatic compound (D). 1 and R 2 For example, R in the general formulae (J-2) and (J-3) may be the same or different. 1 and R 2 The preferred embodiment is represented by the following general formula (J) and R in general formula (1): 1 and R 2 This is similar to the preferred embodiment of Q in the above general formula (J-3) 2 Preferably, Q in the general formula (J-5) represents a group derived from an aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A). 1 Preferably, Q in the general formula (J-3) and the general formula (J-5) represents a group derived from an aromatic compound having two or more carboxyl groups and / or an acid halide or ester thereof (A). 1 and Q 2 are each independently, Q 1 and Q 2 For example, Q in the general formula (J-3) and the general formula (J-5) may be the same or different. 1 and Q 2 A preferred embodiment is represented by the following general formula (J) and Q in general formula (1): 1 and Q 2 This is similar to the preferred embodiment of

[0034] Ar in the above general formula (J-4) 2 Preferably, Ar in the general formula (J-5) represents a group derived from the aromatic monoalcohol (B). 1 Preferably, Ar in the above general formula (J-4) and general formula (J-5) represents a group derived from the aromatic monoalcohol (B).1 and Ar 2 are each independently, for example, preferably a substituted or unsubstituted aromatic group, more preferably a substituted or unsubstituted aryl group or aralkyl group. 1 and Ar 2 For example, Ar in the general formula (J-4) and the general formula (J-5) may be the same or different. 1 and Ar 2 The preferred form of may be the general formula (2) or (3) described below, and further, the preferred Ar in the general formula (J-4) and general formula (J-5) may be 1 and Ar 2 represents Ar in the following general formula (1): 1 and Ar 2 This is similar to the preferred embodiment of

[0035] y in the above general formula (J-2) 1 is preferably an average repetition number of 1 or more, and in particular, from the viewpoint of workability and flexibility of the obtained cured product, the average repetition number y 1 is more preferably 1 to 5. In the above general formula (J-3), z 1 is preferably an average number of repetitions of 1 or more, and in particular, from the viewpoint of workability and flexibility of the resulting cured product, the average number of repetitions z 1 is more preferably 1 to 5. The average repeat number of phosphorus-containing active esters x 1 , y 1 and z 1 can be calculated from the charge ratio or NMR, as will be shown in the Examples section below.

[0036] A more preferred embodiment of the phosphorus-containing active ester of this embodiment is a repeating unit composed of a divalent to tetravalent partial structure represented by the general formula (J-1) above, a divalent partial structure represented by the general formula (J-2) chemically bonded to the divalent to tetravalent partial structure represented by the general formula (J-1) above, and a divalent partial structure represented by the general formula (J-3) above, and a partial structure represented by the general formula (J-4) and / or the general formula (J-5) chemically bonded to the repeating unit as a terminal portion of the repeating unit, wherein the number of repetitions of the repeating unit is x 1 is preferably an average number of repetitions, and is preferably 0.1 or more. In particular, from the viewpoints of workability and flexibility of the resulting cured product, the average number of repetitions is more preferably 0.5 to 3, and even more preferably 0.7 to 2.8. Furthermore, it is preferable that a repeating unit be formed by chemically bonding a divalent partial structure represented by the general formula (J-1) with a divalent partial structure represented by the general formula (J-2) and a divalent partial structure represented by the general formula (J-3).Furthermore, it is preferable that a repeating unit be formed by chemically bonding one or two divalent partial structures represented by the general formula (J-2) and two or one divalent partial structures represented by the general formula (J-3) with a trivalent partial structure represented by the general formula (J-1).Furthermore, it is preferable that a repeating unit be formed by chemically bonding one to three divalent partial structures represented by the general formula (J-2) and one to three divalent partial structures represented by the general formula (J-3) with a tetravalent partial structure represented by the general formula (J-1).

[0037] The phosphorus-containing active ester of the present embodiment is preferably represented by the following general formula (J). [ka] (In the above general formula (J), A represents a group derived from the phosphorus-containing polyhydric alcohol compound (C), and R 1 and R 2 each independently represents a group derived from the ether bond-containing aliphatic compound (D), and Q 1 and Q 2represents a group derived from the aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A), and Ar 1 and Ar 2 each independently represents a group derived from the aromatic monoalcohol (B), M a represents a group represented by the following general formula (ii) or (iii): [ka] [In the above general formula (ii) or (iii), R 3 each independently represents a group derived from the ether bond-containing aliphatic compound (D), and Q 3 and Q 4 each independently represents a group derived from the aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A), and Ar 3 and Ar 4 each independently represents a group derived from the aromatic monoalcohol (B), and x 2 is the average number of repetitions greater than or equal to 0.1, and y 2 is the average number of repetitions greater than or equal to 1.] x 1 is the average number of repetitions greater than or equal to 0.1, and y 1 is the average number of repetitions greater than or equal to 1, and z 1 is the average number of repetitions of 1 or more, and q is 0 or 1. When q is 0, A has two bonds (divalent), and when q is 1, A has three bonds (trivalent). This allows the resulting cured product to have improved elongation, adhesion, and low dielectric properties in a well-balanced manner.

[0038] In the above general formula (J), A represents the following general formula (I): [ka] [In the above general formula (I), M 1 represents an aromatic group, and R 3 and R 4each independently represents a monovalent hydrocarbon group or a divalent hydrocarbon group, R 3 or R 4 When one of R is a divalent hydrocarbon group, the other is also a divalent hydrocarbon group, and R 3 and R 4 are bonded to each other to form a cyclic structure, and * in the above general formula (I) represents a bond to an oxygen atom. 3 and R 4 This shows that they may be bonded to each other.

[0039] In the above general formula (I), M 1 is trivalent and is an aromatic group of the formula (n) 1 +1) hydrogen atoms are removed. For example, M 1 teeth , benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl, and 3 others Examples of the groups include those obtained by removing a hydrogen atom from the above. In addition, the preferred embodiment of the general formula (I) or R 3 and R 4 The preferred form of is the same as that of the above general formula (j).

[0040] In A of the above general formula (J), R 3 and R 4When R are each independently a monovalent hydrocarbon group, they are preferably aromatic groups having 3 to 30 carbon atoms, and more preferably aromatic groups having 6 to 24 carbon atoms. 3 and R 4 When each of the groups independently represents a monovalent hydrocarbon group, particularly preferred forms of A include any of the groups of the following general formulae (I-1) to (I-12). [ka] TIFF0007823383000016.tif208168 (In the above general formulas (I-1) to (I-12), R 3 and R 4 each independently represents an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, an aralkyl group, or a naphthyl group; R 5 each independently represents an alkyl group or an alkoxy group, n i1 represents an integer from 0 to 3, and n i3 represents an integer from 0 to 6, and n i2 , n i4 , n i5 and n i6 represents an integer of 0 to 5.) In the groups represented by the above general formulae (I-1) to (I-6), A is a divalent group. On the other hand, in the groups represented by the above general formulae (I-7) to (I-12), A is a trivalent group, and the third bond can be present on any of the aromatic rings.

[0041] In A of the above general formula (1), R 3 and R 4 When each of the groups is independently a divalent hydrocarbon group, it is preferably an alkyl group, an alkoxy group, an allyl group, or an aryl group. R 3 and R 4 When each of the groups independently represents a divalent hydrocarbon group, particularly preferred forms of A include any of the groups represented by the following general formulae (I-13) to (I-20). [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the above general formulas (I-21) to (I-28), R 5 and R 6 each independently represents an alkyl group or an alkoxy group, n iI7 ~n iI14 represents an integer from 0 to 8, and n i8 , n i10 ~n i12 represents an integer from 0 to 5, and n i9 represents an integer from 0 to 7, and n i7 , n i13 and n i14 represents an integer of 0 to 3. 5 represents an aromatic group, M 1 represents the entire substituent, and R 6 is R 3 and R 4 represents a substituent of the entire cyclic structure in which the rings are bonded to each other.) In the groups represented by the general formulae (I-13) to (I-20), A is a divalent group. On the other hand, in the groups represented by the general formulae (I-21) to (I-28), A is a trivalent group, and the third bond can be present on any of the aromatic rings.

[0042] A in the general formula (J) preferably has a cyclic group, more preferably an aromatic group. This structure of A contains a phosphorus atom and has a high concentration of aromatic rings, which contributes to improving the flame retardancy of the phosphorus-containing active ester, and is therefore preferable. Known active esters having an alicyclic hydrocarbon group in their molecular structure have excellent dielectric properties (low dielectric properties) in the resulting cured product, but are prone to combustion and have insufficient heat resistance. However, the phosphorus-containing active ester of the present embodiment can combine elongation, adhesion, and dielectric properties at a higher level by introducing multiple aromatic rings into its molecular structure. Furthermore, phosphorus-containing active esters having a bulky substituent structure, such as the structure represented by general formula (I), tend to have a lower concentration of active groups involved in the curing reaction compared to active esters without a bulky substituent structure, resulting in inferior heat resistance of the cured product. As a result, the phosphorus-containing active ester of the present disclosure is characterized by excellent elongation, adhesion, and dielectric properties, as well as excellent flame retardancy or heat resistance, and can combine various performances.

[0043] R in the above general formula (J), general formula (ii) and general formula (iii) 1 , R 2 , R ii and R iii Preferably, each independently represents a group derived from the ether bond-containing aliphatic compound (D). 1 and R 2 and R ii and R iii For example, R in the general formula (J-1) 1 , R 2 , R ii and R iiipreferably each independently represent a group derived from the ether bond-containing aliphatic compound (D). For example, the group derived from the ether bond-containing aliphatic compound (D) is preferably a linear, branched, or cyclic divalent hydrocarbon group, more preferably a linear or branched alkylene group. The linear or branched alkylene group more preferably has 2 to 16 carbon atoms, and even more preferably 2 to 10. When the number of carbon atoms is within the above range, the phosphorus-containing active ester has excellent compatibility, which is a preferred embodiment.

[0044] Q in the above general formula (J), general formula (ii) and general formula (iii) 1 , Q 2 , Q 3 and Q 4 Preferably, each independently represents a group derived from an aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A). 1 and Q 2 and Q 3 and Q 4 and may be the same or different from each other. For example, Q in the above general formula (J) 1 , Q 2 , Q 3 and Q 4 A preferred embodiment of each of the groups derived from the aromatic polycarboxylic acids (A) is, for example, a divalent aromatic group, and more preferably an unsubstituted divalent aromatic group. 1 , Q 2 , Q 3 and Q 4 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 , Q 2 , Q 3 and Q 4is more preferably any one of a phenylene group, a naphthalenediyl group, and an anthracenediyl group. These phenylene groups, naphthalenediyl groups, and anthracenediyl groups may be unsubstituted or substituted with a halogen atom, a cyano group, an amino group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Among these, from the viewpoints of industrial availability of raw materials and solubility, Q 1 , Q 2 , Q 3 and Q 4 is more preferably an unsubstituted phenylene group.

[0045] Ar in the above general formula (J), general formula (ii) and general formula (iii) 1 , Ar 2 , Ar 3 and Ar 4 Preferably, each independently represents a group derived from the aromatic monoalcohol (B). For example, a substituted or unsubstituted aromatic group is preferred, and a substituted or unsubstituted aryl group or aralkyl group is more preferred. In the above general formula (J), general formula (ii) and general formula (iii), Ar 1 and Ar 2 and Ar 3 and Ar 4 may be the same as each other or may be different from each other. Ar in the above general formula (J), general formula (ii) and general formula (iii) 1 , Ar 2 , Ar 3 and Ar 4 are each independently, for example, a group derived from the aromatic monoalcohol (B) 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)] 1 , Ar 2 represents the bond to the oxygen atom that bonds to R 21 and R 31each independently represents a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an aralkyl group; k 21 represents an integer of 0 to 7, and k 31 represents an integer of 0 to 5.] is preferably represented by the following.

[0046] In the above general formula (J) and general formula (ii), Ar 1 and Ar 3 are preferably each independently a group having a structure represented by the general formula (3). 2 and Ar 4 are preferably each independently a group having a structure represented by the above general formula (3).

[0047] R in the above general formula (2) 21 is preferably any one of a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, and an aralkyl group, and among these, from the viewpoints of dielectric properties, workability, and flexibility of the obtained cured product, is more preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aralkyl group such as a benzyl group, a diphenylmethyl group, or a naphthylmethyl group, or an arylene group such as a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, or an anthryl group. R in the above general formula (3) 31 is preferably any one of a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, and an aralkyl group, and among these, from the viewpoints of dielectric properties, workability, and flexibility of the obtained cured product, is more preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aralkyl group such as a benzyl group, a diphenylmethyl group, or a naphthylmethyl group, or an arylene group such as a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, or an anthryl group. k in the above general formula (2) 21is preferably an integer of 0 to 7, more preferably an integer of 0 to 5, and from the viewpoint of reactivity or flexibility of the resulting cured product, is even more preferably an integer of 0 to 4. 31 is preferably an integer of 0 to 5, and more preferably an integer of 0 to 4 from the viewpoint of reactivity or flexibility of the resulting cured product.

[0048] x in the above general formula (J) 1 is preferably an average repeat number of 0.1 or more, and from the viewpoint of workability and flexibility of the obtained cured product, is more preferably an average repeat number of 0.5 to 3, and even more preferably an average repeat number of 0.7 to 2.8. 2 is preferably an average number of repetitions of 0.1 or more, and from the viewpoints of workability and flexibility of the resulting cured product, it is more preferably an average number of repetitions of 0.5 to 3, and even more preferably an average number of repetitions of 0.7 to 2.8. y in the above general formula (J) 1 is preferably an average repeat number of 1 or more, and more preferably 1 to 5 from the viewpoints of workability and flexibility of the resulting cured product. 2 is preferably an average repeat number of 1 or more, and more preferably 1 to 5 from the viewpoints of workability and flexibility of the resulting cured product. z in the above general formula (J) 1 is preferably an average number of repetitions of 1 or more, and in particular, from the viewpoint of workability and flexibility of the resulting cured product, the average number of repetitions z 1 is more preferably 1 to 5.

[0049] The phosphorus-containing active ester of this embodiment may be a compound represented by the following general formula (1): In other words, a preferred form of the phosphorus-containing active ester represented by the above general formula (J) is represented by the following general formula (1). [ka] [In the above general formula (1), A represents a group derived from the phosphorus-containing polyhydric alcohol compound (C), and R 1 and R 2 each independently represents a group derived from the ether bond-containing aliphatic compound (D), and Q 1 and Q 2 represents a group derived from the aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A), and Ar 1 and Ar 2 each independently represents a group derived from the aromatic monoalcohol (B), and x 1 is the average number of repetitions greater than or equal to 0.1, and y 1 is the average number of repetitions greater than or equal to 1, and z 1 is an average repeat number of 1 or more. For the sake of convenience, the above-mentioned groups derived from each of the raw material components are terms that represent the correspondence between the symbols in general formula (1) and the raw material components, but do not represent all of the structural moieties derived from each of the raw material components that remain in the phosphorus-containing activated ester after the reaction. This allows the composition to exhibit flame retardancy and to have the resulting cured product have improved elongation, adhesion, and low dielectric properties in a well-balanced manner.

[0050] In the general formula (1), the preferred form of A is the same as in the general formula (J). Therefore, in the general formula (1), A preferably has a cyclic group, and more preferably has an aromatic group. This structure of A contains a phosphorus atom and has a high concentration of aromatic rings, which contributes to the effect of improving the flame retardancy based on the phosphorus-containing active ester, and is therefore more preferred. Known active esters having an alicyclic hydrocarbon group in their molecular structure have excellent dielectric properties (low dielectric properties) in the resulting cured product, but are prone to combustion and have insufficient heat resistance. However, by introducing multiple aromatic rings into the molecular structure, the phosphorus-containing active ester of the present embodiment can combine not only dielectric properties, elongation, and adhesion, but also high levels of flame retardancy. Furthermore, phosphorus-containing active esters having a bulky substituent structure, such as the structure represented by general formula (I), tend to have a lower concentration of active groups involved in the curing reaction compared to active esters without a bulky substituent structure, resulting in inferior heat resistance of the cured product. As a result, the phosphorus-containing active ester of the present disclosure is characterized by excellent dielectric properties, elongation, and adhesion, as well as excellent flame retardancy or heat resistance, and can combine various performance capabilities.

[0051] R in the above general formula (1) 1 or R 2 The preferred embodiments of each of the above are R 1 or R 2 The preferred embodiments are the same as those of the above general formula (1). 1 and R 2 is more preferably a linear or branched alkylene group. The number of carbon atoms in the linear or branched alkylene group is more preferably 2 to 16, and even more preferably 2 to 10. When the number of carbon atoms is within the above range, the phosphorus-containing active ester has excellent compatibility, which is a preferred embodiment.

[0052] Q in the above general formula (1) 1 or Q 2 represents Q in the above general formula (J). 1 or Q 2 The preferred form is the same as that of Q.1 and Q 2 may be the same as each other or may be different from each other.

[0053] Ar in the above general formula (1) 1 and Ar 2 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)] 1 or Ar 2 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 of 0 to 7, and k 31 represents an integer of 0 to 5.] is preferably represented by the following.

[0054] In the above general formula (1), Ar 1 and Ar 2 may be the same as each other or may be different from each other. In the above general formula (1), Ar 1 is preferably a group having a structure represented by the above general formula (3). 2 is preferably a group having the structure represented by the above general formula (3). Ar in the above general formula (1) 1 and Ar 2 The preferred form of may be the above general formula (2) or (3), and further, Ar in the above general formula (J) 1 or Ar 2 It may be the same as the preferred form of

[0055] In the above general formula (1), x 1is preferably an average number of repetitions of 0.1 or more, and from the viewpoints of workability and flexibility of the resulting cured product, it is more preferably an average number of repetitions of 0.5 to 3, and even more preferably an average number of repetitions of 0.7 to 2.8. The average repeat number of phosphorus-containing active esters x 1 can be calculated from the charge ratio, NMR, etc. For example, when calculated from the charge ratio, it is calculated by the following mathematical formula (1). Formula (1): (average repeat number x in the obtained phosphorus-containing active ester) 1 ) = (number of moles of hydroxyl groups in the reaction product (E) of the phosphorus-containing polyhydric alcohol compound (C) and the ether bond-containing aliphatic compound (D)) / [(number of moles of active ester groups in the active ester group-containing intermediate product (a') produced from the reaction raw materials) - (number of moles of hydroxyl groups in the reaction product (E) of the phosphorus-containing polyhydric alcohol compound (C) and the ether bond-containing aliphatic compound (D)] 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 (A) with an aromatic monoalcohol (B) as reaction raw materials.

[0056] y in the above general formula (1) 1 is preferably an average repetition number of 1 or more, and in particular, from the viewpoint of workability and flexibility of the obtained cured product, the average repetition number y 1 is more preferably 1 to 5. In the above general formula (1), z 1 is preferably an average number of repetitions of 1 or more, and in particular, from the viewpoint of workability and flexibility of the resulting cured product, the average number of repetitions z 1 is more preferably 1 to 5. The average repeat number y of the phosphorus-containing active ester 1 and z 1 can be calculated from the charge ratio or NMR, as will be shown in the Examples section below.

[0057] <Reaction raw material for phosphorus-containing activated ester> Aromatic polycarboxylic acids (A) (Q of the above general formula (1) 1 and / or Q 2 (a compound having a partial structure represented by the general formula (1)) and an aromatic monoalcohol (B) (Ar 1 and / or Ar 2 a phosphorus-containing polyhydric alcohol compound (C) (a compound having a partial structure represented by A in the above general formula (1)), and an ether bond-containing aliphatic compound (D) (a compound having a partial structure represented by R in the above general formula (1) 1 and / or R 2 A phosphorus-containing active ester can be obtained by using a compound having a partial structure represented by the following formula (III) as a reaction raw material. In the structure of the phosphorus-containing active ester, a structural portion (e.g., A in the above general formula (1)) exhibiting flame retardancy derived from the phosphorus-containing polyhydric alcohol compound (C) and an aromatic ring (e.g., Q in the above general formula (1)) having high curability at the terminal are present. 1 and / or Q 2 and Ar 1 and / or Ar 2 ) (specifically, a polyaryloxycarbonyl structure) and an alkylene ether group (for example, (R 1 O) or (R 2 O)) and an ester compound containing the same, and therefore has high reactivity. The reaction raw materials for the phosphorus-containing active ester will be described below. - an aromatic compound having two or more carboxyl groups and / or an acid halide or ester thereof (A) - In this embodiment, an aromatic compound having two or more carboxyl groups and / or an acid halide or ester thereof (A) (Q of the above general formula (1)) 1 and / or Q 2 The compound having a partial structure represented by the formula (I) is a carboxylic acid having two or more carboxyl groups, or a derivative thereof, specifically a carboxylate, an acid halide, or an ester.

[0058] The aromatic polycarboxylic acid (A) 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 or an ethyloxycarbonyl group; or an aryloxycarbonyl group such as a phenyloxycarbonyl group or a naphthyloxycarbonyl group. In other words, when the carboxyl group or the like moiety is a halogenated acyl group, the aromatic polycarboxylic acid (A) 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 (A) is an esterified product. The aromatic polycarboxylic acids (A) preferably have a carboxyl group, an acyl halide group, or an aryloxycarbonyl group, more preferably have a carboxyl group or an acyl halide group, and even more preferably have a carboxyl group, an acyl chloride group, or an acyl bromide group. The aromatic ring is not particularly limited, and examples thereof include a monocyclic aromatic ring, a fused aromatic ring, an aromatic ring assembly, an aromatic ring connected by an alkylene chain, etc. From the viewpoints of flexibility of the obtained cured product, ease of industrial availability of raw materials, and workability, the aromatic ring is preferably a monocyclic aromatic ring or a fused aromatic ring.

[0059] The valence (number) of the carboxyl groups in the aromatic polycarboxylic acids (A) is preferably from divalent to tetravalent, and more preferably divalent.

[0060] Specific examples of the aromatic polycarboxylic acids (A) 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.

[0061] Of the above-mentioned examples, from the viewpoints of flexibility of the resulting cured product, ease of industrial availability of raw materials, and workability, preferred aromatic polycarboxylic acids (A) are benzenedicarboxylic acid, benzenetricarboxylic acid, naphthalenedicarboxylic acid, and acid halides thereof, more preferred are isophthalic acid, terephthalic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 1,3,5-benzenetricarboxylic acid, and acid halides thereof, and even more preferred are isophthalic acid chloride and terephthalic acid chloride. The aromatic polycarboxylic acids (A) may be used alone or in combination of two or more.

[0062] -Aromatic monoalcohol (B)- The aromatic monoalcohol (B) is an aromatic compound having an aromatic ring and one phenolic hydroxyl group. Specific examples of the aromatic monoalcohol (B) 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 aromatic monoalcohol (B) from the viewpoint of superior dielectric properties. The aromatic monoalcohol (B) may be used alone or in combination of two or more.

[0063] -Phosphorus-containing polyhydric alcohol compound (C)- In this embodiment, the phosphorus-containing polyhydric alcohol compound (C) is preferably a compound containing a phosphorus atom and at least two hydroxyl groups. Therefore, the phosphorus-containing polyhydric alcohol compound (C) also includes phosphoric acid, phosphorous acid, and phosphate esters. Furthermore, the phosphorus in the phosphorus-containing polyhydric alcohol compound (C) is not particularly limited to the valence (-3, -1, +1, +3, +5) or the bonding form of the phosphorus, as long as it is in a form that exhibits flame retardancy. However, for example, it is preferably in the form of pentavalent phosphorus in which an oxo group (=O) is directly bonded to the phosphorus atom, i.e., an oxophosphorus (V) group (≡P(=O)). In addition, the hydroxyl equivalent of the phosphorus-containing polyhydric alcohol compound (C) in this embodiment must be less than 1000 g / eq. The hydroxyl equivalent is preferably 50 g / eq or more and less than 800 g / eq, and more preferably 100 g / eq or more and less than 500 g / eq. When the hydroxyl equivalent is less than 500 g / eq, the heat resistance of the cured product is excellent. The hydroxyl equivalent is a value measured in accordance with JIS K 0070. The valence (number) of the hydroxyl groups in the phosphorus-containing polyhydric alcohol compound (C) is preferably from divalent to hexavalent, and more preferably divalent.

[0064] The phosphorus-containing polyhydric alcohol compound (C) may or may not contain an aromatic ring, but preferably contains an aromatic ring. The phosphorus-containing polyhydric alcohol compound (C) is preferably a compound having a phosphorus atom and two or more hydroxyl groups, and having a hydrocarbon group having a linear or branched alkylene chain (divalent aliphatic hydrocarbon group), a linear or branched alkylene ether chain (alkyleneoxy group), or an aromatic ring. Specifically, the phosphorus-containing polyhydric alcohol compound (C) is represented by the following general formula (II): [ka] [In the above general formula (II), M 1II represents a monovalent to hexavalent hydrocarbon group, and R 3II and R 4II each independently represents a monovalent to divalent hydrocarbon group, R 3II or R 4II may bond to each other to form a cyclic structure, and nc1 represents an integer of 2 to 5. It is preferable that R in the general formula (II) represents an integer of 2 to 5. The general formula (II) corresponds to the general formula (c1). Therefore, 3II -(R 4II )P(=O)-M 1II - is a partial structure of A c1 It is possible. The phosphorus-containing polyhydric alcohol compound (C) may be a commercially available product. Examples of commercially available products include HCA-HQ (10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) manufactured by Sanko Co., Ltd., and HCA=NQ (10-[2 ,5-(dihydroxynaphthyl)]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), CPHO-HQ (a mixture of 1,4-cyclooctylenephosphonyl-1,4-hydroquinone and 1,5-cyclooctylenephosphonyl-1,4-hydroquinone) manufactured by Nippon Chemical Industry Co., Ltd., and phosphorus-containing dicarboxylic acid monomers such as HCA-maleic acid adduct, HCA-citraconic acid adduct, and HCA-itaconic acid adduct (trade name M-ACID, manufactured by Sanko Co., Ltd.). The phosphorus content in the phosphorus-containing polyhydric alcohol compound (C) is preferably 3% by mass or more, and more preferably in the range of 4 to 25% by mass. When the phosphorus content is within the above range, the product phosphorus-containing active ester can be expected to have a flame retardant effect. The phosphorus content is measured by calculation using the method described in the Examples section.

[0065] -Ether bond-containing aliphatic compound (D)- In this embodiment, the ether bond-containing aliphatic compound (D) (R 1 and / or R 2 The compound having a partial structure represented by the formula (II) is an aliphatic compound having one or more ether bonds, and examples thereof include linear or branched ethers, cyclic ethers (alkylene oxides), carbonate compounds, and alkylene polyols, with cyclic ethers (alkylene oxides), carbonate compounds, and alkylene polyols being preferred. Examples of the cyclic ether (alkylene oxide) include compounds having an epoxy group, such as ethylene oxide, propylene oxide, and butylene oxide. Examples of the carbonate compound include ethylene carbonate, propylene carbonate, and butylene carbonate. The alkylene polyol is preferably an aliphatic polyol, for example, a straight-chain aliphatic diol compound 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, or 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, or 2,3-dimethyl-1, Examples of branched chain aliphatic diol compounds include 4-butanediol, 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.

[0066] In this embodiment, the reaction raw materials may further contain, as necessary, a compound (F) that is reactive with the aromatic polycarboxylic acid, its acid halide and / or its ester (A), the aromatic monoalcohol (B), the phosphorus-containing polyhydric alcohol aromatic compound (C), or the ether bond-containing aliphatic compound (D). Examples of the compound (F) include polyaromatics such as m-dihydroxybenzene, 2,4-toluenediol, 3,5-toluenediol, p-xylene-2,6-diol, m-xylene-4,6-diol, p-dihydroxybenzene, 2,5-toluenediol, p-xylene-2,5-diol, dihydroxynaphthalene, and dihydroxyanthracene. The content of the compound (F) or a group derived from the compound (F) is, for example, preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, relative to the total amount (100% by mass) of the phosphorus-containing active ester.

[0067] As described above, the phosphorus-containing active ester in the present disclosure is a compound obtained by using the aromatic compound (A) having a carboxylic acid halogen group, the aromatic monoalcohol (B), the phosphorus-containing polyhydric alcohol aromatic compound (C), and the ether bond-containing aliphatic compound (D) as reaction raw materials. On the other hand, when the phosphorus-containing active ester in the present disclosure is specified by a different expression independent of the reaction raw materials, the phosphorus-containing active ester in this embodiment is represented by the following general formula (1'): [ka] [In the above general formula (1'), each A independently represents a divalent hydrocarbon group, and R 11 and R 12 each independently represents a linear or branched alkylene 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 21and 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. x 1 is the average number of repetitions greater than or equal to 0.1, and y 1 is the average number of repetitions greater than or equal to 1, and z 1 is the average repeat number of 1 or more. The phosphorus-containing active ester represented by the general formula (1') has multiple ester bonds and contains a chain-like alkylene group or alkylene ether group with relatively low polarity, making it easier to function as a flexible segment and enabling the production of a cured product with excellent adhesion or low dielectric properties, making it useful. A more preferred example of the phosphorus-containing active ester of the present embodiment is represented by the above general formula (1′), in which each A independently represents an aromatic group, R 11 and R 12 each independently represents a linear or branched alkylene group; Q 11 and Q 12 each independently represents a 1,3-phenylene group or a 1,4-phenylene group; x 1 represents the average number of repetitions between 0.01 and 10, and y 1 is the average number of repetitions greater than or equal to 1, and z 1 is the average number of repetitions greater than or equal to 1, Ar 11 and Ar 12 each independently represents a structure represented by the general formula (2) or (3), and * in the general formula (2) and the general formula (3) represents Ar in the general formula (1). 11 or Ar 12 represents the bond to the oxygen atom that bonds to R 21 and R 31 each independently represents a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, or an aralkyl group; k 21represents an integer from 0 to 7, and k 31 represents an integer of 0 to 5.] is preferably represented by the following.

[0068] <Another preferred form of phosphorus-containing active ester> Another preferred embodiment of the phosphorus-containing activated ester of this embodiment is a reaction product of the ester compound (a') (also referred to as intermediate product (a')) and intermediate product (b'), which is a reaction product of a phosphorus-containing polyhydric alcohol compound (C) and an ether bond-containing compound, as reaction raw materials (I). The intermediate product (a') may also be a reaction product of the aromatic polycarboxylic acid, its acid halide and / or its ester (A), and an aromatic monoalcohol (B) as reaction raw materials (II). Furthermore, intermediate product (b') may also be a reaction product of the phosphorus-containing polyhydric alcohol compound (C) and an ether bond-containing compound (D) as reaction raw materials (III). An ester compound (a') having an ester bond is obtained by reacting an aromatic polycarboxylic acid (A) with an aromatic monoalcohol (B). Then, an intermediate product (b') having two or more hydroxyl groups having ether bonds is obtained by reacting a phosphorus-containing polyhydric alcohol compound (C) with an ether bond-containing compound. On the other hand, by reacting the ester compound (a') with the intermediate product (b'), an ester exchange reaction occurs, and a phosphorus-containing activated ester containing an aromatic ring-containing group (e.g., an aryloxycarbonyl group) at the terminal can be obtained.

[0069] In this embodiment, the use of a phosphorus-containing active ester results in a cured product with a low dielectric loss tangent and excellent flame retardancy, heat resistance, moist heat resistance, and adhesion, making it a preferred embodiment. Although the reason for this is not entirely clear, the resulting phosphorus-containing active ester contains an aryloxycarbonyl group (active ester group) at its terminal, which makes it highly reactive with the epoxy groups of the epoxy resin described below. This high reactivity can prevent or suppress the generation of hydroxyl groups resulting from the ring-opening of the epoxy group, making it a preferred embodiment. Furthermore, since the phosphorus-containing active ester has no or almost no hydroxyl groups in its molecule, the cured product obtained by reaction of the phosphorus-containing active ester also has no or almost no hydroxyl groups derived from the phosphorus-containing active ester. Using such an active ester can prevent or suppress the generation of hydroxyl groups during curing. Generally, highly polar hydroxyl groups are known to increase the dielectric loss tangent, and the use of the phosphorus-containing active ester is particularly useful because it can achieve a low dielectric loss tangent in the cured product.

[0070] Furthermore, since the phosphorus-containing active ester has two or more ester bonds that are reactive with the epoxy groups of the epoxy resin described below, the crosslink density of the cured product can be increased and the heat resistance can be improved.

[0071] The phosphorus-containing active ester of the present embodiment has a flexible segment such as an alkylene group or an alkyleneoxy group (alkylene ether chain), and has no or almost no hydroxyl groups, and therefore has a low polarity structure. This allows for the provision of a curable composition (for example, an epoxy resin composition containing an epoxy resin) that can exhibit excellent flame retardancy, flexibility, moisture absorption resistance, adhesion to copper foil and the like due to the flexibility, and low dielectric properties in the obtained cured product, as well as cured products, insulating materials, resist materials, and the like obtained using the curable composition, which are preferred embodiments.

[0072] <Characteristics of phosphorus-containing activated esters> When the total number of aromatic ester groups in the phosphorus-containing active ester structure is taken as the number of functional groups of the phosphorus-containing active ester, the functional group equivalent of the phosphorus-containing active ester of the present 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 1000 g / eq, because this provides a cured product with excellent curability and a low dielectric constant and dielectric dissipation factor (low dielectric properties). The phosphorus content in the phosphorus-containing active ester of the present embodiment is preferably 1.8% by mass or more, more preferably 1.8 to 25% by mass, and even more preferably 1.9 to 24% by mass, from the viewpoints of flame retardancy and low dielectric loss tangent of the resulting cured product, etc. The number average molecular weight (Mn) of the phosphorus-containing active ester of the present disclosure is preferably 320 to 3000, and more preferably 360 to 2400. A number average molecular weight (Mn) of 320 or more is preferred because it provides an excellent dielectric loss tangent. On the other hand, a number average molecular weight (Mn) of 3000 or less is preferred because it provides excellent moldability. The functional group equivalent weight, phosphorus content, and number average molecular weight (Mn) of the phosphorus-containing active ester are measured by calculation using the method described in the Examples section. From the viewpoints of handleability when preparing a curable composition described later and an excellent balance between excellent elongation and dielectric properties of the cured product, the phosphorus-containing active ester of this embodiment preferably has a softening point of 200° C. or lower, and more preferably 180° C. or lower. The softening point of the phosphorus-containing active ester of this embodiment is measured in accordance with JIS K7234.

[0073] The phosphorus-containing active ester of the present embodiment comprises a rigid mesogen having aromatic rings connected by an ester bond, a flexible segment such as an alkylene chain or an alkylene ether chain, and The present invention provides a curable composition (for example, an epoxy resin composition containing an epoxy resin) that has a flame-retardant phosphorus-containing group (preferably an oxophosphorus (V) group (a mesogen having ≡P(=O))) and has no or substantially no hydroxyl groups, resulting in a low-polarity structure, and that can exhibit excellent elongation, adhesion to copper foil and the like due to flexibility, and low dielectric properties in the resulting cured product. It is also possible to provide a semiconductor encapsulating material, a semiconductor device, a prepreg, a circuit board, a build-up film, and the like, that use the curable composition.

[0074] <Method for synthesizing phosphorus-containing active esters> The synthesis method of the phosphorus-containing active ester is not particularly limited, except that the aromatic polycarboxylic acid (A), the aromatic monoalcohol (B), the phosphorus-containing polyhydric alcohol compound (C), and the ether bond-containing aliphatic compound (D) are used as raw materials and reacted. However, in the synthesis of the phosphorus-containing active ester, (1) a first reaction step in which an aromatic polycarboxylic acid (A) is reacted with an aromatic monoalcohol (B) to obtain an intermediate product (a'); and (2) a second reaction step in which the phosphorus-containing polyhydric alcohol compound (C) is reacted with the ether bond-containing aliphatic compound (D) to obtain the intermediate product (b'); (3) a third reaction step in which the intermediate product (a') is reacted with the intermediate product (b') to obtain a phosphorus-containing activated ester as a reaction product; It is preferable to use a method including the following steps, because it is possible to obtain a phosphorus-containing active ester relatively easily. In this case, in the first reaction step, an ester compound having an ester bond formed therein is obtained as intermediate product (a'), and in the second reaction step, an ether compound having a terminal hydroxyl group obtained by addition / condensation of an -O-hydrocarbon group- (e.g., oxy-alkylene) of the ether bond-containing aliphatic compound (D) to the hydroxyl group of the phosphorus-containing polyhydric alcohol compound (C) is obtained as intermediate product (b'), and then in the third reaction step, an ester exchange reaction occurs to obtain a phosphorus-containing activated ester having an aryloxycarbonyl group structure at its terminal.

[0075] 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.

[0076] 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.

[0077] The reaction ratio of the aromatic polycarboxylic acid (A) and the aromatic monoalcohol (B) can be appropriately changed depending on the desired molecular design. However, from the viewpoint of reducing unreacted terminals and reducing excess reaction raw materials, the ratio of the aromatic monoalcohol (B) to 1 mole of the aromatic polycarboxylic acid (A) is preferably in the range of 1.1 to 5.0 moles, more preferably 1.5 to 4.0 moles, and even more preferably 2.0 to 3.0 moles.

[0078] After the first reaction step is completed, if an aqueous solution is used in the presence of an alkali catalyst, the reaction solution is allowed to stand for liquid separation to remove the aqueous layer, and the remaining organic layer is washed with water. This washing is repeated until the aqueous layer becomes nearly neutral (about pH 7), thereby obtaining intermediate product (a'), which is the reaction product of the aromatic polycarboxylic acid (A) and the aromatic monoalcohol (B), with a reduced content of inorganic salts that adversely affect insulating properties. This allows the content of inorganic salts that adversely affect insulating properties in the obtained intermediate product (a') to be reduced.

[0079] Next, in the second reaction step, intermediate product (b') is obtained by heating and stirring phosphorus-containing polyhydric alcohol compound (C) and ether bond-containing aliphatic compound (D) under a base catalyst. For example, intermediate product (b') can be obtained by condensation reaction of phosphorus-containing polyhydric alcohol compound (C) represented by general formula (II) with a cyclic ether or carbonate compound, condensation reaction of at least one phosphoric acid selected from the group consisting of phosphoric acid, phosphonic acid, phosphinic acid, phosphane oxide, phosphorous acid, phosphonous acid, and phosphinous acid with an alkylene polyol, or condensation reaction of phosphorus-containing polyhydric alcohol compound (C) with an alkylene polyol, such as HCA-maleic acid adduct, HCA-citraconic acid adduct, or HCA-itaconic acid adduct (trade name M-ACID, manufactured by Sanko Co., Ltd.). Alternatively, intermediate product (b') may be a commercially available product, such as a phosphorus-containing polyester polyol condensate having terminal hydroxyl groups (trade name M-ESTER, manufactured by Sanko Co., Ltd., ME-P8). Examples of the base catalyst used in the second reaction step include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, triethylamine, pyridine, diazabicycloundecene, diazabicyclononene, triphenylphosphine, etc. These base catalysts may be used alone or in combination of two or more, and diazabicycloundecene, diazabicyclononene, and triphenylphosphine are preferred because of their high reaction efficiency. The second reaction step may be carried out without solvent (no organic solvent is used) or in an organic solvent, although there are no particular limitations. Examples of the organic solvent include hydrocarbon solvents such as pentane and hexane; ketone solvents such as acetone, methyl ethyl 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. The conditions for the second reaction step are not particularly limited, but for example, the intermediate product (b') can be obtained by stirring and reacting at a temperature of 50 to 250°C for 1 to 24 hours. The intermediate product (b') may have a structure in which the hydrogen atoms of the hydroxyl groups of the phosphorus-containing polyhydric alcohol compound (C) have been substituted with alkylene oxides such as alkylene polyols.

[0080] In the third reaction step, the intermediate product (a') obtained in the first reaction step is reacted with the intermediate product (b') obtained in the second reaction step. This causes a transesterification reaction, resulting in the production of the phosphorus-containing activated ester of the present disclosure. The conditions for the third reaction step are not particularly limited, but may include stirring and reaction at a temperature of 50 to 250°C for 1 to 24 hours. Furthermore, in the second reaction step, the reaction can be accelerated by adding an alkali catalyst, particularly an amine catalyst (an alkylamine such as triethylamine, an arylamine such as triphenylamine, a fused amine such as DBU or DBN, or a heterocyclic amine such as imidazole or pyridine).

[0081] During the reaction in the third reaction step, an antioxidant may be used to prevent deterioration due to contamination with trace amounts of oxygen. Specific examples of the antioxidant include p-methoxyphenol, p-methoxycresol, 4-methoxy-1-naphthol, 4,4'-dialkoxy-2,2'-bi-1-naphthol, 3-(N-salicyloyl)amino-1,2,4-triazole, N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, styrenated phenol, N-isopropyl-N'-phenylbenzene-1,4-diamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, "4-[[4,6-bis(octylthio)- Phenol compounds such as 1,3,5-triazin-2-yl]amino]-1,6-di-tert-butylphenol, quinone compounds such as hydroquinone, methylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone, anthraquinone, and diphenoquinone, melamine, p-phenylenediamine, 4-aminodiphenylamine, N,N''-diphenyl-p-phenylenediamine, Ni-propyl-N''-phenyl-p-phenylenediamine, N-(1,3,5-triazin-2-yl)amino-1,6-di-tert-butylphenol, and the like.Amine compounds such as 3-dimethylbutyl)-N''-phenyl-p-phenylenediamine, diphenylamine, 4,4''-dicumyl-diphenylamine, 4,4''-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine with 2,4,4-trimethylpentene, and reaction products of diphenylamine with 2,4,4-trimethylpentene, phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl)methyl]-2,2-dione, 2,2-bis(2,2-dione), ... Thioether compounds such as (decylthio)propionyl]oxy}methyl)-1,3-propanediyl bis[3-(dodecylthio)propionate], ditridecan-1-yl 3,3'-sulfanediyl dipropanoate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitrosoaniline, N-nitroso-N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N Nitroso compounds such as n-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, and 2-nitroso-5-methylaminophenol hydrochloride, esters of phosphoric acid and octadecan-1-ol, triphenyl phosphite, and 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, phosphite compounds such as tris(2,4-di-tert-butylphenyl) phosphite, bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate Examples of antioxidants include zinc compounds such as zinc dibutyl dithiocarbamate, nickel compounds such as bis(N,N-dibutylcarbamodithioato-S,S')nickel, and sulfur compounds such as 1,3-dihydro-2H-benzimidazole-2-thione, 4,6-bis(octylthiomethyl)-o-cresol, 2-methyl-4,6-bis[(octan-1-ylsulfanyl)methyl]phenol, dilauryl thiodipropionate, and distearyl 3,3'-thiodipropionate. These antioxidants can be used alone or in combination. Examples of commercially available antioxidants include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd. In the third reaction step, the same solvent as that used in the first reaction step can be used.

[0082] The reaction ratio of intermediate product (a') and intermediate product (b') can be appropriately changed depending on the desired molecular design. However, from the viewpoint of improving excellent adhesion, excellent elongation, and low dielectric properties in a balanced manner, the hydroxyl group equivalent of intermediate product (b') relative to 1 equivalent of active ester group of intermediate product (a') is preferably in the range of 0.1 to 0.9 mol, more preferably in the range of 0.2 to 0.8 mol, and even more preferably in the range of 0.3 to 0.8 mol.

[0083] 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 aromatic monoalcohol (B), which can increase the purity of the resulting phosphorus-containing active ester.

[0084] (Resin having an acid group and a polymerizable unsaturated group) The resin composition of the present embodiment contains a resin having an acid group and a polymerizable unsaturated group as an essential component. Examples of the resin having an acid group and a polymerizable unsaturated group of the present embodiment include the following [1] to [6]: [1] an epoxy resin (B1) having an acid group and a polymerizable unsaturated group, [2] Urethane resin (B2) having an acid group and a polymerizable unsaturated group [3] (Meth)acrylate resin (B3) having an acid group and a polymerizable unsaturated group, [4] Amide-imide resin (B4) having an acid group and a polymerizable unsaturated group, [5] Acrylamide resin (B5) having an acid group and a polymerizable unsaturated group, [6] Ester resin (B6) having an acid group and a polymerizable unsaturated group, The epoxy resin (B1) to the urethane resin (B6) will be explained in the following order.

[0085] <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> Examples of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group of the present embodiment include an epoxy (meth)acrylate resin having an acid group, which is produced from an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), and a polybasic acid anhydride (b1-3) as essential reaction raw materials; and an epoxy (meth)acrylate resin having an acid group and a urethane bond, which is produced from an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), a polybasic acid anhydride (b1-3), a polyisocyanate compound (b1-4), and a (meth)acrylate compound (b1-5) having a hydroxyl group as reaction raw materials.

[0086] The specific structure of the epoxy resin (b1-1) is not particularly limited as long as it has a plurality of epoxy groups in the resin. Examples of the epoxy resin (b1-1) include bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, biphenol-type epoxy resins, hydrogenated biphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol novolac-type epoxy resins, naphthol novolac-type epoxy resins, naphthol-phenol co-condensed novolac-type epoxy resins, naphthol-cresol co-condensed novolac-type epoxy resins, phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, dicyclopentadiene-phenol addition reaction-type epoxy resins, biphenyl aralkyl-type epoxy resins, fluorene-type epoxy resins, xanthene-type epoxy resins, dihydroxybenzene-type epoxy resins, trihydroxybenzene-type epoxy resins, and oxazolidone-type epoxy resins. These epoxy resins can be used alone or in combination of two or more.

[0087] Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Examples of the hydrogenated bisphenol epoxy resin include hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol B epoxy resin, hydrogenated bisphenol E epoxy resin, hydrogenated bisphenol F epoxy resin, and hydrogenated bisphenol S epoxy resin. Examples of the biphenol type epoxy resin include 4,4'-biphenol type epoxy resin, 2,2'-biphenol type epoxy resin, tetramethyl-4,4'-biphenol type epoxy resin, and tetramethyl-2,2'-biphenol type epoxy resin. Examples of the hydrogenated biphenol type epoxy resin include hydrogenated 4,4'-biphenol type epoxy resin, hydrogenated 2,2'-biphenol type epoxy resin, hydrogenated tetramethyl-4,4'-biphenol type epoxy resin, and hydrogenated tetramethyl-2,2'-biphenol type epoxy resin. The epoxy resin (b1-1) can be used alone or in combination of two or more kinds.

[0088] Examples of the unsaturated monobasic acid (b1-2) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Acid halides and esters of the unsaturated monobasic acids can also be used. Furthermore, compounds represented by the following general formula (4) can also be used. [ka] [In the above general formula (4), X 41 represents an alkylene chain having 1 to 10 carbon atoms, a polyoxyalkylene chain, a (poly)ester chain, an aromatic hydrocarbon chain, or a (poly)carbonate chain; X 41 A hydrogen atom in the structure of Y may be substituted with a halogen atom or an alkoxy group; 41 is a hydrogen atom or a methyl group.

[0089] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain. An example of the (poly)ester chain is a (poly)ester chain represented by the following general formula (5). [ka] [In the above general formula (5), R 51 and R 52 represents an alkylene group having 1 to 10 carbon atoms, and n represents an integer of 1 to 5.

[0090] Examples of the aromatic hydrocarbon chain include a phenylene chain, a naphthylene chain, a biphenylene chain, a phenylnaphthylene chain, a binaphthylene chain, etc. Furthermore, a hydrocarbon chain having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, or a phenanthrene ring as a partial structure can also be used. An example of the (poly)carbonate chain is a (poly)carbonate chain represented by the following general formula (6). [ka] [In the above general formula (6), R 61 represents an alkylene group having 1 to 10 carbon atoms, and n 61 represents an integer from 1 to 5.] The molecular weight of the compound represented by formula (4) is preferably in the range of 100 to 500, more preferably in the range of 150 to 400. The unsaturated monobasic acids (b1-2) can be used alone or in combination of two or more kinds.

[0091] Examples of the polybasic acid anhydride (b1-3) include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, aromatic polybasic acid anhydrides, acid halides of aliphatic polybasic acid anhydrides, acid halides of alicyclic polybasic acid anhydrides, and acid halides of aromatic polybasic acid anhydrides.

[0092] Examples of the aliphatic polybasic acid anhydrides include anhydrides of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, etc. The aliphatic hydrocarbon group of the aliphatic polybasic acid anhydride may be either linear or branched, and may have an unsaturated bond in the structure. In the present disclosure, the alicyclic polybasic acid anhydride is one in which an acid anhydride group is bonded to an alicyclic structure, and the presence or absence of aromatic rings in other structural positions is not important. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydrides. Examples of the aromatic polybasic acid anhydrides include anhydrides of phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid. The polybasic acid anhydrides (b1-3) can be used alone or in combination of two or more. Among these, tetrahydrophthalic anhydride, succinic anhydride, and cyclohexanedicarboxylic anhydride are preferred because they can provide a curable composition capable of forming a cured product that can improve elongation, adhesion, and low dielectric properties in a balanced manner.

[0093] Examples of the polyisocyanate compound (b1-4) include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate. aromatic diisocyanate compounds such as methyl methyl ether, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, and o-tolidine diisocyanate; polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following general formula (7); and isocyanurate-modified products, biuret-modified products, and allophanate-modified products of these. The polyisocyanate compounds (b1-4) can be used alone or in combination of two or more kinds. [ka] [In the above general formula (7), R 13 and R 15 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; R 15 each independently represents an alkyl group having 1 to 4 carbon atoms, i7 is 0 or an integer of 1 to 3, and m is an integer of 1 or greater.]

[0094] Examples of the (meth)acrylate compound (b1-5) having a hydroxyl group include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. In addition, (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds described above, and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the various hydroxyl group-containing (meth)acrylate compounds described above, can also be used. Among these, those having a molecular weight of 1,000 or less are preferred, since they provide a curable composition capable of forming a cured product that can improve elongation, adhesion, and low dielectric properties in a balanced manner. Furthermore, when the hydroxyl group-containing (meth)acrylate compound (b1-4) is an oxyalkylene-modified compound or a lactone-modified compound, it is preferred that the weight average molecular weight (Mw) is 1,000 or less. The (meth)acrylate compound (b1-4) having a hydroxyl group can be used alone or in combination of two or more kinds.

[0095] The method for producing the epoxy resin (B1) having an acid group and a polymerizable unsaturated group of the present embodiment is not particularly limited, and any method may be used. The production of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary. In this embodiment, the method for producing the epoxy resin (B1) having an acid group and a polymerizable unsaturated group is not particularly limited, as long as it uses an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), and a polybasic acid anhydride (b1-3) as essential reaction raw materials, or an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), a polybasic acid anhydride (b1-3), a polyisocyanate compound (b1-4), and a (meth)acrylate compound (b1-5) having a hydroxyl group as reaction raw materials. For example, the epoxy resin (B1) may be produced by a method in which all of the reaction raw materials are reacted at once, or by a method in which the reaction raw materials are reacted sequentially. Among these, a method in which the epoxy resin (b1-1) is first reacted with the unsaturated monobasic acid (b1-2), and then the polybasic acid anhydride (b1-3) is reacted is preferred because it allows for easy reaction control. The reaction can be carried out, for example, by reacting an epoxy resin (b1-1) with an unsaturated monobasic acid (b1-2) in the presence of a basic catalyst at a temperature of 100 to 150°C, and then adding a polybasic acid anhydride (b1-3) to the reaction system and reacting at a temperature of 80 to 120°C. In this embodiment, the reaction ratio of the epoxy resin (b1-1) and the unsaturated monobasic acid (b1-2) is preferably in the range of 0.9 to 1.1 moles of the unsaturated monobasic acid (b1-2) per mole of epoxy groups in the epoxy resin (b1-1). The reaction ratio of the polybasic acid anhydride (b1-3) is preferably in the range of 0.2 to 1.0 moles per mole of epoxy groups in the epoxy resin (b1-1).

[0096] Examples of the organic solvent include hydrocarbon solvents such as toluene, xylene, heptane, hexane, and mineral spirits; ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, cyclohexanone, and dimethylacetamide; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene, xylene, and solvent naphtha; alicyclic solvents such as cyclohexane and methylcyclohexane; carbitol, cellosolve, methanol, ethanol, propanol, isopropanol, butanol, and cyclohexanol. Examples of suitable organic solvents include alcohol solvents such as ethanol and propylene glycol monomethyl ether; ether solvents such as propyl ether, methyl cellosolve, cellosolve, butyl cellosolve, and methyl carbitol; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; vegetable oils and fats such as soybean oil, linseed oil, rapeseed oil, and safflower oil; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. These organic solvents can be used alone or in combination of two or more.

[0097] In addition, commercially available organic solvents can also be used. Examples of commercially available organic solvents include "No. 1 Spindle Oil," "No. 3 Solvent," "No. 4 Solvent," "No. 5 Solvent," "No. 6 Solvent," "Naphtesol H," "Alkene 56NT," "AF Solvent No. 4," "AF Solvent No. 5," "AF Solvent No. 6," and "AF Solvent No. 7" manufactured by ENEOS Corporation; "Diadol 13" and "Dialene 168" manufactured by Mitsubishi Chemical Corporation; "F Oxocol" and "F Oxocol 180" manufactured by Nissan Chemical Industries, Ltd.; "Supersol LA35" and "Supersol LA38" manufactured by Idemitsu Kosan Co., Ltd.; and "ExxonMobil Examples include Exxor D80, Exxor D110, Exxor D120, Exxor D130, Exxor D160, Exxor D100K, Exxor D120K, Exxor D130K, Exxor D280, Exxor D300, and Exxor D320 manufactured by Exxor Chemical Co., Ltd. The organic solvents can be used alone or in combination of two or more. In the present embodiment, the amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, as this improves the reaction efficiency.

[0098] Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, tri quaternary ammonium salts such as octylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octoate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, etc. can also be used. The basic catalysts can be used alone or in combination of two or more. The amount of the basic catalyst added is preferably in the range of 0.001 to 5 parts by mass per 100 parts by mass of the total of the reaction raw materials.

[0099] In the present embodiment, the acid value of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group is preferably in the range of 30 to 150 mgKOH / g, more preferably in the range of 40 to 120 mgKOH / g, because a curable composition capable of forming a cured product capable of improving elongation, adhesion, and low dielectric properties in a well-balanced manner can be obtained. Note that the acid value of the epoxy resin (B1) having an acid group and a polymerizable unsaturated group in the present disclosure is a value measured by the neutralization titration method of JIS 0070 (1992).

[0100] <Urethane resin having an acid group and a polymerizable unsaturated group (B2)> Examples of the urethane resin (B2) having an acid group and a polymerizable unsaturated group of the present embodiment include a resin obtained by reacting a polyisocyanate compound (b1-4), a hydroxyl group-containing (meth)acrylate compound (b1-5), a carboxyl group-containing polyol compound (b2-1), and, if necessary, a polybasic acid anhydride (b1-3) and a polyol compound (b2-2) other than the carboxyl group-containing polyol compound (b2-1); a resin obtained by reacting a polyisocyanate compound (b1-4) with a hydroxyl group-containing (meth)acrylate compound (b1-5), a carboxyl group-containing polyol compound (b2-1), and, if necessary, a polybasic acid anhydride (b1-3), and a polyol compound (b2-2) other than the carboxyl group-containing polyol compound (b2-1); Examples of the hydroxyl group-containing (meth)acrylate compound (b1-5) include a resin obtained by reacting a hydroxyl group-containing (meth)acrylate compound (b1-5) with a polybasic acid anhydride (b1-3) and a polyol compound (b2-2) other than the carboxyl group-containing polyol compound (b2-1); or a resin obtained by reacting an epoxy resin (b1-1), an unsaturated monobasic acid (b1-2), a polybasic acid anhydride (b1-3), a polyisocyanate compound (b1-4) and a hydroxyl group-containing (meth)acrylate compound (b1-5).

[0101] Examples of the carboxyl group-containing polyol compound (b2-1) include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, etc. The carboxyl group-containing polyol compounds can be used alone or in combination of two or more. Examples of polyol compounds (b2-2) other than the carboxyl group-containing polyol compound (b2-1) include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; aromatic polyol compounds such as biphenol and bisphenol; (poly)oxyalkylene modified compounds in which (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains have been introduced into the molecular structure of the above-mentioned various polyol compounds; and lactone modified compounds in which (poly)lactone structures have been introduced into the molecular structure of the above-mentioned various polyol compounds. The polyol compounds other than the carboxyl group-containing polyol compounds can be used alone or in combination of two or more.

[0102] The method for producing the urethane resin (B2) having an acid group and a polymerizable unsaturated group in this embodiment is not particularly limited, and any method may be used. The production of the urethane resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary. The organic solvent may be the same as the organic solvent described above in the section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group>, and the organic solvent may be used alone or in combination of two or more. The basic catalyst may be the same as the basic catalyst described above in the section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group>, and the basic catalyst may be used alone or in combination of two or more.

[0103] <(Meth)acrylate Resin Having an Acid Group and a Polymerizable Unsaturated Group (B3)> The (meth)acrylate resin (B3) having an acid group and a polymerizable unsaturated group in this embodiment may be any resin as long as it has an acid group and a (meth)acrylate group, and may include a (meth)acrylate ester in which a hydrogen atom of a carboxylic acid is substituted with an alkyl group. For example, a reaction product obtained by polymerizing a (meth)acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group as an essential component to obtain a (meth)acrylic resin intermediate, and then reacting the resulting (meth)acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group that can react with the functional group, thereby introducing a (meth)acryloyl group, or a resin obtained by reacting a polybasic acid anhydride (b1-3) with the hydroxyl group in the reaction product, may be mentioned.

[0104] In this embodiment, the (meth)acrylic resin intermediate may be a copolymer of the (meth)acrylate compound (α) and, if necessary, other polymerizable unsaturated group-containing compounds. Examples of such other polymerizable unsaturated group-containing compounds include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alicyclic structure-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; aromatic ring-containing (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, and phenoxyethyl acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. The other polymerizable unsaturated group-containing compounds can be used alone or in combination of two or more kinds.

[0105] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group possessed by the (meth)acrylate compound (α), but the following combinations are preferred from the viewpoint of reactivity. That is, when a hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate compound (β). When a carboxyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred to use a glycidyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When an isocyanate group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred to use a hydroxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). When a glycidyl group-containing (meth)acrylate is used as the (meth)acrylate compound (α), it is preferable to use a carboxyl group-containing (meth)acrylate as the (meth)acrylate compound (β). The (meth)acrylate compound (β) can be used alone or in combination of two or more kinds.

[0106] The method for producing the (meth)acrylate resin (B3) having an acid group and a polymerizable unsaturated group in this embodiment is not particularly limited, and any method may be used. The production of the (meth)acrylate resin (B3) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary. As the organic solvent, the same organic solvents as those described in the above section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> can be used, and the organic solvents can be used alone or in combination of two or more. As the basic catalyst, the same basic catalysts as those described in the above section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> can be used, and the basic catalysts can be used alone or in combination of two or more.

[0107] The acid value of the (meth)acrylate resin (B3) having an acid group and a polymerizable unsaturated group in this embodiment is preferably in the range of 30 to 150 mgKOH / g, more preferably in the range of 40 to 120 mgKOH / g, because a curable composition capable of forming a cured product capable of improving elongation, adhesion, and low dielectric properties in a well-balanced manner can be obtained. Note that the acid value of the (meth)acrylate resin (B3) having an acid group and a polymerizable unsaturated group in the present disclosure is a value measured by the neutralization titration method of JIS K 0070 (1992).

[0108] <Amide-imide resin having an acid group and a polymerizable unsaturated group (B4)> In this embodiment, the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group may be, for example, a compound obtained by reacting an amide-imide resin (b4-1) having an acid group and / or an acid anhydride group with a (meth)acrylate compound (b1-5) having a hydroxyl group and / or a (meth)acrylate compound having an epoxy group, and, if necessary, with a compound having one or more reactive functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an isocyanate group, a glycidyl group, and an acid anhydride group. The compound having the reactive functional group may or may not have a (meth)acryloyl group. The amide-imide resin (b4-1) having an acid group and / or an acid anhydride group may have either an acid group or an acid anhydride group, or both. From the viewpoint of reactivity and reaction control with the (meth)acrylate compound (1-5) having a hydroxyl group or the epoxy compound having a (meth)acryloyl group, the amide-imide resin (b4-1) preferably has an acid anhydride group, and more preferably has both an acid group and an acid anhydride group. The acid value of the solid content of the amide-imide resin (b4-1) measured under neutral conditions, i.e., conditions under which the acid anhydride group is not ring-opened, is preferably in the range of 60 to 350 mg KOH / g. On the other hand, the acid value measured under conditions under which the acid anhydride group is ring-opened, such as in the presence of water, is preferably in the range of 61 to 360 mg KOH / g.

[0109] Furthermore, the amide-imide resin (b4-1) may contain, as necessary, a polybasic acid as a reaction raw material in addition to the polyisocyanate compound (b1-4) and the polybasic acid anhydride (b1-3). The polybasic acid may be any compound having two or more carboxyl groups in one molecule. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 -dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, biphenyl dicarboxylic acid, biphenyl tricarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, etc. Furthermore, as the polybasic acid, for example, a copolymer of a conjugated diene vinyl monomer and acrylonitrile, which has a carboxyl group in its molecule, can also be used. The above polybasic acids can be used alone or in combination of two or more kinds.

[0110] The (meth)acrylate compound having an epoxy group is not particularly limited in structure as long as it has a (meth)acryloyl group and an epoxy group in its molecular structure, and a wide variety of compounds can be used. Examples include glycidyl group-containing (meth)acrylate monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate, as well as mono(meth)acrylates of diglycidyl ether compounds such as hydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The above (meth)acrylate compounds having an epoxy group can be used alone or in combination of two or more kinds.

[0111] The specific structure or production method of the amide-imide resin (b4-1) having an acid group and / or an acid anhydride group is not particularly limited, and a wide variety of general amide-imide resins can be used. The amide-imide resin (b4-1) of this embodiment is preferably obtained, for example, from a polyisocyanate compound (b1-4) and a polybasic acid anhydride (b1-3) as reaction raw materials. In the present embodiment, the polyisocyanate compound (b1-4) is preferably an alicyclic diisocyanate compound or a modified product thereof, or an aliphatic diisocyanate compound or a modified product thereof, since a resin composition having an acid group and a polymerizable unsaturated group and having high solvent solubility can be obtained, and more preferably an alicyclic diisocyanate or an isocyanurate-modified product thereof, or an aliphatic diisocyanate or an isocyanurate-modified product thereof. In this embodiment, the proportion of the total mass of the alicyclic diisocyanate compound or modified product thereof and the aliphatic diisocyanate compound or modified product thereof in the total mass of the polyisocyanate compound (b1-4) is preferably 70 mass% or more, and more preferably 90 mass% or more. Furthermore, when an alicyclic diisocyanate compound or a modified product thereof is used in combination with an aliphatic diisocyanate compound or a modified product thereof, the mass ratio of the two (alicyclic diisocyanate compound or a modified product thereof / aliphatic diisocyanate compound or a modified product thereof) is preferably in the range of 30 / 70 to 70 / 30.

[0112] The method for producing the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group in this embodiment is not particularly limited, and any method may be used. The production of the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary. As the basic catalyst, the same basic catalysts as those described in the above section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group> can be used, and the basic catalysts can be used alone or in combination of two or more. The organic solvent may be the same as the organic solvents described in the above section <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group>, and the organic solvents may be used alone or in combination of two or more.

[0113] In this embodiment, the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group can be prepared by using other reaction raw materials in addition to the reaction raw materials of the amide-imide resin (b4-1) having an acid group and / or an acid anhydride group, the hydroxyl-containing (meth)acrylate compound (b1-5) and / or the (meth)acrylate compound (b4-2) having an epoxy group, depending on the desired resin performance, etc. In this case, the proportion of the total mass of the components (b4-1) to (b4-2) in the total mass of the reaction raw materials for the resin (B4) having an acid group and a polymerizable unsaturated group is preferably 80 mass% or more, more preferably 90 mass% or more.

[0114] In this embodiment, the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group may be produced by any method without particular limitation. For example, the amide-imide resin (b4-1) and the reaction raw materials including the hydroxyl group-containing (meth)acrylate compound (b1-5) and / or the epoxy group-containing (meth)acrylate compound (b4-2) may be reacted all at once, or the reaction raw materials may be reacted sequentially. Furthermore, for example, the reaction between the amide-imide resin (b4-1) and the hydroxyl group-containing (meth)acrylate compound (b1-5) may be carried out by heating and stirring at a temperature of about 80 to 140°C in the presence of a suitable basic catalyst. The production of the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and a basic or acidic catalyst may be used, if necessary.

[0115] The basic catalyst may be the same as the acidic catalyst and basic catalyst described in the section above under <Epoxy resin (B1) having an acid group and a polymerizable unsaturated group>, and these may be used alone or in combination of two or more. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Solid acid catalysts having a strong acid such as a sulfonyl group can also be used. These acid catalysts can be used alone or in combination of two or more.

[0116] The acid value of the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group in this embodiment is preferably in the range of 30 to 150 mgKOH / g, more preferably in the range of 40 to 120 mgKOH / g, because a curable composition capable of forming a cured product capable of improving elongation, adhesion, and low dielectric properties in a well-balanced manner can be obtained. Note that the acid value of the amide-imide resin (B4) having an acid group and a polymerizable unsaturated group in the present disclosure is a value measured by the neutralization titration method of JIS K 0070 (1992).

[0117] <Acrylamide resin having an acid group and a polymerizable unsaturated group (B5)> Examples of the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group of this embodiment include a resin obtained by reacting a phenolic hydroxyl group-containing compound (b5-1), an alkylene carbonate (b5-2a) or an alkylene oxide (b5-2b), an N-alkoxyalkyl (meth)acrylamide compound (b5-3), a polybasic acid anhydride (b1-3), and, if necessary, an unsaturated monobasic acid (b1-2) as reaction raw materials.

[0118] In this embodiment, the phenolic hydroxyl group-containing compound (b5-1) refers to a compound having at least one phenolic hydroxyl group in its molecule. Examples of the phenolic hydroxyl group-containing compound (b5-1) include a compound represented by any one of the following general formulas (8.1) to (8.5), a reaction product obtained by using, as essential reaction raw materials, an aromatic polyhydroxy compound (b5-4) and a compound represented by any one of the following general formulas (9.1) to (9.5), and a novolac-type phenolic resin obtained by using, as reaction raw materials, one or more of the aromatic polyhydroxy compound (b5-4) and other compounds (b5-5) having one phenolic hydroxyl group in their molecules. [ka] (In the above general formulas (8.1) to (8.5), R 81 ~R 84 and R 87 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, or a halogen atom; R 85 and R 86 each independently represents a hydrogen atom or a methyl group; j 81 ~j 84 and j 87 Each independently represents an integer of 0 or 1 or more, preferably 0 or an integer of 1 to 3, and more preferably 0 or 1. 81 ~k 84 and k 87each independently represents an integer of 1 or more, preferably 2 or 3. The positions of the substituents on the aromatic rings in the general formulas (8.1) to (8.5) are arbitrary. For example, in the naphthalene ring of the general formula (8.2), they may be substituted with any hydrogen atom on the ring. In the general formula (8.3), they may be substituted with any hydrogen atom on the benzene ring present in one biphenyl molecule. In the general formula (8.4), they may be substituted with any hydrogen atom on the benzene ring present in one aralkyl molecule. In the general formula (8.5), they may be substituted with any hydrogen atom on the benzene ring present in one aralkyl molecule. When the number of substituents in one molecule is j, 81 ~j 84 and k 81 ~k 84 This indicates that [ka] (In the above general formulas (9.1) to (9.5), h 91 represents 0 or 1, R 91 ~R 96 each independently represents a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group; k 91 ~k 96 each independently represents 0 or an integer of 1 to 4, and Z 91 ~Z 96 each independently represents a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group; Y 91 represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, and n 91 represents an integer from 1 to 4.) The compounds represented by the above general formulas (9.1) to (9.5) can be used alone or in combination of two or more kinds.

[0119] Examples of the aromatic polyhydroxy compound (b5-4) include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, bisphenol, and compounds having one or more substituents on the aromatic nucleus thereof. Examples of the substituent on the aromatic nucleus include monovalent aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl; alkoxy groups such as methoxy, ethoxy, propyloxy, and butoxy; halogen atoms such as fluorine, chlorine, and bromine; phenyl, naphthyl, and anthryl groups, and aryl groups having the aliphatic hydrocarbon group, alkoxy group, or halogen atom substituted on the aromatic nucleus; phenyloxy, naphthyloxy, and aryloxy groups having the aliphatic hydrocarbon group, alkoxy group, or halogen atom substituted on the aromatic nucleus; phenylmethyl, phenylethyl, naphthylmethyl, and naphthylethyl groups, and aralkyl groups having the aliphatic hydrocarbon group, alkoxy group, or halogen atom substituted on the aromatic nucleus. These aromatic polyhydroxy compounds can be used alone or in combination of two or more. Among these, compounds containing no halogen are preferred because they can provide resins having acid groups and polymerizable unsaturated groups with high insulating reliability.

[0120] Examples of the novolac phenolic resin include resins obtained by reacting one or more compounds having one phenolic hydroxyl group in the molecule with an aldehyde compound in the presence of an acid catalyst.

[0121] The above-mentioned other compounds (b5-5) having one phenolic hydroxyl group in the molecule may be any aromatic compound having one hydroxyl group on the aromatic nucleus, such as phenol or a phenol compound having one or more substituents on the phenolic aromatic nucleus, naphthol or a naphthol compound having one or more substituents on the naphthol aromatic nucleus, and anthracenol or anthracenol compound having one or more substituents on the anthracenol aromatic nucleus. Examples of the substituent on the aromatic nucleus include monovalent aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, aryl groups, aryloxy groups, and aralkyl groups, with specific examples being as described above. These compounds having one phenolic hydroxyl group can be used alone or in combination of two or more.

[0122] Examples of the aldehyde compound include formaldehyde; alkyl aldehydes such as acetaldehyde, propyl aldehyde, butyl aldehyde, isobutyl aldehyde, pentyl aldehyde, and hexyl aldehyde; hydroxybenzaldehydes such as salicyl aldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, and 3,4-dihydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde; Examples of the benzaldehyde include aldehydes having both a hydroxy group and an alkoxy group, such as 4-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, and 4-hydroxy-3,5-dimethoxybenzaldehyde; alkoxybenzaldehydes, such as methoxybenzaldehyde and ethoxybenzaldehyde; hydroxynaphthaldehydes, such as 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, and 6-hydroxy-2-naphthaldehyde; and halogenated benzaldehydes, such as brombenzaldehyde.

[0123] Examples of alkylene carbonates (b5-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. Among these, ethylene carbonate or propylene carbonate is preferred because it can provide a curable composition that can improve elongation, adhesion, and low dielectric properties in a well-balanced manner. The alkylene carbonates can be used alone or in combination of two or more.

[0124] Examples of alkylene oxides (b5-2b) include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. Among these, ethylene oxide or propylene oxide is preferred because it provides a curable composition that can improve elongation, adhesion, and low dielectric properties in a balanced manner. The alkylene oxides can be used alone or in combination of two or more.

[0125] Examples of the N-alkoxyalkyl(meth)acrylamide compound (b5-3) include N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-ethoxyethyl(meth)acrylamide, N-butoxyethyl(meth)acrylamide, etc. Among these, N-methoxymethyl(meth)acrylamide is preferred because it can provide a resin composition that can improve elongation, adhesion, and low dielectric properties in a balanced manner. The N-alkoxyalkyl(meth)acrylamide compounds (b5-3) can be used alone or in combination of two or more kinds.

[0126] In the present embodiment, when the N-alkoxyalkyl(meth)acrylamide compound (b5-3) is used as a reaction raw material for the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group, the equivalent ratio of the N-alkoxyalkyl(meth)acrylamide compound (b5-3) to the polybasic acid anhydride (b1-3) [(b5-3) / (b1-3)] is preferably in the range of 0.2 to 7, more preferably in the range of 0.25 to 6.7, since a curable composition capable of forming a cured product that can improve elongation, adhesion, and low dielectric properties in a balanced manner can be obtained.

[0127] In this embodiment, the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group may be produced by any method without particular limitation. For example, the resin may be produced by reacting all of the reactant materials at once, or by sequentially reacting the reactant materials. Among these, a preferred method is one in which the phenolic hydroxyl group-containing compound (b5-1) is first reacted with an alkylene carbonate (b5-2a) or an alkylene oxide (b5-2b) (e.g., in the presence of a basic catalyst at a temperature of 100 to 200°C), followed by reaction with an unsaturated monobasic acid (b1-2) and / or an N-alkoxyalkyl (meth)acrylamide compound (b2-3b) (e.g., in the presence of an acidic catalyst at a temperature of 80 to 140°C), followed by reaction with a polybasic acid anhydride (b1-3) (e.g., reaction at a temperature of 80 to 140°C), because this method makes it easier to control the reaction. The acrylamide resin (B5) having an acid group and a polymerizable unsaturated group in this embodiment is a resin obtained from the above-mentioned reaction raw materials. Examples of the acrylamide resin (B5) include a resin having a resin structure in which the structural moiety (I) represented by the following general formula (10.1) and the structural moiety (II) represented by the following general formula (10.2) are repeated as structural units, and a resin having a resin structure in which the structural moiety (III) represented by the following formula (10.3) and the structural moiety (IV) represented by the following formula (10.4) are repeated as structural units. [ka] [In the above formula (10.1) or (10.2), R b2 and R b8 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms; R b3 and R b9 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; n 1 and n 2 each independently represents 1 or 2; R b4 and R b10 each independently represents a methylene group or a structural moiety represented by any one of the following general formulas (11.1) to (11.5), and R b5 and R b6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R b5 and R b6 may be linked to form a saturated or unsaturated ring, R b11 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, and R b12 represents a hydrogen atom or a methyl group, and R b1 and R b7 are each independently the R b3 and the R b9 or the structural moiety (I) represented by formula (10.1) or the structural moiety (II) represented by formula (10.2) is R marked with an *. b4 or R b10 ] [ka] [In the above general formula (10.3) or (10.4), R b2 and R b8 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R b3 and R b9 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; n 3 and n 4 each independently represents 1 or 2; R b4 and Rb10 each independently represents a methylene group or a structural moiety represented by any one of the following formulas (11.1) to (11.5), and R b5 and R b6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R b5 and R b6 may be linked to form a saturated or unsaturated ring, R b11 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, and R b12 represents a hydrogen atom or a methyl group, and R b1 and R b7 are each independently the R b3 and the R b9 or the structural moiety (III) represented by general formula (10.3) or the structural moiety (IV) represented by general formula (10.4) is R marked with an *. b4 or R b10 ] [ka] [In the above general formulas (11.1) to (11.5), h 91 represents 0 or 1, R 91 ~R 96 each independently represents a monovalent aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group; n 91 ~n 96 each independently represents 0 or an integer of 1 to 4, and Y 91 represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, and n 91 represents an integer from 1 to 4, and R 111 ~R 116 each independently represents a hydrogen atom or a methyl group, and W represents the following formula (12.1) or (12.2). [ka] [In the above formula (12.1) or (12.2), R 121 and R 124each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms; R 122 and R 123 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, provided that R 122 and R 123 may be linked to form a saturated or unsaturated ring, R 125 represents a divalent hydrocarbon group having 1 to 12 carbon atoms, and R 126 represents a hydrogen atom or a methyl group.

[0128] The acid value of the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group in this embodiment is preferably in the range of 30 to 150 mgKOH / g, more preferably in the range of 40 to 120 mgKOH / g, because a curable composition capable of forming a cured product capable of improving elongation, adhesion, and low dielectric properties in a well-balanced manner can be obtained. Note that the acid value of the acrylamide resin (B5) having an acid group and a polymerizable unsaturated group in the present disclosure is a value measured based on the neutralization titration method of JIS K 0070 (1992).

[0129] <Ester resin having an acid group and a polymerizable unsaturated group (B6)> Examples of the ester resin (B6) having an acid group and a polymerizable unsaturated group in this embodiment include a resin obtained by reacting a phenolic hydroxyl group-containing compound (b5-1), an alkylene oxide (b5-2b) or an alkylene carbonate (b5-2a), an unsaturated monobasic acid (b1-2), and a polybasic acid anhydride (b1-3).

[0130] As the alkylene oxide (b5-2b), the same alkylene oxides as those exemplified above as the alkylene oxide (b5-2b) can be used. Among these, ethylene oxide or propylene oxide is preferred because it gives a curable composition capable of forming a cured product that can improve elongation, adhesion, and low dielectric properties in a balanced manner. The alkylene oxide (b5-2b) can be used alone or in combination of two or more kinds.

[0131] The alkylene carbonate (b5-2a) may be the same as those exemplified above for the alkylene carbonate (b5-2a). Among these, ethylene carbonate or propylene carbonate is preferred because it can provide a curable composition capable of forming a cured product that can improve elongation, adhesion, and low dielectric properties in a well-balanced manner. The alkylene carbonates (b5-2a) can be used alone or in combination of two or more kinds.

[0132] The method for producing the ester resin (B6) having an acid group and a polymerizable unsaturated group of this embodiment is not particularly limited, and any method may be used. The production of the ester resin having an acid group and a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst or an acidic catalyst, if necessary.

[0133] As the organic solvent, the same organic solvents as those exemplified above can be used, and the organic solvents can be used alone or in combination of two or more. As the basic catalyst, the same organic solvents as those exemplified above can be used, and the basic catalysts can be used alone or in combination of two or more. As the acidic catalyst, the same organic solvents as those exemplified above can be used, and the acidic catalysts can be used alone or in combination of two or more. The above are the essential components contained in the resin composition of this embodiment, which contains a resin having an acid group and a polymerizable unsaturated group, and a phosphorus-containing active ester.

[0134] (Optional addition ingredient) Furthermore, the resin composition 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.

[0135] The method for producing the resin composition of the present embodiment is not particularly limited, and the resin composition can be produced by kneading the various components described above using a kneader such as a roll mixer.

[0136] [Curable composition] The curable composition of this embodiment preferably contains the above-mentioned resin composition and a photopolymerization initiator. More specifically, a suitable curable composition of this embodiment contains the above-mentioned resin composition (essentially containing a phosphorus-containing active ester and a resin having an acid group and a polymerizable unsaturated group), a photopolymerization initiator, and, if necessary, a curing agent, a solvent, other resins, and additives. The curing agent may be an epoxy resin or another curing agent other than the epoxy resin (hereinafter referred to as "other curing agent"). The other resin may be a resin other than a phosphorus-containing active ester and a resin having an acid group and a polymerizable unsaturated group. The additive may be a filler, a flame retardant, a curing accelerator, an antioxidant, or an ultraviolet inhibitor.

[0137] In the curable composition of the present embodiment, the content of the phosphorus-containing active ester compound is preferably in the range of 5 to 95 mass %, more preferably in the range of 20 to 80 mass %, based on the solid content of the curable composition. In the curable composition of the present embodiment, the content of the resin having an acid group and a polymerizable unsaturated group is preferably in the range of 5 to 95 mass %, more preferably in the range of 20 to 80 mass %, of the solid content of the curable composition.

[0138] In the curable composition of the present embodiment, the content of the resin composition described above is preferably 10 to 95 mass %, and more preferably 20 to 80 mass %, relative to the total amount (100 mass %) of the curable composition. In the curable composition of the present embodiment, the content of the curing agent is preferably 0 to 50 mass %, and more preferably 5 to 40 mass %, relative to the total amount (100 mass %) of the curable composition. In the curable composition of the present embodiment, the content of the additive is preferably 0 to 10 mass %, and more preferably 0.1 to 5 mass %, relative to the total amount (100 mass %) of the curable composition. Hereinafter, the components that can be contained in the curable composition of the present embodiment, namely, the photopolymerization initiator, the curing agent, the solvent, the other resins, and the additives, will be described in detail.

[0139] (Photopolymerization initiator) The photopolymerization initiator can be selected appropriately depending on the type of active energy ray to be irradiated. It may also be used in combination with a photosensitizer such as an amine compound, a urea compound, a sulfur-containing compound, a phosphorus-containing compound, a chlorine-containing compound, or a nitrile compound. The photopolymerization initiator is preferably a radical polymerization initiator. Specific examples of such photopolymerization initiators include alkylphenone-based photopolymerization initiators such as 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and intramolecular hydrogen abstraction photopolymerization initiators such as benzophenone compounds. Further, specific examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. Commercially available photopolymerization initiators that can be used in this embodiment include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", "Omnirad-907", "Omnirad-4265", "Omnirad-1000", "Omnirad-651", "Omnirad-TPO", "Omnirad-819", "Omnirad-2022", "Omnirad-2100", "Omnirad-754", "Omnirad-784", and "Omnirad-50". 0," "Omnirad-81" (manufactured by IGM), "Kayacure-DETX," "Kayacure-MBP," "Kayacure-DMBI," "Kayacure-EPA," "Kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Baicure-10," "Baicure-55" (manufactured by Stauffer Chemical Co., Ltd.), "Trigonal P1" (manufactured by Akzo), "Sandray 1000" (manufactured by Sandoz), "Deep" (manufactured by Upjohn), "Quantacure-PDO," "Quantacure-ITX," "Quantacure-EPD" (manufactured by Ward-Blenkinsop), and "Runtecure-1104" (manufactured by Runtec).

[0140] The content of the photopolymerization initiator in the curable 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 phosphorus-containing active ester compound and the resin having an acid group and a polymerizable unsaturated group.

[0141] (Other various additives) The curable composition of the present embodiment may also contain appropriate amounts of various additives, such as curing agents, curing accelerators, other resins, organic solvents, flame retardants, fillers, pigments, antifoaming agents, viscosity modifiers, leveling agents, and storage stabilizers, as needed, within the scope of the purpose.

[0142] (hardening agent) Examples of the curing agent of the present embodiment include epoxy resins and other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents, etc.), and epoxy resins are preferred.

[0143] <Epoxy resin> The epoxy resin that is a suitable curing agent in this embodiment is not particularly limited, but is preferably, for example, a curable resin that contains two or more epoxy groups in the molecule and can be cured by forming a crosslinked network with the epoxy groups. The epoxy resin of the present embodiment is not particularly limited, but may be a novolac epoxy resin such as a phenol novolac epoxy resin, a cresol novolac epoxy resin, an α-naphthol novolac epoxy resin, a β-naphthol novolac epoxy resin, a bisphenol A novolac epoxy resin, or a biphenyl novolac epoxy resin; aralkyl-type epoxy resins such as phenol aralkyl-type epoxy resins, naphthol aralkyl-type epoxy resins, and phenol biphenyl aralkyl-type epoxy resins; Bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol AP-type epoxy resin, bisphenol AF-type epoxy resin, bisphenol B-type epoxy resin, bisphenol BP-type epoxy resin, bisphenol C-type epoxy resin, bisphenol E-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, and tetrabromobisphenol A-type epoxy resin; biphenyl-type epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton; Naphthalene-type epoxy resin; Binaphthol-type epoxy resin; Binaphthyl-type epoxy resin; Dicyclopentadiene-type epoxy resins such as dicyclopentadiene phenol-type epoxy resins; Glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane-type epoxy resins, triglycidyl-p-aminophenol-type epoxy resins, and diaminodiphenylsulfone-type glycidylamine-type epoxy resins; diglycidyl ester type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resins and hexahydrophthalic anhydride glycidyl ester type epoxy resins; Examples thereof include benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. Among these epoxy resins, so-called glycidyl ether type epoxy resins obtained by epoxidizing a phenol compound are preferred, and among them, novolac type epoxy resins, aralkyl type epoxy resins, and dicyclopentadiene type epoxy resins are more preferred from the viewpoint of dielectric properties. The above-mentioned epoxy resins may be used alone or in combination of two or more.

[0144] The epoxy equivalent of the epoxy resin of this embodiment is preferably 120 to 400 g / eq, and more preferably 150 to 300 g / eq. If the epoxy equivalent of the epoxy resin is 120 g / eq or more, the resulting cured product will have better dielectric properties, which is preferable, while if the epoxy equivalent of the epoxy resin is 400 g / eq or less, the elongation, adhesion, and low dielectric properties will be well balanced, which is preferable.

[0145] The softening point of the epoxy resin of this embodiment is preferably 20 to 200°C, more preferably 40 to 150°C, from the viewpoint of improving elongation, adhesion, and low dielectric properties in a balanced manner.

[0146] In this embodiment, with respect to the amount of epoxy resin used, when the ester groups in the phosphorus-containing active ester and the acid groups in the resin (B) having an acid group and a polymerizable unsaturated group are taken as (total) functional groups, the functional group equivalent ratio of the amount of epoxy resin used ((phosphorus-containing active ester + resin (B) having an acid group and a polymerizable unsaturated group) / epoxy resin) is preferably 0.2 to 2, more preferably 0.4 to 1.5. A functional group equivalent ratio of 0.2 or more is preferable because it can result in a curable composition that can form a cured product that can improve the elongation, adhesion, and low dielectric properties of the resulting cured product in a balanced manner. If the functional group equivalent ratio exceeds 2, heat resistance and curability will decrease, so it is preferable to use within the above range.

[0147] (Other hardeners) The curable composition of the present embodiment may contain another curing agent together with or instead of the epoxy resin. Examples of the other curing agent include, but are not limited to, an amine curing agent, an acid anhydride curing agent, and a phenolic resin curing agent. The amine curing agent is not particularly limited, but examples thereof include aliphatic amines such as diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, menthenediamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N-dimethylpiperazine, and triethylenediamine; and aromatic amines such as m-xylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0148] Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, methylbutenyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexene dicarboxylic anhydride.

[0149] Examples of the phenolic resin curing agent include phenol novolac resin, cresol novolac resin, naphthol novolac resin, bisphenol novolac resin, biphenyl novolac resin, dicyclopentadiene-phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, triphenolmethane type resin, tetraphenolethane type resin, and aminotriazine-modified phenolic resin. Any of the other curing agents mentioned above may be used alone or in combination of two or more.

[0150] In this embodiment, with respect to the amount of other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents), when the ester groups in the phosphorus-containing active ester and the acid groups in the resin (B) having an acid group and a polymerizable unsaturated group are taken as the (total) functional groups, the functional group equivalent ratio of the amount of the other curing agents used ((phosphorus-containing active ester + resin (B) having an acid group and a polymerizable unsaturated group) / other curing agents) is preferably 0.2 to 2, more preferably 0.4 to 1.5. A functional group equivalent ratio of 0.2 or more is preferred because it can improve the elongation, adhesion, and low dielectric properties of the resulting cured product in a balanced manner. If the functional group equivalent ratio exceeds 2, curability decreases, so it is preferable to use within the above range.

[0151] <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.

[0152] 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.

[0153] 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).

[0154] 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.

[0155] 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.

[0156] Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea. Of the above-mentioned curing accelerators, it is preferable to use 2-ethyl-4-methylimidazole and N,N-dimethyl-4-aminopyridine (DMAP).

[0157] The content of the curing accelerator in the curable composition of this embodiment can be adjusted as appropriate to obtain the desired curability, but is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group. A content of 0.01 part by mass or more of the curing accelerator is preferred because it provides excellent curability. On the other hand, a content of 5 parts by mass or less of the curing accelerator is preferred because it provides excellent insulation reliability. From the same perspective, 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, per 100 parts by mass of the total of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group.

[0158] (other resins) The curable composition of the present embodiment may contain other resins in addition to the epoxy resin or other curing agent, or in place of the epoxy resin or other curing agent. Specific examples of the other resins include, but are not limited to, maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolac resins, cyanate ester resins, styrene-maleic anhydride resins, allyl group-containing resins such as diallyl bisphenol and triallyl isocyanurate, polyphosphate esters, phosphate ester-carbonate copolymers, etc. These other resins may be used alone or in combination of two or more. The content of other resins in the curable composition of the present embodiment is preferably 50 mass % or less of the total.

[0159] (solvent) The curable composition of the present embodiment may be prepared without a solvent or may contain a solvent, which has the function of adjusting the viscosity of the curable composition. Specific examples of the solvent include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, and 1,2,4-trimethylbenzene; and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more. The content of the solvent in the curable composition of this embodiment is preferably 0 to 90 mass %, more preferably 10 to 90 mass %, and even more preferably 20 to 80 mass %, based on the total amount (100 mass %) of the curable composition. A solvent content of 10 mass % or more is preferred because of excellent handleability. On the other hand, a solvent content of 90 mass % or less is preferred from the viewpoint of economy.

[0160] (additives) The curable composition of the present embodiment may contain additives, such as the curing accelerators, flame retardants, and fillers.

[0161] <Flame retardant> The flame retardant of the present embodiment is not particularly limited, but examples thereof include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, and halogen-based flame retardants. The inorganic phosphorus-based flame retardant is not particularly limited, but examples thereof include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphoric acid amides.

[0162] The organic phosphorus flame retardant is not particularly limited, but examples thereof include methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, and stearyl acid phosphate. phosphate esters such as isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, and (2-hydroxyethyl) methacrylate acid phosphate; diphenylphosphines such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and diphenylphosphine oxide; 10-(2,5-dihydroxyphenyl)-10H-9-oxa phosphorus-containing phenols such as 10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphinyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol, and 1,5-cyclooctylenephosphinyl-1,4-phenyldiol; 9,10-dihydro-9-oxa-10-phos cyclic phosphorus compounds such as 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; and compounds obtained by reacting the above-mentioned phosphate esters, diphenylphosphine, or phosphorus-containing phenols with epoxy resins, aldehyde compounds, or phenol compounds. The halogen-based flame retardant is not particularly limited, but examples thereof include brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2-bis(tetrabromophthalimide), 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, tetrabromophthalic acid, etc. The above-mentioned flame retardants may be used alone or in combination of two or more.

[0163] The content of the flame retardant in this embodiment is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the total amount of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group. A flame retardant content of 0.1 parts by mass or more is preferred because it can impart flame retardancy. On the other hand, a flame retardant content of 50 parts by mass or less is preferred because it can impart flame retardancy while maintaining dielectric properties. From the same viewpoint, the content of the flame retardant is more preferably 1 part by mass or more, and more preferably 30 parts by mass or less, relative to 100 parts by mass of the total amount of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group.

[0164] (filler) Examples of the filler in this embodiment include organic fillers and inorganic fillers. The organic fillers have functions such as improving elongation and mechanical strength. The inorganic fillers have functions such as reducing the thermal expansion coefficient and imparting flame retardancy. The organic filler is not particularly limited, but examples thereof include polyamide particles. The inorganic filler is not particularly limited, but may include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black, etc. Among these, silica is preferably used. In this case, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. may be used as the silica.

[0165] 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.

[0166] The content of the filler in this embodiment is preferably 0.5 to 95 parts by mass, and more preferably 5 to 80 parts by mass, relative to 100 parts by mass of the total amount of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group. A filler content of 0.5 parts by mass or more is preferred because the effects of the filler can be fully imparted. On the other hand, the content of the filler is preferably 95 parts by mass or less so as not to increase the viscosity of the blend and impair moldability. From the same viewpoint, the content of the filler is more preferably 5 parts by mass or more, and more preferably 80 parts by mass or less, relative to 100 parts by mass of the total amount of the phosphorus-containing active ester and the resin having an acid group and a polymerizable unsaturated group. The method for producing the curable 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.

[0167] [Cured product] The cured product in this embodiment is obtained by curing the above-described curable composition. Since the phosphorus-containing active ester contained in the curable composition itself has a low dielectric loss tangent, the cured product obtained from the curable composition also has a low dielectric loss tangent. Furthermore, the obtained cured product can exhibit flexibility, adhesion to metals such as copper foil due to the flexibility, and low dielectric properties, which is a preferred embodiment. The cured product of this embodiment can be obtained by irradiating the curable composition with active energy rays. Examples of the active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere in order to efficiently carry out the curing reaction by ultraviolet rays.

[0168] In this embodiment, an ultraviolet lamp is generally used as the ultraviolet light source from the viewpoints of practicality and economy, and specific examples include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED. The cumulative light amount of the active energy rays is not particularly limited, but is preferably 0.1 to 50 kJ / m 2 is preferably 0.5 to 10 kJ / m 2 It is more preferable that the integrated light amount is within the above range, since it is possible to prevent or suppress the occurrence of uncured portions. The irradiation of the active energy rays may be carried out in one step, or may be carried out in two or more steps.

[0169] In the present embodiment, as another method for obtaining a cured product by subjecting the curable composition to a curing reaction, for example, the heating temperature during heat curing is not particularly limited, but is preferably 100 to 300°C, and the heating time is preferably 1 to 24 hours.

[0170] Applications in which the curable composition or cured product of this embodiment can be used include printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for buildup boards, insulating materials for circuit boards such as buildup adhesive films, resist materials, resin casting materials, adhesives, semiconductor encapsulation materials, semiconductor devices, prepregs, conductive pastes, buildup films, buildup substrates, fiber-reinforced composite materials, and molded articles obtained by curing the above-mentioned composite materials. Among these various applications, the curable composition of the present disclosure can be used as an insulating material for so-called electronic component-embedded substrates in which passive components such as capacitors and active components such as IC chips are embedded within the substrate. Furthermore, taking advantage of the properties of the cured product, such as excellent flexibility, adhesion, low dielectric properties, and heat resistance, the curable composition of the present disclosure is preferably used in semiconductor encapsulation materials, resist materials, semiconductor devices, prepregs, flexible wiring boards, circuit boards, buildup films, buildup substrates, multilayer printed wiring boards, fiber-reinforced composite materials, and molded articles obtained by curing the above-mentioned composite materials.

[0171] [Insulating material] The insulating material of this embodiment is made of the curable composition described above. Preferably, the insulating material of this embodiment is obtained by irradiating the curable composition described above with active energy rays to cure it. The insulating material of this embodiment has excellent elongation, adhesion, and low dielectric properties. Examples of the insulating material include the interlayer insulating material for build-up substrates described above, insulating materials for circuit boards such as adhesive films for build-up substrates, insulating materials for circuit boards, and insulating materials for substrates with built-in electronic components. For example, a build-up substrate can be produced from the curable composition by a method comprising the following three steps: The first step involves applying the curable composition containing an appropriate blend of rubber, filler, etc., to a circuit board with a circuit formed thereon using a spray coating method, curtain coating method, or the like, and then curing the composition. The second step involves subsequently drilling through-holes, etc., as needed, treating the surface with a roughening agent, rinsing the surface with hot water to form irregularities, and plating with a metal such as copper. The third step involves repeating these operations as desired to alternately build up resin insulating layers and conductor layers with a predetermined circuit pattern. It is preferable to drill through-holes after forming the outermost resin insulating layer. The first step can also be performed by laminating a build-up film that has been coated to the desired thickness and dried in advance, in addition to the solution coating method described above. Furthermore, the build-up substrate of the present disclosure can be produced by forming a roughened surface and eliminating the plating process by heat-pressing a copper foil with a resin, which is prepared by semi-curing the resin composition on the copper foil, onto a wiring board on which a circuit has been formed, at 170 to 250°C.

[0172] [Resist material] The resist member in this embodiment is composed of the curable composition described above. For example, the curable composition is applied onto a substrate, the organic solvent is volatilized and dried in a temperature range of about 60 to 100°C, and then exposed to active energy rays through a photomask on which a desired pattern is formed, and the unexposed portion is developed with an aqueous alkali solution, and further heat-cured in a temperature range of about 140 to 180°C to obtain the resist member. The resist member of this embodiment is excellent in low dielectric characteristics and elongation.

Example

[0173] Hereinafter, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited to the following examples in any way. In the following, "parts" and "%" are based on mass unless otherwise specified. Regarding GPC measurement, 1 1H-NMR measurement, 13 13C-NMR measurement, FD-MS spectrum measurement, they were measured under the following conditions and the like.

[0174] (Evaluation method) <GPC measurement> Measurement was carried out using the following measuring device and measuring conditions, and GPC charts of diphenyl isophthalate derivatives, phenolic hydroxyl group-containing resins, and active esters obtained in the following synthesis examples, examples, etc. were obtained. From the results of the GPC charts, it was confirmed that the target products (diphenyl isophthalate derivative (a'), phosphorus-containing active ester, and resin (B) having an acid group and a polymerizable unsaturated group) were generated from the decrease and disappearance of the raw material peaks. Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "GPC workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Developing solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Standard: In accordance with the measurement manual of the "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrenes with known molecular weights were used. (Polystyrene used) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation Sample: A 50 μl of a tetrahydrofuran solution of diphenyl isophthalate derivative (a') obtained in the following synthesis examples and examples, etc., and 1.0% by mass of the phosphorus-containing active ester in terms of solid content, filtered through a microfilter, was used.

[0175] <FD-MS spectrum measurement> The FD-MS spectrum was measured using the following measuring apparatus and measurement conditions. From this result, the mass peak corresponding to the compound with the repeat number p 11 = 1 was confirmed. Measuring apparatus: JMS-T100GC AccuTOF Measurement conditions Measurement range: m / z = 4.00 - 2000.00 Rate of change: 51.2 mA / min Final current value: 45 mA Cathode voltage: -10 kV Recording interval: 0.07 sec

[0176] < 1 H-NMR measurement> 1 H-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE Magnetic field strength: 600MHz Accumulation count: 32 times Solvent: DMSO-d6 Sample concentration: 30% by mass The aforementioned 1 From the results of the H-NMR chart, peaks derived from the target products were confirmed, confirming that the target products were obtained in each reaction. < 13 C-NMR measurement> 13 C-NMR: “JNM-ECA600” manufactured by JEOL RESONANCE Magnetic field strength: 150MHz Accumulation count: 320 times Solvent: DMSO-d6 Sample concentration: 30% by mass The aforementioned 13 From the results of the C-NMR chart, peaks derived from the target products were confirmed, confirming that the target products were obtained in each reaction.

[0177] <Theoretical phosphorus content> Theoretical phosphorus content (%) = 100 × [charged amount of phosphorus-containing raw material (parts by mass) × (phosphorus content of phosphorus-containing raw material (% by mass) / 100)] / (theoretical yield of phosphorus-containing compound synthesized using phosphorus-containing raw material) When a commercial product was used, the phosphorus content of the phosphorus-containing raw material was the value listed in the product catalog. The phosphorus-containing compound refers to the phosphorus-containing polyhydric alcohol compound (C), the phosphorus-containing active ester, and the phosphorus-containing intermediate product (b') used in the examples and comparative examples.

[0178] [Method for measuring elongation] The elongation was measured based on a tensile test. Specifically, a test piece 1 (cured product) similar to that described in the "Method for evaluating adhesion" section below was cut into a size of 10 mm x 80 mm, and a tensile test was performed on the 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

[0179] [Method for measuring dielectric constant] The curable compositions obtained in each of the Examples and Comparative Examples were 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 a 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.

[0180] [Method for measuring dielectric loss tangent] The curable compositions obtained in each of the Examples and Comparative Examples were 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 a 10 kJ / m 2 After irradiating the glass substrate with ultraviolet light, the coating was heated at 160°C for 1 hour to obtain a cured coating film. The cured coating film was then peeled off from the glass substrate to obtain a cured product. The product was then stored in a room at 23°C and 50% humidity for 24 hours to prepare a test specimen. The dielectric loss tangent of the test specimen at 1 GHz was measured using the cavity resonance method with an Agilent Technologies Network Analyzer E8362C.

[0181] [Method for evaluating adhesion] The adhesion was evaluated by measuring peel strength. Specifically, the curable 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) using a 50 μm applicator, and the applied compositions were irradiated with 10 kJ / m using a metal halide lamp. 2 After irradiating with ultraviolet light, the specimen 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 was cut into a size of 1 cm wide and 12 cm long, and the 90° peel strength (N / cm) was measured using a peel tester (A&D Tensilon, manufactured by A&D Co., Ltd., peel speed 50 mm / min). A higher value indicates better adhesion.

[0182] (Synthesis Example 1): Synthesis of diphenyl isophthalate derivative (1) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 864.0 parts by mass (8.0 mol) of o-cresol and 4140.0 parts by mass of toluene, and the system was purged with nitrogen under reduced pressure to allow dissolution. Next, 808 parts by mass of isophthalic acid chloride (molar number of acid chloride groups: 4.0 mol) was charged, and the system was purged with nitrogen under reduced pressure to allow dissolution. Subsequently, 2.07 parts by mass of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the system was controlled to 60°C or below, and 1648.0 parts by mass of 20% by mass aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued under the above conditions for 1.0 hour. After completion of the reaction, 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 to obtain diphenyl isophthalate derivative (1). GPC chart of the diphenyl isophthalate derivative (1): 1 The 1 H-NMR chart and FD-MS spectrum chart are shown in FIGS. 1 to 3, respectively.

[0183] (Synthesis Example 2): Synthesis of phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 200.0 parts by mass of 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., product name: HCA-HQ), 156.4 parts by mass of propylene carbonate, and 1.07 parts by mass of triphenylphosphine (hereinafter referred to as TPP). The temperature was raised to 190°C and the reaction was continued until completion, yielding a phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ). The hydroxyl equivalent of the phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) was confirmed to be 253 g / eq. The GPC chart of the phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) was as follows: 13 The C-NMR chart and FD-MS spectrum chart are shown in Figures 3 to 6, respectively.

[0184] (Synthesis Example 3): Synthesis of phosphorus-containing active ester (1) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 137.0 g of the isophthalic acid diphenyl derivative (1) obtained in Synthesis Example 1 above, 100.0 g of the phosphorus-containing polyhydric alcohol compound (PC-HCA-HQ) obtained in Synthesis Example 2 above, and 0.24 parts by mass of diazabicycloundecene (hereinafter abbreviated as "DBU") as a catalyst. The temperature was raised to 190°C and the reaction was carried out for 3 hours. Subsequently, the reaction was further carried out while removing o-cresol by vacuum distillation, thereby obtaining phosphorus-containing active ester (1). The functional group equivalent of the obtained phosphorus-containing active ester (1) was 486 g / eq based on the charge ratio. The GPC chart of the phosphorus-containing active ester (1) is as follows: 13 The C-NMR chart and FD-MS spectrum chart are shown in FIGS. 7 to 9, respectively.

[0185] (Synthesis Example 4): Synthesis of phosphorus-containing polyhydric alcohol compound (EC-HCA-HQ) A phosphorus-containing polyhydric alcohol compound (EC-HCA-HQ) was prepared by adding 200 parts by weight of 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., product name: HCA-HQ), 199.5 parts by weight of ethylene carbonate, and 0.96 parts by weight of TPP to a recovery flask equipped with a stirrer and stirring at 180°C until the reaction was complete. The hydroxyl equivalent of the phosphorus-containing polyhydric alcohol compound (EC-HCA-HQ) was confirmed to be 227 g / eq. The GPC chart of the phosphorus-containing polyhydric alcohol compound (EC-HCA-HQ) is shown in Figure 10.

[0186] (Synthesis Example 5): Synthesis of phosphorus-containing active ester (2) A phosphorus-containing active ester (2) was synthesized by the same procedure as in Synthesis Example 3, except that 60.0 parts by mass of EC-HCA-HQ prepared in Synthesis Example 4 above, 91.7 parts by mass of diphenyl isophthalate derivative (1), and 0.15 parts by mass of DBU were used instead of PC-HCA-HQ prepared in Synthesis Example 3 above. The functional group equivalent of the obtained active ester (2) was 465 g / eq based on the charge ratio. A GPC chart of the phosphorus-containing active ester (2) is shown in Figure 11.

[0187] (Synthesis Example 6): Synthesis of phosphorus-containing polyhydric alcohol compound (PC-HCA-NQ) 10-[ was used instead of HCA-HQ used in the above Synthesis Example 4. 2,5- A phosphorus-containing polyhydric alcohol compound (PC-HCA-NQ) was synthesized by the same procedure as in Synthesis Example 4, except that the starting materials were changed to 68.2 parts by mass of ethylene carbonate ((dihydroxynaphthyl)]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., Ltd., trade name: HCA=NQ), and 0.50 parts by mass of DBU. The hydroxyl equivalent of PC-HCA-NQ was determined to be 245 g / eq based on the charge ratio. A GPC chart of the phosphorus-containing polyhydric alcohol compound (PC-HCA-NQ) is shown in Figure 12.

[0188] (Synthesis Example 7): Synthesis of phosphorus-containing active ester (3) Phosphorus-containing active ester (3) was synthesized by the same procedure as in Synthesis Example 3, except that 71.5 parts by mass of PC-HCA-NQ synthesized in Synthesis Example 6 above, 100.9 parts by mass of diphenyl isophthalate derivative (1), and 0.34 parts by mass of DBU were used instead of PC-HCA-HQ synthesized in Synthesis Example 3 above, and 0.17 parts by mass of 4-dimethylaminopyridine (DMAP) was added. The functional group equivalent of the resulting phosphorus-containing active ester (3) was 484 g / eq, based on the charge ratio. A GPC chart of the phosphorus-containing active ester (3) is shown in Figure 13.

[0189] (Synthesis Example 8): Synthesis of phosphorus-containing polyhydric alcohol compound (PC-PPQ) A phosphorus-containing polyhydric alcohol compound (PC-PPQ) was synthesized by the same procedure as in Synthesis Example 2, except that the HCA-HQ used in Synthesis Example 2 was replaced with 100.0 parts by mass of diphenylphosphinyl hydroquinone (manufactured by Hokko Sangyo Co., Ltd., product name: PPQ (registered trademark)), 72.4 parts by mass of propylene carbonate, and 0.52 parts by mass of TPP. The hydroxyl equivalent of PC-PPQ was confirmed to be 208 g / eq. The GPC chart of the phosphorus-containing polyhydric alcohol compound (PC-PPQ) is shown in Figure 14.

[0190] (Synthesis Example 9): Synthesis of phosphorus-containing active ester (4) The same procedure as in Synthesis Example 3 was carried out, except that 70.0 parts by mass of PC-PPQ synthesized in Synthesis Example 8 above, 116.5 parts by mass of diphenyl isophthalate derivative (1), and 1.86 parts by mass of DBU were used instead of PC-HCA-HQ in Synthesis Example 3, to synthesize phosphorus-containing active ester (4). The functional group equivalent of the resulting phosphorus-containing active ester (4) was 447 g / eq, based on the charge ratio. A GPC chart of the phosphorus-containing active ester (4) is shown in Figure 15.

[0191] Synthesis Example 10: Preparation of Resin (1) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 123 parts by weight of diethylene glycol monoethyl ether acetate, and 214 parts by weight of orthocresol novolac epoxy resin "EPICLON N-680" (manufactured by DIC Corporation, softening point 86°C, epoxy equivalent: 214 g / eq) was dissolved therein. 0.9 parts by weight of dibutylhydroxytoluene and 0.2 parts by weight of methoquinone were added, followed by 72 parts by weight of acrylic acid and 1.4 parts by weight of triphenylphosphine. The mixture was reacted at 120°C for 10 hours while blowing air into it. Next, 72 parts by weight of diethylene glycol monoethyl ether acetate and 76 parts by weight of tetrahydrophthalic anhydride were added, and the mixture was reacted at 110°C for 3 hours to obtain Resin (1) having acid groups and polymerizable unsaturated groups. The nonvolatile content of this Resin (1) having acid groups and polymerizable unsaturated groups was 65% by weight, and the acid value of the solid content was 80 mgKOH / g. The acid value is a value measured based on the neutralization titration method of JIS K 0070 (1992).

[0192] (Synthesis Example 11): Preparation of Resin (2) Having an Acid Group and a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 499.7 parts by weight of diethylene glycol monomethyl ether acetate, and 244.3 parts by weight of an isocyanurate-modified isophorone diisocyanate (EVONIK "VESTANAT T-1890 / 100", NCO% = 17.2%) and 192.0 parts by weight of trimellitic anhydride were dissolved therein. 1.0 part by weight of dibutylhydroxytoluene was added. The mixture was reacted at 160°C for 6 hours under a nitrogen atmosphere, and the NCO% was confirmed to be 0.1 or less. Next, 0.4 parts by weight of methoquinone was added as a thermal polymerization inhibitor, followed by 147.6 parts by weight of a pentaerythritol polyacrylate mixture (Toagosei Co., Ltd. "Aronix M-306", hydroxyl value: 159.7 mg KOH / g) and 3.5 parts by weight of triphenylphosphine. The mixture was reacted at 110°C for 5 hours while blowing air into it. Then, 165.0 parts by mass of glycidyl methacrylate was added and reacted for 6 hours at 110° C. Next, 110.4 parts by mass of succinic anhydride was added and reacted for 5 hours at 110° C. to obtain a resin (2) having an acid group and a polymerizable unsaturated group. The acid value of the solid content of the resin (2) was 80 mgKOH / g.

[0193] (Comparative Synthesis Example 1) Synthesis of Comparative Intermediate (1) A flask equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer was charged with 330 parts by weight of a polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / eq, softening point 85°C) and 1,184 parts by weight of toluene. The system was then reduced pressure and replaced with nitrogen to dissolve the resin. Next, 101 parts by weight of isophthalic acid chloride was charged, followed by 0.59 parts by weight of tetrabutylammonium bromide (TBAB). While purging with nitrogen gas, the system was controlled to below 60°C, and 206 parts by weight of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was continued under these conditions for 1.0 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 reactants, 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 was removed by decanting, and then toluene was removed by vacuum dehydration to synthesize comparative intermediate (1). The GPC chart of comparative intermediate (1) is shown in FIG.

[0194] (Comparative Synthesis Example 2) Synthesis of phosphorus atom-containing compound (1) A flask equipped with a thermometer, a condenser, a fractionating column, and a stirrer was charged with 77.0 parts by mass of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 48.5 parts by mass of p-anisaldehyde, and 197.5 parts by mass of the comparative intermediate (1). The mixture was heated to 90°C and stirred while blowing in nitrogen. The mixture was then heated to 180°C and stirred for 5 hours, and then further heated to 190°C and stirred for 9 hours. Water was removed from the reaction mixture under reduced pressure with heating, to synthesize phosphorus-containing compound (1). The GPC chart of the phosphorus-containing compound (1) is shown in Figure 17.

[0195] (Comparative Synthesis Example 3) Phosphorus Atom-Containing Ester Compound (1) A flask equipped with a thermometer, dropping funnel, condenser, distillation column, and stirrer was charged with 193.8 parts by mass of phosphorus-containing compound (1) and 678.0 parts by mass of methyl isobutyl ketone. The system was then purged with nitrogen under reduced pressure to dissolve the compound. Next, 42.2 parts by mass of benzoyl chloride and 0.56 parts by mass of TBAP were added. The system was controlled to 60°C or below while purging with nitrogen gas, and 78 parts by mass of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued under the above conditions for 1.0 hour. After the reaction was completed, the mixture was allowed to stand and separated, and the aqueous layer was removed. Water was then added to the methyl isobutyl ketone layer containing the dissolved reactants, and the mixture was stirred and mixed for approximately 15 minutes. The mixture was then allowed to stand and separated, 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 methyl isobutyl ketone, and the phosphorus-containing ester compound (1) was synthesized. The GPC chart of the phosphorus atom-containing ester compound (1) is shown in FIG.

[0196] (Example 1: Preparation of resin composition (1) and curable composition (1)) A resin composition (1) was prepared by mixing 15 parts by mass of the phosphorus-containing active ester (1) obtained in Synthesis Example 3 and 62 parts by mass of the resin (1) having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 11. Furthermore, 15 parts by mass of the phosphorus-containing active ester (1) obtained in Synthesis Example 3, 62 parts by mass of the resin (1) having an acid group and a polymerizable unsaturated group obtained in Synthesis Example 11, 19.9 parts by mass of an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, 3.9 parts by mass of a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), 0.4 parts by mass of 2-ethyl-4-methylimidazole, and 0.3 parts by mass of 4-dimethylaminopyridine were mixed to obtain a curable composition (1).

[0197] Examples 2 to 9: Preparation of resin compositions and curable compositions The phosphorus-containing active esters (1) to (4) obtained in the above synthesis examples and the resins (1) to (2) having an acid group and a polymerizable unsaturated group were mixed in the composition ratios shown in Table 1 to prepare resin compositions (1) to (4).

[0198] Resin compositions (1) to (4) obtained in the above examples were mixed with an orthocresol novolac epoxy resin (EPICLON N-680 manufactured by DIC Corporation, epoxy equivalent: 214) as a curing agent, a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), 2-ethyl-4-methylimidazole, and 4-dimethylaminopyridine in the compositional ratios shown in Table 1 to obtain curable compositions (1) to (9). Then, various evaluations were performed on the curable compositions (1) to (9) according to the procedures of the evaluation methods described in the above (Evaluation Method) column. The results are shown in Table 1 below.

[0199] Comparative Examples 1 and 2: Preparation of Compositions As in Examples 1 to 9, compositions (C1) to (C2) and curable compositions (C1) to (C2) of Comparative Examples 1 and 2 were prepared by mixing the components in the ratios shown in Table 1. Various evaluations were then carried out on the curable compositions (C1) to (C2) of Comparative Examples 1 and 2. The results are shown in Table 1 below.

[0200] [Table 1]

[0201] From the results in Table 1, it can be seen that when the resin compositions of the Examples were used, cured products with superior elongation, adhesion, and dielectric properties were obtained compared to the Comparative Examples. [Industrial Applicability]

[0202] According to the present disclosure, it is possible to provide a resin composition having excellent elongation, adhesion, and dielectric properties in the resulting cured product, a curable composition containing the composition, and a resin composition, a curable composition, a cured product, an insulating material, and a resist member obtained using the curable composition.

Claims

1. a phosphorus-containing activated ester represented by the following general formula (1), which is prepared by reacting an aromatic compound having two or more carboxyl groups and / or an acid halide or ester thereof (A), an aromatic monoalcohol (B), a phosphorus-containing polyhydric alcohol compound (C), and an ether bond-containing aliphatic compound (D) as reaction raw materials; A resin composition comprising: a resin having an acid group and a polymerizable unsaturated group; 【Chemistry 1】 [In the above general formula (1), A represents a group derived from the phosphorus-containing polyhydric alcohol compound (C), R 1 and R 2 each independently represent a group derived from the ether bond-containing aliphatic compound (D), Q 1 and Q 2 each independently represent a group derived from the aromatic compound having two or more carboxyl groups and / or its acid halide or ester (A), Ar 1 and Ar 2 each independently represent a group derived from the aromatic monoalcohol (B), x 1 is an average repeat number of 0.1 or more, y 1 is an average repeat number of 1 or more, and z 1 is an average repeat number of 1 or more.]

2. In the general formula (1), A represents the following general formula (I): 【Chemistry 2】 [In the above general formula (I), M １ represents an aromatic group, R ３ and R ４ each independently represents a monovalent hydrocarbon group or a divalent hydrocarbon group, R ３ or R ４ When one of R is a divalent hydrocarbon group, the other is also a divalent hydrocarbon group, and R ３ and R ４ are bonded to each other to form a cyclic structure, and * in the general formula (I) represents a bond bonding to the oxygen atom. R １ and R ２ each independently represents a linear or branched alkylene group, Q １ and Q ２ represents a divalent aromatic group, Ar １ and Ar ２ The resin composition according to claim 1 , wherein each independently represents a monovalent aromatic group.

3. A resin composition described in claim 1, wherein the content of the phosphorus-containing active ester represented by the general formula (1) is in the range of 90 to 10 mass% relative to the total amount (100 mass%) of the resin composition.

4. A curable composition comprising the resin composition according to any one of claims 1 to 3 and a curing agent, wherein the curing agent is an epoxy resin, an amine curing agent, an acid anhydride curing agent, or a phenolic resin curing agent.

5. A cured product obtained by curing the curable composition according to claim 4.

6. An insulating material comprising the cured product according to claim 5.

7. A resist member comprising the cured product according to claim 5.

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