Resin composition, curable composition, cured product, and article

Abstract

To provide a resin composition which can obtain a cured product that can exhibit excellent adhesion, low linear expansion and low dielectric characteristics, a curable composition containing the resin composition, and a cured product, an insulation material and a resist member which are obtained by using the curable composition.SOLUTION: A resin composition contains a polyindene compound (A) which contains an indene compound and a chain olefin compound that may be substituted by an alkyl group or an aryl group, and has a leaving group at its terminal and three or more carbon atoms as reaction raw materials, and a compound (B) having a polymerizable unsaturated group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a resin composition, a curable composition containing the resin composition, a cured product obtained from the curable composition, and an article. [Background technology]

[0002] BACKGROUND ART In recent years, curable compositions such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been widely used in fields such as inks, paints, coating agents, adhesives, and optical components. BACKGROUND ART In recent years, curable compositions such as active energy ray-curable compositions that can be cured by active energy rays such as ultraviolet rays and thermosetting compositions that can be cured by heat have been widely used in fields such as inks, paints, coating agents, adhesives, and optical components.

[0003] In particular, since the coating agent is required to have various properties such as curability, heat resistance, and low dielectric properties depending on the application, it is important to manufacture it using appropriate materials that match the above properties. In this regard, there are technologies described in Patent Documents 1 and 2 as compositions that tend to have excellent low dielectric properties in the cured product. The above-mentioned Patent Document 1 describes a technology in which a curable resin mixture containing a specific cyclopentadiene structure as a curable functional group exhibits low dielectric properties. The above-mentioned Patent Document 2 also describes a technology in which a curable composition containing a polyfunctional vinyl aromatic copolymer containing a structural unit (a) derived from a divinyl aromatic compound, a structural unit (b) derived from a monovinyl aromatic compound, and a structural unit (c) derived from a cycloolefin compound exhibits low dielectric properties. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 031935 [Patent Document 2] Japanese Patent Application Publication No. 2018-039995 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the curable resin mixture having a cyclopentadiene structure described in Patent Document 1 does not have a polymerizable group, so when used in the above-mentioned coating agent, the cured product itself does not have sufficient durability for practical use, and the adhesion to the substrate and low linear expansion required for printed wiring board materials have not been considered. Furthermore, the curable composition of Patent Document 3 does not meet current market demands for various physical properties of the cured product, including low dielectric properties. Therefore, there is room for consideration regarding the application of the technologies of Patent Documents 1 and 2 to the above-mentioned coating agent. Therefore, an object of the present disclosure is to provide a resin composition capable of producing a cured coating film having excellent adhesion, low linear expansion, and low dielectric properties, a curable composition containing the resin composition, a cured product obtained using the curable composition, and an article using the cured product. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that a resin composition containing a specific polyindene compound (A) and a compound (B) having a polymerizable unsaturated group exhibits excellent adhesion, low linear expansion, and low dielectric properties, and have thus completed the present invention.

[0007] The resin composition of the present disclosure contains a polyindene compound (A) and a compound (B) having a polymerizable unsaturated group. More specifically, the resin composition of the present embodiment contains the polyindene compound (A) obtained by reacting an indene compound and a chain olefin compound having 3 or more carbon atoms and a terminal leaving group which may be substituted with an alkyl group or an aryl group, and the compound (B) having a polymerizable unsaturated group. [Effects of the Invention]

[0008] According to the present disclosure, it is possible to provide a resin composition capable of producing a cured coating film having excellent adhesion, low linear expansion, and low dielectric properties, and a curable composition containing the resin composition. Furthermore, according to the present disclosure, it is possible to provide a cured product obtained using the curable composition, and an article using the cured product. 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 polyindene compound (A) (hereinafter also referred to as component (A)) and a compound (B) (hereinafter also referred to as component (B)) having a polymerizable unsaturated group. The polyindene compound (A) can be prepared from an indene compound and a chain olefin compound having 3 or more carbon atoms and a terminal leaving group, which may be substituted with an alkyl group or an aryl group, as reaction raw materials. The polyindene compound (A) has a high carbon and hydrogen atom content due to its chemical structure, and therefore exhibits excellent low dielectric properties. As a result, by combining the polyindene compound (A) with the compound (B) having a polymerizable unsaturated group, a cured product can be formed that exhibits excellent adhesion, low linear expansion, and low dielectric properties as a whole composition.

[0011] In the resin composition of the present disclosure, the content of the polyindene compound (A) is preferably in the range of 1 to 50 mass% relative to the total amount (100 mass%) of the resin composition, from the viewpoint of achieving a balanced improvement in excellent adhesion, low linear expansion, and low dielectric properties. The upper or lower limit of the content of the polyindene compound (A) is preferably 1 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more, and is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less. In the resin composition of the present disclosure, the content of the compound (B) having a polymerizable unsaturated group is preferably in the range of 10 to 95% 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 (B) having 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 95% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.

[0012] In this embodiment, the mass ratio of the solid content of the polyindene compound (A) to the compound (B) having a polymerizable unsaturated group [(A) / (B)] is in the range of 1 / 100 to 100 / 1, preferably 5 / 95 to 50 / 50, from the viewpoint of achieving a good balance between excellent adhesion, low linear expansion, and low dielectric properties. From the same viewpoint, the upper or lower limit of the mass ratio [(A) / (B)] is more preferably 10 / 90 or more, even more preferably 20 / 80 or more, and more preferably 40 / 60 or less.

[0013] The resin composition of the present embodiment may further contain optional additive components as optional components in addition to the polyindene compound (A) and the compound (B) having a polymerizable unsaturated group, which are essential components. The resin composition of the present embodiment may be substantially composed of only the component (A), the component (B), and any optional additional components, or may be composed of only the component (A) and the component (B). From the viewpoint of achieving a balanced improvement in excellent adhesion, low linear expansion, and low dielectric properties, the total content of the (A) component and the (B) component in the total amount (100 mass%) of the resin composition of this embodiment is preferably 40 mass% or more, more preferably 50 mass% or more, and is preferably 95 mass% or less, more preferably 90 mass% or less, and even more preferably 85 mass% or less. The above phrase "consisting only of component (A), component (B), 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 made up of component (A) and component (B), or component (A), component (B), and optional additional components. The resin composition of the present embodiment may contain unavoidable impurities in addition to the component (A), the component (B), and any optional additional components, as long as the effects of the present disclosure are not impaired. Hereinafter, the main terms contained in the components of the resin composition described in this specification will be explained, and then the components contained in the resin composition of this embodiment, namely the polyindene compound (A), the compound (B) having a polymerizable unsaturated group, and the optional added components, will be explained.

[0014] (Terminology explanation) Unless otherwise specified herein, the following terms apply. The "aromatic" or "aromatic group" herein 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" or "aromatic group" herein may have a hydrogen atom of the aromatic ring substituted with a substituent, for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 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" or "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 12 carbon atoms, an alkoxy group having 1 to 12 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. Furthermore, the "aryl group" may have a hydrogen atom in the aromatic ring substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, or a halogen atom. Examples of the "arylene group" include 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 the aromatic ring in the aralkyl group may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. Examples of the "aralkylene group" include divalent groups obtained by removing any one hydrogen atom from the aforementioned "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, examples of a "monovalent hydrocarbon group" include the above-mentioned alkyl groups, and one or more -CH2- in the alkyl group may be substituted with -O- or -S- so that they are not adjacent to each other, or one or more -CH2-CH2- in the alkyl group may be substituted with -CH=CH- so that they are not adjacent to each other. As used herein, examples of a "divalent hydrocarbon group" include the above-mentioned alkylene groups, and one or more -CH2- in the alkylene group may be substituted with -O- or -S- so that they are not adjacent to each other, or one or more -CH2-CH2- in the alkylene group may be substituted with -CH=CH2- so that they are not adjacent to each other. 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.

[0015] (Polyindene Compound (A)) The polyindene compound (A) of the present embodiment may be a compound having a structural unit represented by the general formula (1) described below, or a compound produced by reacting an indene compound with a chain olefin compound having 3 or more carbon atoms and a leaving group at its terminal, which may be substituted with an alkyl group or an aryl group (hereinafter also referred to as an olefin compound). The polyindene compound (A) has an extremely low or substantially no polar functional group content, and therefore exhibits excellent low dielectric properties. Furthermore, by combining the polyindene compound (A) with a compound (B) having a specific polymerizable unsaturated group, it is possible to obtain a cured product exhibiting excellent adhesion, low linear expansion, and low dielectric properties as a whole composition. In other words, the polyindene compound (A) according to the present embodiment preferably has a structure in which a structural unit derived from an indene compound in the reaction raw materials and a group having an unsaturated bond derived from an olefin compound excluding a leaving group in the reaction raw materials are linked by a chemical bond. The above-mentioned "structural unit derived from an indene compound" refers to a group obtained by removing one or more hydrogen atoms from the condensed aromatic ring of an indene compound. For example, when the indene compound is represented by the general formula (a) described below, a group obtained by removing one or two hydrogen atoms from the indene ring of the general formula (a) is called a structural unit derived from an indene compound. The above-mentioned "group having an unsaturated bond derived from an olefin compound excluding a leaving group" refers to a group obtained by removing only the leaving group from a chain olefin compound having 3 or more carbon atoms and having a leaving group at its terminal, which may be substituted with an alkyl group or an aryl group. As described below, examples of the leaving group in the olefin compound include a hydroxyl group, a halogen atom, an ester group (-OCO-R a ), sulfate ester group (-OSO2-R b ) or a phosphate ester group (-OP(=O)-(OR c ) 2) and the like. a , R b and R c each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. The polyindene compound (A) of this embodiment will be described below in two forms: one specified by the structural unit represented by general formula (1) and the other specified by the reaction raw materials.

[0016] (Polyindene compound (A) represented by general formula (1)) The polyindene compound (A) of this embodiment may have a structural unit represented by the following general formula (1). [ka] (In the above general formula (1), R i1 are each independently a hydrogen atom, an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, an aralkyl group, or R i2 represents R i2 each independently represents a group obtained by removing a terminal leaving group from a chain olefin compound having 3 or more carbon atoms and which has a terminal leaving group and which may be substituted with an alkyl group or an aryl group, or a chain alkenyl group having 3 or more carbon atoms and which may be substituted with an alkyl group or an aryl group; R i3 each independently represents an indanyl group or an indenyl group, p i1 represents an integer between 1 and 4, and p i2 represents an integer between 1 and 3, and p i3 represents an integer between 0 and 2, and p i2 +p i2 represents an integer between 1 and 3, and * represents a bond to another atom.) As shown in the chemical structure of general formula (1), the resin composition of this embodiment contains a polyindene compound (A) whose molecular composition is composed entirely of carbon and hydrogen atoms. Therefore, the polyindene compound (A) molecule is substantially free of polar functional groups, thereby reducing the dielectric loss tangent and dielectric constant of the entire resin composition. Furthermore, the presence of unsaturated bonds derived from the olefin compound improves the curability of the entire composition, and the cured product itself can have sufficient durability for practical use. The fused ring in the parentheses in the general formula (1) is a structural unit derived from an indene compound. In the general formula (1), * represents a bond to another atom. The dashed line in the general formula (1) is either absent or represents a single bond. When the dashed line is absent, the fused ring in the parentheses in the general formula (1) can be an indane ring. On the other hand, when the dashed line is a single bond, the dashed portion becomes a double bond (an unsaturated bond between the carbon atoms at the second and third positions), and therefore the fused ring in the parentheses in the general formula (1) can be an indene ring. In the above general formula (1), R i1 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aryloxy group, an aralkyl group, or R i2 It is more preferable that the aryl group represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or R i2 The alkyl group, aryloxy group, or aralkyl group having 1 to 12 carbon atoms includes the groups described in the definitions section above. i1 The preferred aryl group as the aryl group is unsubstituted or optionally substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, or a halogen atom, and 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 is preferably a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, an anthryl group, an azulenyl group, an indenyl group, or an indanyl group, which is unsubstituted or optionally substituted with an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, or a halogen atom.

[0017] R in the above general formula (1) i1 The position may be any of the 1st to 7th positions of the fused ring (indane ring or indene ring), and for example, the 1st, 2nd, 3rd, 4th and 7th positions are preferred. In the above general formula (1), R i2Each independently represents a chain alkenyl group having 3 or more carbon atoms, which may be substituted with an alkyl group or an aryl group. i2 is a group obtained by removing a terminal leaving group from a chain olefin compound having 3 or more carbon atoms, which may be substituted with an alkyl group or an aryl group, and which has the terminal leaving group, and is also referred to as a structural unit derived from an olefin compound. i2 The position may be any of the 1st to 7th positions of the fused ring (indane ring or indene ring), and for example, the 1st, 2nd, 3rd, 4th and 7th positions are preferred. R in the above general formula (1) i3 The position may be any of the 1st to 7th positions of the fused ring (indane ring or indene ring), and for example, the 1st, 2nd, 3rd, 4th and 7th positions are preferred. The repeat number of the structural unit represented by the general formula (1) (so-called degree of polymerization) is preferably within the range of 1 to 20, more preferably within the range of 1 to 10, and even more preferably within the range of 1 to 5. When the repeat number of the structural unit represented by the general formula (1) is within the above range, the number average molecular weight (Mn) tends to fall within the range of 100 to 10,000, and it is possible to obtain molecules with an extremely low content of polar functional groups or essentially no polar functional groups. Note that the repeat number (so-called degree of polymerization) in this specification was calculated from Mw / Mn.

[0018] In this embodiment, R in general formula (1) i2 is represented by the following general formula (2): [ka] (In the above general formula (2), R iia , R iib and R iic each independently represents a hydrogen atom, an alkyl group, or an aryl group; p ii1 represents an integer of 1 or more, and * represents a bond to another atom. Furthermore, since the polyindene compound (A) has an unsaturated bond represented by the general formula (2), the curability of the entire composition is improved, and the cured product itself can have durability sufficient for practical use. The group represented by the general formula (2) preferably represents a group obtained by removing a terminal leaving group from a chain olefin compound having 3 or more carbon atoms, which may be substituted with an alkyl group or an aryl group (in other words, a structural unit derived from an olefin compound). In the general formula (2), * represents a bond to another atom, and the bonding position of the group represented by the general formula (2) to the fused ring (indane ring or indene ring) in the parentheses in the general formula (1) may be any of the 1st to 7th positions, and for example, the 1st, 2nd, 3rd, 4th, and 7th positions are preferred.

[0019] In the general formula (2), 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. A hydrogen atom on the aromatic ring of these aryl groups may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom. In the above general formula (2), examples of the alkyl group 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, a (n-)heptyl group, a (n-)octyl group, a (n-)nonyl group, a (n-)decyl group, a (n-)undecyl group, a (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.

[0020] In the above general formula (2), p ii1 represents preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 8 or less, and even more preferably an integer of 1 or more and 6 or less. In the present embodiment, a preferred embodiment of general formula (2) is R iia or R iibare preferably each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, or an anthryl group. In the present embodiment, a preferred embodiment of general formula (2) is R iic is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, or a naphthyl group. In this embodiment, examples of the group represented by general formula (2) include those represented by the following general formulae (2-1) to (2-4). [ka] (In the above general formulas (2-1) to (2-4), p ii1 each independently represents an integer of 1 or more and 15 or less.)

[0021] In the above general formula (1), p i1 represents an integer of preferably 1 or more and 4 or less, more preferably an integer of 1 or more and 3 or less, and even more preferably an integer of 1 or more and 2 or less. In the above general formula (1), p i2 represents an integer of 1 or more and 3 or less, and more preferably an integer of 1 or more and 2 or less. In the above general formula (1), p i3 represents an integer of 0 or more and 2 or less, and is more preferably 0 or 1. In the above general formula (1), p i2 +p i3 is preferably 1 or more and 3 or less.

[0022] In the polyindene compound (A) of this embodiment, R bonded to one fused ring in the general formula (1) i2 The total number (average value) of these groups is preferably 1 or more and 4 or less. In other words, the number of groups having an unsaturated bond derived from an olefin compound, excluding leaving groups, chemically bonded to one indene ring (one fused ring represented by the above general formula (1)) in the polyindene compound (A) is preferably 1 or more and 4 or less. R chemically bonded to one fused ring i2When the total number of (or groups derived from an olefin compound) is within the above range, the crosslink density of the thermosetting resin can be improved. In addition, R i2 or the average number of groups having an unsaturated bond derived from an olefin compound excluding leaving groups per fused ring is shown in the Examples section below. 1 H-NMR and 13 Calculated using C-NMR.

[0023] In the polyindene compound (A) of the present embodiment, the proportion of the structural unit represented by the general formula (1) relative to the entire polyindene compound (A) is preferably 10 mol % or more, more preferably 20 mol % or more, and even more preferably 25 mol % or more. The method for calculating the proportion of the structural unit represented by the general formula (1) is as shown in the Examples section below. 1 H-NMR and 13 Calculated using C-NMR.

[0024] In this embodiment, R in general formula (1) i3 are each independently an indenyl group or an indanyl group, and a hydrogen atom on the aromatic ring of the indenyl group or the indanyl group may be substituted with, for example, an alkyl group having 1 to 12 carbon atoms.

[0025] (Polyindene compound (A) represented by reaction raw materials) Hereinafter, the indene compound and the chain olefin compound having 3 or more carbon atoms and a leaving group at its terminal, which may be substituted with an alkyl group or an aryl group, which are components of the reaction raw materials for the polyindene compound (A) of this embodiment will be described, and then the method for producing the polyindene compound (A) will be described. <Indene compounds> The indene compound in this embodiment may have an indene ring, and specifically, is preferably represented by the following general formula (a). [ka] (In the above general formula (a), R a1 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, or an aralkyl group; p a1 represents an integer between 0 and 7.) In the general formula (a), R a1 is bonded to any of the carbon atoms 1 to 7 of the indene ring in the square brackets. a1 may be chemically bonded. In the present embodiment, preferred indene compounds include those represented by the general formula (a) p a1 Examples include indene, where .

[0026] <Olefin compounds> In this embodiment, the chain olefin compound having 3 or more carbon atoms and a leaving group at its terminal, which may be substituted with an alkyl group or an aryl group, is an olefin compound having a linear or branched molecular structure having at least one leaving group and at least one unsaturated bond at its terminal, and which may be substituted with an alkyl group or an aryl group, and which has 3 or more carbon atoms. The olefin compound preferably has 3 or more and 30 or less carbon atoms, more preferably 4 or more and 26 or less carbon atoms, and even more preferably 5 or more and 22 or less carbon atoms.

[0027] Specifically, the olefin compound in this embodiment is preferably represented by the following general formula (b). [ka] (In the above general formula (b), R iia , R iib and R iic each independently represents a hydrogen atom, an alkyl group, or an aryl group; p ii1 represents an integer of 1 or more, and X represents a leaving group.

[0028] In the above general formula (b), X represents a leaving group, specifically, a hydroxyl group, a halogen atom, an ester group (—OCO—Ra ), sulfate ester group (-OSO2-R b ) or a phosphate ester group (-OP(=O)-(OR c When the leaving group is one of the groups listed above, the reaction proceeds smoothly in the presence of an acid or a base, and electrophilic reactions and the like tend to proceed more easily with respect to the indene ring of the indene compound.

[0029] In the above general formula (b), X, which is a leaving group, is an ester group or a sulfate ester group (—OSO2-R b ), then R a and R b is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, or isohexyl group.

[0030] In the above general formula (b), X, which is a leaving group, is a phosphate ester group (-OP(=O)-(OR c )2) If there are two R c may be the same or different and are preferably alkyl groups having 1 to 12 carbon atoms, more preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, or isohexyl group.

[0031] In the above general formula (b), when the leaving group X is a halogen atom, X is preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom, and more preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In the above general formula (b), R iia , R iib , R iic and p ii1The embodiments and preferred embodiments are the same as those of the general formula (2) above, and therefore will not be described here.

[0032] Preferred olefin compounds in this embodiment are, for example, those represented by general formulas (b-1) to (b-4). [ka] In the above general formulas (b-1) to (b-4), X represents a halogen atom, an ester group (—OCO—R a ), sulfate ester group (-OSO2-R b ) or a phosphate ester group (-OP(=O)-(OR c )2) and R a ~R c each independently represents an alkyl group having 1 to 12 carbon atoms, and p ii1 is an integer between 1 and 15.)

[0033] In the present embodiment, the molar ratio of the olefin compound to the indene compound (olefin compound / indene compound) in the reaction raw materials for the polyindene compound (A) is preferably 0.5 to 5 / 1, and more preferably 1 to 4 / 1. When the molar ratio of the olefin compound to the indene compound in the reaction raw materials for the polyindene compound (A) is within the above range, it is preferable in terms of realizing a lower dielectric loss tangent.

[0034] The number average molecular weight (Mn) of the polyindene compound (A) of the present disclosure is preferably in the range of 100 to 10,000, and more preferably in the range of 100 to 5,000. The lower limit of the number average molecular weight (Mn) of the polyindene compound (A) is preferably 100, 150, 180, 200, or 250, and the upper limit of the number average molecular weight (Mn) of the polyindene compound (A) is preferably 10,000, 5,000, 3,000, 2,000, 1,500, 1,200, or 980. The weight average molecular weight (Mw) of the polyindene compound (A) is preferably in the range of 100 to 30,000, and more preferably in the range of 100 to 10,000. The lower limit of the weight average molecular weight (Mw) of the polyindene compound (A) is preferably 100, 250, 280, 320, or 350, and the upper limit of the weight average molecular weight (Mw) of the polyindene compound (A) is preferably 30,000, 10,000, 6,000, 4,000, 2,500, 1,200, or 990. The preferred ranges of the number average molecular weight (Mn) and the weight average molecular weight (Mw) can be any ranges obtained by combining the respective upper and lower limits. The number-average molecular weight or weight-average molecular weight of the polyindene compound (A) within the above range is preferable in terms of realizing a lower dielectric tangent. In view of excellent low dielectric properties and low linear expansion coefficient, the polyindene compound (A) of the present disclosure preferably has a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) calculated by gel permeation chromatography (GPC) measurement in the range of 1 to 10, more preferably 1 to 7, and even more preferably 1 to 5. The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polyindene compound (A) of the present embodiment are measured using gel permeation chromatography (hereinafter abbreviated as "GPC") under the measurement conditions described in the examples described later.

[0035] <Another aspect of the resin composition according to this embodiment> In another embodiment of the resin composition of the present disclosure, the polyindene compound (A) may not be specified by the above-described reaction raw materials. Specifically, the resin composition of the present disclosure is a resin composition containing the polyindene compound (A) and a compound (B) having a polymerizable unsaturated group, The polyindene compound (A) contains, in one molecule, a compound represented by the following general formula (A): [ka] (In the above general formula (A), R 11are each independently a hydrogen atom, an alkyl group, an alkoxy group, an allyl group, an aryl group, an aryloxy group, an aralkyl group, or R 12 represents R 12 each independently represents a group having an unsaturated hydrocarbon bond, and R 13 each independently represents an indenyl group or an indanyl group, p i1 represents an integer between 1 and 4, and p i2 represents an integer between 1 and 3, and p i3 represents an integer between 0 and 2, and p i2 +p i3 represents an integer of 1 or more and 3 or less, and * represents a bond to another atom. In the above general formula (1), the group having an unsaturated hydrocarbon bond is preferably a chain alkenyl group having 3 or more carbon atoms which may be substituted with an alkyl group or an aryl group, and is represented by the following general formula (2): [ka] (In the above general formula (2), R iia , R iib and R iic each independently represents a hydrogen atom, an alkyl group, or an aryl group; p ii1 represents an integer of 1 or more, and * represents a bond to another atom.) Furthermore, when the polyindene compound (A) has an unsaturated hydrocarbon bond, the curability of the entire composition is improved, and the cured product itself can have durability sufficient for practical use. In the above general formula (A), R 11 A preferred embodiment of the formula (1) is R i1 is the same as R 12 A preferred embodiment of the formula (1) is R i2 is the same as R 13 A preferred embodiment of the formula (1) is R i3 In addition, p in the above general formula (A) is the same as i1 , p i2 and p i3 A preferred embodiment of the formula (1) is p i1 , p i2 and pi3 is the same as

[0036] (Method for producing polyindene compound (A)) The method for producing the polyindene compound (A) of the present disclosure will be described below. The polyindene compound (A) of the present embodiment may be produced by any method, including using an indene compound and an olefin compound as reaction raw materials, or by any method that includes the structural unit represented by the general formula (1). An example of a method for producing the polyindene compound (A) of the present disclosure includes a production method including the following steps: Step: A step of reacting an indene compound with a chain olefin compound having 3 or more carbon atoms and having a leaving group at its terminal, which may be substituted with an alkyl group or an aryl group, in the presence of an acid or a base to obtain the polyindene compound (A) of the present embodiment. The blending ratio of the indene compound and the olefin compound is preferably 0.5 to 5 moles, more preferably 1 to 4 moles, in terms of the molar ratio of the olefin compound to 1 mole of the indene compound, taking into consideration the balance of physical properties such as moldability during production of the resulting cured product and curability. In addition, specific methods for carrying out the above reaction generally involve charging all the reaction raw materials at once and reacting them at a predetermined temperature, or charging an olefin compound and an acid group or a base and maintaining the temperature at a predetermined level while adding an indene compound or other compounds dropwise. In this case, the dropwise addition time is usually 0.1 to 12 hours, preferably 6 hours or less. After the reaction, if a solvent is used, the solvent and unreacted materials can be distilled off as necessary to obtain the target polyindene compound (A). If no solvent is used, the target polyindene compound (A) can be obtained by distilling off the unreacted materials.

[0037] In the method for producing the polyindene compound (A) of this embodiment, the acid or base is appropriately selected depending on the type of olefin compound used. For example, when the olefin compound used as a reaction raw material satisfies the condition that the leaving group X in the above general formula (b) is a halogen atom (i.e., an olefin compound having a halogen atom such as an allyl halide), by allowing a base to act on the reaction raw material containing the olefin compound having the halogen atom and an indene compound, the group represented by the above general formula (2) (e.g., an allyl group) is modified into the indene ring of the indene compound. At this time, the generated hydrogen halide can simultaneously polymerize the indene compound. Furthermore, for example, when the olefin compound used as a reaction raw material satisfies the condition that the leaving group X in the above general formula (b) is a hydroxyl group (i.e., an olefin compound having a hydroxyl group such as allyl alcohol), by treating the reaction raw material containing the olefin compound having the hydroxyl group and an indene compound with an acid (e.g., a Bronsted acid), the group represented by the above general formula (2) (e.g., a cinnamyl group) is modified into the indene ring of the indene compound. In this case, the dehydration reaction of the alcohol by the acid (e.g., a Bronsted acid) and the polymerization of the indene compound can proceed simultaneously.

[0038] The base that can be used in this embodiment may be either an organic base or an inorganic base. Examples of the organic base include alkali metal alkoxides such as sodium methoxide, lithium methoxide, sodium ethoxide, lithium ethoxide, sodium tertiary butoxide, and potassium tertiary butoxide; trialkylamines such as triethylamine and ethyldiisopropylamine; aniline derivatives having an alkyl group with 1 to 4 carbon atoms such as N,N-dimethylaniline and N,N-diethylaniline; pyridine derivatives that may have an alkyl substituent with 1 to 4 carbon atoms such as pyridine and 2,6-lutidine; and nitrogen-containing heterocyclic compounds such as 1,8-diazabicyclo[5.4.0]-7-undecene. On the other hand, examples of the inorganic base include alkali metal hydrides such as sodium hydride and lithium hydride; alkaline earth metal hydrides such as calcium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal or alkaline earth metal carbonates or bicarbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; and alkali metal or alkaline earth metal halide compounds such as potassium fluoride, cesium fluoride and potassium iodide. These bases may be used alone or in combination of two or more. In this embodiment, preferred bases include alkyl metal alkoxides, nitrogen-containing heterocyclic compounds, and hydroxides of alkali metals or alkaline earth metals, and potassium tert-butoxide or sodium tert-butoxide is more preferred. The amount of the base added is preferably in the range of 1 to 15 times (molar) the number of moles of the olefin compound.

[0039] The acid usable in this embodiment may be any of organic acids, inorganic acids, and solid acids, and is preferably a Bronsted acid. Examples of the organic acid include aliphatic sulfonic acids such as methanesulfonic acid and fluoromethanesulfonic acid; aromatic sulfonic acids such as 3-morpholinopropanesulfonic acid, piperazine-1,4-bis(2-ethanesulfonic acid), 10-camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; alkyl phosphates such as dimethyl phosphate and diethyl phosphate; alkyl sulfuric acids such as dimethyl sulfate, diethyl sulfate, and lauryl sulfate; aromatic sulfuric acids such as phenyl sulfate and phenyl fluoride sulfate; and various acids such as oxalic acid. Examples of the inorganic acid include phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, boric acid, etc. Examples of the solid acid include activated clay, acid clay, silica alumina, zeolite, strongly acidic ion exchange resin, etc. These acids may be used alone or in combination of two or more. Preferred Bronsted acids in this embodiment include hydrochloric acid, sulfuric acid, fluorosulfonic acid, chlorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, 2-aminoethanesulfonic acid, 2-[4-(2-hydroxyethyl)-1-piperazinyl]ethanesulfonic acid, 3-morpholinopropanesulfonic acid, piperazine-1,4-bis(2-ethanesulfonic acid), 10-camphorsulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 4-chlorobenzenesulfonic acid, sulfanilic acid, 3-pyridinesulfonic acid, 2-aminoethanesulfinic acid, benzenesulfinic acid, and 4-methylbenzenesulfinic acid. The amount of the acid added is preferably in the range of 0.5 to 15 mol % based on the number of moles of the olefin compound.

[0040] In this embodiment, the reaction temperature of the olefin compound and the indene compound in the presence of an acid group or a base may usually be in the range of 40 to 200°C, and more preferably 60 to 180°C. The reaction temperature can be appropriately selected depending on the catalyst used, the reaction conditions, or the types of reaction raw materials. For example, when an olefin compound and an indene compound are reacted in the presence of a base, the reaction temperature is preferably 20 to 180°C. On the other hand, for example, when an olefin compound and an indene compound are reacted in the presence of an acid, the reaction temperature is preferably 60 to 180°C. In this embodiment, the reaction time between an olefin compound and an indene compound in the presence of an acid group or a base is usually within the range of 0.5 to 24 hours, but the reaction time can be appropriately selected depending on the catalyst used, reaction conditions, and the types of reaction raw materials. For example, when an olefin compound and an indene compound are reacted in the presence of a base, the reaction time is preferably 0.5 to 24 hours. On the other hand, for example, when an olefin compound and an indene compound are reacted in the presence of an acid, the reaction time is preferably 0.5 to 24 hours. The reaction atmosphere between the olefin compound and the indene compound can be appropriately selected from air, inert gas (nitrogen, argon, helium), and the like.

[0041] In the method for producing the polyindene compound (A) of this embodiment, since the indene compound (e.g., indene or a derivative thereof) also serves as the solvent, other solvents are not necessarily used, but it is also possible to use a solvent. For example, a method may be employed in which, using an azeotropically dehydrating solvent such as toluene, xylene, or chlorobenzene, water contained in the catalyst and the like is azeotropically dehydrated as necessary, the solvent is distilled off, and then the reaction is carried out within the above-mentioned reaction temperature range.

[0042] (Compound (B) having a polymerizable unsaturated group) The compound (B) having a polymerizable unsaturated group of this embodiment is one of the essential components of the resin composition of this embodiment. As long as the component (B) has a polymerizable unsaturated group, there are no particular limitations on the specific structure or molecular weight, and a wide variety of resins or compounds can be used. The compound (B) having a polymerizable unsaturated group may be used alone or in combination of two or more. It is preferable that the compound (B) having a polymerizable unsaturated group has a polymerizable unsaturated group but does not have an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.

[0043] In this embodiment, examples of the polymerizable unsaturated group contained in component (B) include a (meth)acryloyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, a maleimide group, and a vinyl ether group.

[0044] Specific examples of the compound (B) having a polymerizable unsaturated group include a (meth)acrylate compound (B0) and a resin having a polymerizable unsaturated group.

[0045] The (meth)acrylate compound (B0) is not particularly limited as long as it has a (meth)acryloyl group, and examples thereof include aliphatic mono(meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate; cyclohexyl (meth)acrylate, Alicyclic mono(meth)acrylate compounds such as isobornyl (meth)acrylate and adamantyl mono(meth)acrylate; heterocyclic mono(meth)acrylate compounds such as glycidyl (meth)acrylate and tetrahydrofurfuryl acrylate; benzyl (meth)acrylate, phenyl (meth)acrylate, phenylbenzyl (meth)acrylate, phenoxy (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, Mono(meth)acrylate compounds such as aromatic mono(meth)acrylate compounds such as 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, benzyl benzyl (meth)acrylate, and phenylphenoxyethyl (meth)acrylate; (poly)oxyalkylene-modified mono(meth)acrylate compounds in which a polyoxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate monomers; lactone-modified mono(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds; aliphatic di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate;Alicyclic di(meth)acrylate compounds such as 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane di(meth)acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; and compounds containing (poly)oxyethylene groups in the molecular structure of the above-mentioned various di(meth)acrylate compounds. Polyoxyalkylene-modified di(meth)acrylate compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced; lactone-modified di(meth)acrylate compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds; aliphatic tri(meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate and glycerin tri(meth)acrylate; the molecular structure of the above-mentioned aliphatic tri(meth)acrylate compounds (Poly)oxyalkylene-modified tri(meth)acrylate compounds having a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain introduced into the structure; lactone-modified tri(meth)acrylate compounds having a (poly)lactone structure introduced into the molecular structure of the aliphatic tri(meth)acrylate compounds; pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, aliphatic poly(meth)acrylate compounds having tetrafunctional or higher functionality such as acrylate; (poly)oxyalkylene-modified poly(meth)acrylate compounds having tetrafunctional or higher functionality in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound; and lactone-modified poly(meth)acrylate compounds having tetrafunctional or higher functionality in which a (poly)lactone structure has been introduced into the molecular structure of the aliphatic poly(meth)acrylate compound;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 (meth)acrylate compounds having a hydroxyl group, such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate; (meth)acrylate compounds having a hydroxyl group, such as (poly)oxyethylene chains, (poly)oxypropylene chains, (poly)oxytetramethylolpropane chains, and the like, in the molecular structure of the (meth)acrylate compounds having a hydroxyl group. Examples of the (meth)acrylate compound include (poly)oxyalkylene modified compounds having a (poly)oxyalkylene chain such as a ethylene chain introduced therein; lactone modified compounds having a (poly)lactone structure introduced into the molecular structure of the (meth)acrylate compound having a hydroxyl group; (meth)acrylate compounds having an isocyanate group such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate; (meth)acrylate monomers having a glycidyl group such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and (meth)acrylate compounds having an epoxy group such as mono(meth)acrylates of diglycidyl ether compounds of hydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. The (meth)acrylate compound (B0) may be used alone or in combination of two or more.

[0046] The resin having a polymerizable unsaturated group may be any polymer material having a polymerizable unsaturated group in the resin, and examples thereof include the following [1] to [6]: [1] an epoxy resin (B1) having a polymerizable unsaturated group, [2] a urethane resin (B2) having a polymerizable unsaturated group, [3] an acrylic resin (B3) having a polymerizable unsaturated group, [4] Amide-imide resin (B4) having a polymerizable unsaturated group, [5] Acrylamide resin (B5) having a polymerizable unsaturated group, [6] Ester resin (B6) having a polymerizable unsaturated group, etc.

[0047] <Epoxy resin having polymerizable unsaturated group (B1)> Examples of the epoxy resin (B1) having a polymerizable unsaturated group (hereinafter also referred to as resin (B1)) of this embodiment include an epoxy (meth)acrylate resin obtained by reacting an epoxy resin with an unsaturated monobasic acid, and optionally a polybasic acid anhydride; and an epoxy (meth)acrylate resin having a urethane group obtained by reacting an epoxy resin with an unsaturated monobasic acid, a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, and optionally a polybasic acid anhydride. As mentioned above, polybasic acid anhydrides can be used as reaction raw materials for resin (B1), but it is preferable not to use them. It is preferable that the resin (B1) has a polymerizable unsaturated group but no acid group.

[0048] Examples of the epoxy resin 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 may be used alone or in combination of two or more.

[0049] 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.

[0050] 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.

[0051] Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Esters, acid halides, and acid anhydrides of the unsaturated monobasic acids can also be used. Furthermore, examples of the unsaturated monobasic acid include those represented by the following general formula (4): [ka] [In the above general formula (3), X 31 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 31 A hydrogen atom in the structure of Y may be substituted with a halogen atom or an alkoxy group; 31 is a hydrogen atom or a methyl group.] can also be used.

[0052] Examples of the polyoxyalkylene chain include a polyoxyethylene chain and a polyoxypropylene chain. The (poly)ester chain is, for example, a chain represented by the following general formula (4): [ka] [In the above general formula (4), R 41 and R 42 represents an alkylene group having 1 to 10 carbon atoms, and n 41 represents an integer of 1 to 5.] is an example of a (poly)ester chain. These unsaturated monobasic acids may be used alone or in combination of two or more.

[0053] 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.

[0054] The (poly)carbonate chain may be, for example, a chain represented by the following general formula (5): [ka] [In the above general formula (5), R 51 represents an alkylene group having 1 to 10 carbon atoms, and n 51 represents an integer of 1 to 5.] is an example of a (poly)carbonate chain.

[0055] Examples of the polybasic acid anhydride include aliphatic polybasic acid anhydrides, alicyclic polybasic acid anhydrides, and aromatic polybasic acid anhydrides.

[0056] Examples of the aliphatic polybasic acid anhydrides include acid 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. Furthermore, 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.

[0057] In the present invention, the alicyclic polybasic acid anhydride is one in which the acid anhydride group is bonded to an alicyclic structure, and the presence or absence of aromatic rings in other structural positions is not important. Examples of the alicyclic polybasic acid anhydride include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid, and 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydrides.

[0058] 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. These polybasic acid anhydrides may be used alone or in combination of two or more.

[0059] Examples of the polyisocyanate compound 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; Examples of the polyisocyanate compounds include aromatic diisocyanate compounds such as silylene 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, biuret-modified, and allophanate-modified versions of these compounds. These polyisocyanate compounds may be used alone or in combination of two or more. [ka] [In the above general formula (6), R 62 and R 63 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; R 61 each independently represents an alkyl group having 1 to 4 carbon atoms, k 61 is 0 or an integer of 1 to 3, and n 61 is an integer greater than or equal to 1.]

[0060] Examples of the (meth)acrylate compound 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.

[0061] The method for producing the epoxy resin (B1) having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the epoxy resin (B1) having a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and may also use a basic catalyst, if necessary.

[0062] 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 may be used alone or in combination of two or more.

[0063] 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.

[0064] Examples of basic catalysts include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), 1,4-diazabicyclo[2.2.2]octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, and amine compounds such as tetramethylammonium hydroxide; trioctylmethylammonium chloride, trioctylmethylammonium chloride, and trioctylmethylammonium chloride. quaternary ammonium salts such as octylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl(2-hydroxypropyl)phosphonium chloride, triphenylphosphonium chloride, and benzylphosphonium chloride; organic tin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octoate, and 1,1,3,3-tetrabutyl-1,3-dodecanoyldistannoxane; organic metal compounds such as zinc octoate and bismuth octoate; inorganic tin compounds such as tin octoate; and inorganic metal compounds. In addition, alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, etc. can also be used. The basic catalysts may be used alone or in combination of two or more.

[0065] <Urethane resin having polymerizable unsaturated group (B2)> Examples of the urethane resin (B2) having a polymerizable unsaturated group (hereinafter also referred to as resin (B2)) of this embodiment include those obtained by reacting a polyisocyanate compound, a (meth)acrylate compound having a hydroxyl group, and, if necessary, a polyol compound and / or a polybasic acid anhydride. As mentioned above, polybasic acid anhydrides can be used as reaction raw materials for resin (B2), but it is preferable not to use them. It is preferable that the resin (B2) has a polymerizable unsaturated group but does not have an acid group.

[0066] The polyisocyanate compound, the (meth)acrylate compound having a hydroxyl group, and the polybasic acid anhydride are the same as those described above for the resin (B1) and the like.

[0067] Examples of the polyol compounds 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 a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various polyol compounds; lactone-modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various polyol compounds, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The above-mentioned polyol compounds may be used alone or in combination of two or more.

[0068] The method for producing the urethane resin (B2) having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the urethane resin (B2) having a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and a basic catalyst may be used, if necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (B1) and the like.

[0069] <Acrylic resin having polymerizable unsaturated group (B3)> Examples of the acrylic resin (B3) having a polymerizable unsaturated group (hereinafter also referred to as resin (B3)) of this embodiment include a reaction product obtained by polymerizing an acrylic resin intermediate 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, and then reacting the resulting acrylic resin intermediate with a (meth)acrylate compound (β) having a reactive functional group capable of reacting with the functional group to introduce a (meth)acryloyl group, or a product obtained by reacting a polybasic acid anhydride with the hydroxyl group in the reaction product, as needed. As mentioned above, polybasic acid anhydrides can be used as a reaction raw material for resin (B3), but it is preferable not to use them. It is preferable that the resin (B3) has a polymerizable unsaturated group but no acid group.

[0070] The acrylic resin intermediate may be copolymerized with the (meth)acrylate compound (α) and, if necessary, other compounds having polymerizable unsaturated groups. Examples of the compounds having other polymerizable unsaturated groups 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 compounds having a polymerizable unsaturated group may be used alone or in combination of two or more.

[0071] The (meth)acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth)acrylate compound (α), but the following combinations are preferred from the viewpoint of reactivity. That is, when water (meth)acrylate is used as the (meth)acrylate compound (α), it is preferred to use a (meth)acrylate having an isocyanate group as the (meth)acrylate compound (β). When a (meth)acrylate having a carboxyl group is used as the (meth)acrylate compound (α), it is preferred to use a (meth)acrylate having a glycidyl group as the (meth)acrylate compound (β). When a (meth)acrylate having an isocyanate group is used as the (meth)acrylate compound (α), it is preferred to use water (meth)acrylate as the (meth)acrylate compound (β). When a (meth)acrylate having a glycidyl group is used as the (meth)acrylate compound (α), it is preferred to use a (meth)acrylate having a carboxyl group as the (meth)acrylate compound (β). The (meth)acrylate compound (β) may be used alone or in combination of two or more.

[0072] The polybasic acid anhydride is the same as that described above with respect to the resin (B1) and the like.

[0073] The method for producing the acrylic resin (B3) having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylic resin (B3) having a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and a basic catalyst may be used, if necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (B1) and the like.

[0074] <Amide-imide resin having a polymerizable unsaturated group (B4)> Examples of the amide-imide resin (B4) (hereinafter also referred to as resin (B4)) having a polymerizable unsaturated group of this embodiment include those obtained by reacting an amide-imide resin having an acid group and / or an acid anhydride group with a (meth)acrylate compound having a hydroxyl group and / or a (meth)acrylate compound having an epoxy group, and, if necessary, 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 a reactive functional group may or may not have a (meth)acryloyl group. It is preferable that the resin (B4) has a polymerizable unsaturated group but no acid group.

[0075] The amide-imide resin (B4) having a polymerizable unsaturated group may have only an acid group or an acid anhydride group, or may have both. However, from the viewpoint of reactivity and reaction control with a (meth)acrylate compound having a hydroxyl group or an epoxy compound having a (meth)acryloyl group, the amide-imide resin (B4) having a polymerizable unsaturated group preferably has an acid anhydride group, and more preferably has both an acid group and an acid anhydride group. In terms of introducing a UV-curable group into the resin, it is preferable that the amide-imide resin (B4) has both an acid group and an acid anhydride group during synthesis. On the other hand, it is preferable that the final amide-imide resin (B4) does not have an acid group. The acid value of the solid content of the amide-imide resin is preferably in the range of 60 to 350 mgKOH / g measured under neutral conditions, i.e., conditions under which the acid anhydride group is not ring-opened, and is preferably in the range of 61 to 360 mgKOH / g measured under conditions under which the acid anhydride group is ring-opened, such as in the presence of water.

[0076] The amide-imide resin (B4) having the polymerizable unsaturated group may be, for example, one obtained by reacting a polyisocyanate compound with a polybasic acid anhydride. In this case, the polyisocyanate compound and the polybasic acid anhydride are the same as those described above for the resin (B1). As mentioned above, the polybasic acid anhydride can be used as a reactant for the resin (B4), but it is preferable not to use it.

[0077] Furthermore, as reaction raw materials for the amide-imide resin (B4) having a polymerizable unsaturated group, in addition to the polyisocyanate compound and polybasic acid anhydride, a polybasic acid can also be used in combination, if necessary.

[0078] 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 Examples of suitable polybasic acids include 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, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid. Examples of suitable polybasic acids include copolymers of conjugated diene vinyl monomers and acrylonitrile, each having a carboxyl group in its molecule. These polybasic acids may be used alone or in combination of two or more.

[0079] The (meth)acrylate compound having a hydroxyl group is the same as that described above for the resin (B1) and the like.

[0080] Examples of the (meth)acrylate compound having an epoxy group include (meth)acrylate monomers having a glycidyl group, such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and epoxycyclohexylmethyl (meth)acrylate; and mono(meth)acrylates of diglycidyl ether compounds, such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. These (meth)acrylate compounds having an epoxy group may be used alone or in combination of two or more.

[0081] The method for producing the amide-imide resin (B4) having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the amide-imide resin (B4) having a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and a basic catalyst may be used, if necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (B1).

[0082] <Acrylamide resin having a polymerizable unsaturated group (B5)> Examples of the acrylamide resin (B5) having a polymerizable unsaturated group (hereinafter also referred to as resin (B5)) of this embodiment include those obtained by reacting a compound having a phenolic hydroxyl group, an alkylene oxide or alkylene carbonate, an N-alkoxyalkyl (meth)acrylamide compound, and, if necessary, a polybasic acid anhydride and an unsaturated monobasic acid. As mentioned above, polybasic acid anhydrides can be used as reaction raw materials for resin (B5), but it is preferable not to use them. It is preferable that the resin (B5) has a polymerizable unsaturated group but does not have an acid group.

[0083] The compound having a phenolic hydroxyl group refers to a compound having at least one phenolic hydroxyl group in the molecule. Examples of the compound having at least one phenolic hydroxyl group in the molecule include compounds represented by the following general formulas (8.1) to (8.5). [ka] [In the above general formulas (7.1) to (7.5), R 71 ~R 74 and R 77 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 75 and R 76 each independently represents a hydrogen atom or a methyl group; j 71 ~j 75 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. 71 ~k 75 each independently represents an integer of 1 or more, preferably 2 or 3. The positions of the substituents on the aromatic rings in the general formulas (7.1) to (7.5) are arbitrary. For example, in the naphthalene ring of the general formula (7.2), they may be substituted with any hydrogen atom on the ring. In the general formula (7.3), they may be substituted with any hydrogen atom on the benzene ring present in one biphenyl molecule. In the general formula (7.4), they may be substituted with any hydrogen atom on the benzene ring present in one aralkyl molecule. In the general formula (7.5), they may be substituted with any hydrogen atom on the benzene ring present in one molecule. When the number of substituents in one molecule is j, 71 ~j 75 and k 71 ~k 75 This indicates that

[0084] Examples of the compound having a phenolic hydroxyl group include reaction products obtained by using, as essential reaction raw materials, a compound having at least one phenolic hydroxyl group in the molecule and a compound represented by any one of the following general formulas (8.1) to (8.5) and / or formaldehyde. Also usable are novolac-type phenolic resins obtained by using, as reaction raw materials, one or more compounds having at least one phenolic hydroxyl group in the molecule. [ka] [In the above general formulas (8.1) to (8.5), h 81 represents 0 or 1, R 81 ~R 86 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 81 ~k 86 each independently represents 0 or an integer of 1 to 4, and Z 81 ~Z 86 each independently represents a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group; Y 81 represents an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, or a carbonyl group, and n 81 represents an integer from 1 to 4.]

[0085] Specific examples of the above compounds include phenol, cresol, xylenol; dialkylphenols such as dimethylphenol and diethylphenol; trialkylphenols such as trimethylphenol and triethylphenol; diphenylphenol, triphenylphenol, catechol, resorcinol, hydroquinone, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol, tetramethylbisphenol A, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1-naphthol, 2-naphthol, 1,3-naphthalenediol, 1,5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, polyphenylene ether type diol, polynaphthylene ether type diol, phenol novolac resin, cresol novolac resin, bisphenol novolac type resin, naphthol novolac type resin, phenol aralkyl type resin, naphthol aralkyl type resin, and phenol resins having a cyclocyclic structure. The above compounds having a phenolic hydroxyl group may be used alone or in combination of two or more.

[0086] Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and pentylene oxide. The alkylene oxides may be used alone or in combination of two or more. Among these, ethylene oxide or propylene oxide is preferred as the alkylene oxide.

[0087] Examples of the alkylene carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. The alkylene carbonate may be used alone or in combination of two or more. Among these, ethylene carbonate or propylene carbonate is preferred as the alkylene carbonate.

[0088] Examples of the N-alkoxyalkyl(meth)acrylamide compound 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. The N-alkoxyalkyl(meth)acrylamide compounds may be used singly or in combination of two or more.

[0089] The polybasic acid anhydrides and unsaturated monobasic acids are the same as those described above for the resin (B1) and the like.

[0090] The method for producing the acrylamide resin (B5) having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the acrylamide resin (B5) having a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and a basic catalyst or an acidic catalyst may be used, if necessary. In this case, the organic solvent and the basic catalyst are the same as those described above for the resin (B1).

[0091] 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 may be used alone or in combination of two or more.

[0092] <Ester resin having polymerizable unsaturated group (B6)> Examples of the ester resin (B6) having a polymerizable unsaturated group (hereinafter also referred to as resin (B6)) of this embodiment include those obtained by reacting a compound having a phenolic hydroxyl group with an alkylene oxide or alkylene carbonate, an unsaturated monobasic acid, and, if necessary, a polybasic acid anhydride. As mentioned above, polybasic acid anhydrides can be used as reaction raw materials for resin (B6), but it is preferable not to use them. It is preferable that the resin (B6) has a polymerizable unsaturated group but no acid group.

[0093] The compounds having a phenolic hydroxyl group, alkylene oxides, alkylene carbonates, unsaturated monobasic acids, and polybasic acid anhydrides are the same as those described above for resin (B1) and resin (B5).

[0094] The method for producing the ester resin (B6) having a polymerizable unsaturated group is not particularly limited, and any method may be used. The production of the ester resin (B6) having a polymerizable unsaturated group may be carried out in an organic solvent, if necessary, and a basic catalyst or an acid catalyst may be used, if necessary. In this case, the organic solvent, basic catalyst, and acid catalyst are the same as those described above for the resins (B1) and (B5).

[0095] The above are the essential components contained in the resin composition of this embodiment. The method for producing the resin composition of this 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.

[0096] (Optional addition ingredient) The resin composition in the present embodiment may contain, in addition to the polyindene compound (A) and the compound (B) having a polymerizable unsaturated group described above, optional added components such as various known stabilizers such as an ultraviolet stabilizer and a storage stabilizer, other resins described in the section on curable compositions described later, solvents described in the section on curable compositions described later, or additives described in the section on curable compositions described later.

[0097] [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 the polyindene compound (A) and the compound (B) having a polymerizable unsaturated group), a photopolymerization initiator, and, if necessary, a curing agent, a solvent, other resins, and additives. Examples of the curing agent include epoxy resins and other curing agents (hereinafter also referred to as other curing agents) other than the epoxy resins. Examples of the other resins include resins other than the polyindene compound (A) and the compound (B) having a polymerizable unsaturated group. Examples of the additives include curing accelerators, flame retardants, fillers, pigments, antifoaming agents, viscosity modifiers, leveling agents, storage stabilizers, antioxidants, and ultraviolet inhibitors.

[0098] In the curable composition of the present embodiment, the content of the polyindene compound (A) is preferably in the range of 5 to 95 mass %, more preferably in the range of 20 to 80 mass %, based on the solid content of the curable composition. In the curable composition of the present embodiment, the content of the compound (B) having a polymerizable unsaturated group 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.

[0099] 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.

[0100] (Photopolymerization initiator) As described above, in this embodiment, the resin composition containing a photopolymerization initiator is a curable resin composition. The photopolymerization initiator may be used alone or in combination of two or more. The photopolymerization initiator of this embodiment 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).

[0101] 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 polyindene compound (A) and the compound (B) having a polymerizable unsaturated group.

[0102] (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.

[0103] <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.

[0104] The epoxy equivalent of the epoxy resin of this embodiment is preferably 120 to 400 g / eq, and more preferably 150 to 300 g / eq. If the epoxy equivalent of the epoxy resin is 120 g / eq or more, the resulting cured product will have better dielectric properties, which is preferable, while if the epoxy equivalent of the epoxy resin is 400 g / eq or less, the resulting cured product will have an excellent balance of adhesion, low linear expansion, and low dielectric properties, which is preferable.

[0105] 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 adhesion, low linear expansion, and low dielectric properties in a well-balanced manner.

[0106] In this embodiment, with respect to the amount of epoxy resin used, when the acid groups in the compound (B) having a polymerizable unsaturated group are taken as the (total) functional groups, the functional group equivalent ratio of the amount of epoxy resin used ((compound (B) having a polymerizable unsaturated group) / epoxy resin) is preferably 0.2 to 2, more preferably 0.4 to 1.5. When the functional group equivalent ratio is 0.2 or more, the resulting cured product can have a lower dielectric tangent and higher flexibility, which is preferable. When the functional group equivalent ratio exceeds 2, heat resistance and curability decrease, so it is preferable to use within the above range.

[0107] <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.

[0108] 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.

[0109] 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.

[0110] In this embodiment, with respect to the amount of other curing agents (amine curing agents, acid anhydride curing agents, phenolic resin curing agents) used, when the acid groups in the compound (B) having 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 ((compound (B) having a polymerizable unsaturated group) / other curing agents) is preferably 0.2 to 2, more preferably 0.4 to 1.5. A functional group equivalent ratio of 0.2 or more is preferred because the resulting cured product can have a lower dielectric tangent and higher flexibility. If the functional group equivalent ratio exceeds 2, heat resistance and curability decrease, so it is preferable to use within the above range.

[0111] (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.

[0112] (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.

[0113] (additives) The curable composition of the present embodiment may contain additives. Examples of the additives include a curing accelerator, a flame retardant, a filler, a pigment, an antifoaming agent, a viscosity modifier, a leveling agent, a storage stabilizer, a polymerization inhibitor, an antioxidant, and an ultraviolet protection agent. That is, the curable composition of the present embodiment may contain appropriate amounts of various other additives, such as the other resins, the solvents, the curing agents, the curing accelerators, the flame retardants, the fillers, the pigments, the antifoaming agents, the viscosity modifiers, the leveling agents, the storage stabilizers, the antioxidants, and the ultraviolet protection agents, as needed, within the scope of the intended purpose.

[0114] <Curing accelerator> The curing accelerator of the present embodiment 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.

[0115] 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.

[0116] 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).

[0117] 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.

[0118] 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.

[0119] 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).

[0120] 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 combined total of the (A) and (B) components. A content of 0.01 part by mass or more of the curing accelerator is preferred because it provides excellent curability. On the other hand, a content of 5 parts by mass or less of the curing accelerator is preferred because it provides excellent insulation reliability. From the same viewpoint, the content of the curing accelerator is more preferably 0.1 part by mass or more, and more preferably 3 parts by mass or less, per 100 parts by mass of the combined total of the (A) and (B) components.

[0121] <Polymerization inhibitor> The polymerization inhibitor of the present embodiment is not particularly limited, but examples thereof include p-methoxyphenol (methoquinone), 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, Phenolic compounds such as 4-trimethyl-1,2-dihydroquinoline; 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,Amine compounds such as 3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, poly(2,2,4-trimethyl-1,2-dihydroquinoline), styrenated diphenylamine, reaction products of styrenated diphenylamine with 2,4,4-trimethylpentene, and reaction products of diphenylamine with 2,4,4-trimethylpentene; phenothiazine, distearyl thiodipropionate, 2,2-bis({[3-(dodecyl) Thioether compounds such as (methylthio)propionyl]oxy}methyl)-1,3-propanediyl bis[3-(dodecylthio)propionate] and ditridecan-1-yl 3,3'-sulfanediyl dipropanoate; N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, etc.; N,N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitrosoaniline, -N,N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-Nn-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine ammonium salt, nitrosobenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-Nn -Propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride and other nitroso compounds; esters of phosphoric acid and octadecan-1-ol, triphenyl phosphite, 3,9-dioctadecan-1-yl-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]Undecane, trisnonylphenyl phosphite, phosphorous acid-(1-methylethylidene)-di-4,1-phenylenetetra-C12-15-alkyl ester, 2-ethylhexyl diphenyl phosphite, diphenyl isodecyl phosphite, triisodecyl phosphite, phosphite compounds such as tris(2,4-di-tert-butylphenyl) phosphite; bis(dimethyldithiocarbamato-κ(2)S,S')zinc, zinc diethyldithiocarbamate Examples of polymerization inhibitors 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. Polymerization inhibitors may be used alone or in combination.

[0122] <Antioxidants> The antioxidant of this embodiment is not particularly limited, and the same compounds as those exemplified as the polymerization inhibitor can be used. The antioxidant may be used alone or in combination of two or more. Examples of commercially available polymerization inhibitors and antioxidants include "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "Sumilizer BBM-S" and "Sumilizer GA-80" manufactured by Sumitomo Chemical Co., Ltd.

[0123] <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.

[0124] 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.

[0125] The content of the flame retardant in this embodiment is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the combined total of the (A) and (B) components. A flame retardant content of 0.1 parts by mass or more is preferred because it can provide flame retardancy. On the other hand, a flame retardant content of 50 parts by mass or less is preferred because it can provide flame retardancy while maintaining dielectric properties. From the same viewpoint, the content of the flame retardant is more preferably 1 part by mass or more, and more preferably 30 parts by mass or less, relative to 100 parts by mass of the combined total of the (A) and (B) components.

[0126] <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.

[0127] 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.

[0128] The content of the filler in this embodiment is preferably 0.5 to 95 parts by mass, and more preferably 5 to 80 parts by mass, relative to 100 parts by mass of the combined amount of the (A) and (B) components. A filler content of 0.5 parts by mass or more is preferred because it allows the filler to fully exert its effects. On the other hand, the content of the filler is preferably 95 parts by mass or less so as not to increase the viscosity of the blend and impair moldability. From the same viewpoint, the content of the filler is more preferably 5 parts by mass or more, and more preferably 80 parts by mass or less, relative to 100 parts by mass of the combined amount of the (A) and (B) components. The method for producing the curable 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.

[0129] [Cured product] The cured product in this embodiment is obtained by curing the above-described curable composition. Since the polyindene compound (A) contained in the curable composition itself has a low dielectric loss tangent because it has substantially no polar functional groups, 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.

[0130] 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.

[0131] 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.

[0132] Applications for the curable composition or cured product of this embodiment include printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for buildup boards, insulating materials for circuit boards such as buildup adhesive films, resin casting materials, adhesives, semiconductor encapsulation materials, semiconductor devices, prepregs, conductive pastes, buildup films, buildup substrates, fiber-reinforced composite materials, and molded articles obtained by curing the above-mentioned composite materials. Among these various applications, the curable composition of the present invention can be used as an insulating material for so-called electronic component-embedded substrates, in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. Furthermore, among the above, taking advantage of the properties of the cured product, such as excellent flexibility, adhesion, low dielectric properties, and heat resistance, the curable composition of the present invention is preferably used for semiconductor encapsulation materials, semiconductor devices, prepregs, flexible wiring boards, circuit boards, buildup films, buildup substrates, multilayer printed wiring boards, fiber-reinforced composite materials, and molded articles obtained by curing the above-mentioned composite materials.

[0133] [Goods] The article of the present embodiment is characterized by having a coating film made of the above-described cured product. In such an article of the present embodiment, the coating film can function as an insulating material having excellent heat resistance and coating appearance.

[0134] The article of this embodiment is typically a printed wiring board or a substrate for a semiconductor package, having a solder resist film (the coating film) formed in appropriate positions on the surface layer.

[0135] [Insulating material] The insulating material in this embodiment is made of the curable composition described above. Examples of such insulating materials include the interlayer insulating material for build-up substrates, insulating materials for circuit boards such as build-up adhesive films, insulating materials for circuit boards, and insulating materials for substrates with built-in electronic components. For example, a method for producing a build-up substrate from the curable composition includes the following three steps. In the first step, the curable composition containing an appropriate blend of rubber, filler, etc. is applied to a circuit board having a circuit formed thereon using a spray coating method, curtain coating method, or the like, followed by curing. In the second step, the desired through-holes or other holes are drilled as needed, followed by treatment with a roughening agent and rinsing the surface with hot water to form irregularities, followed by plating with a metal such as copper. In the third step, these operations are repeated as desired to alternately build up resin insulating layers and conductor layers with the desired circuit pattern. It is preferable to drill the through-holes after forming the outermost resin insulating layer. The first step can be carried out not only by the above-mentioned solution coating but also by laminating a build-up film that has been coated to a desired thickness and dried in advance. Furthermore, the build-up substrate of the present invention can be produced by forming a roughened surface and omitting the plating process by thermocompressing a copper foil on which a circuit has been formed, the copper foil being prepared by semi-curing the resin composition, at 170 to 250°C.

[0136] [Resist material] The resist member in the present embodiment is made 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 it is exposed to active energy rays through a photomask on which a desired pattern is formed, and the unexposed portion is developed with an alkaline aqueous 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.

Examples

[0137] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. 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 were carried out under the following conditions.

[0138] (Evaluation method) <GPC measurement> Using the following measuring device and measuring conditions, GPC charts of the polyindene compound (A) and the compound (B) having a polymerizable unsaturated group obtained in the following synthesis examples and examples were obtained. From the results of the GPC chart, it was confirmed that the target products (polyindene compound (A) and compound (B) having a polymerizable unsaturated group) were produced 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 Measuring 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: Solutions (50 μl) of polyindene compounds (A-1) to (A-4), hydrocarbon resin (C-1), and resins (B-1) to (B-2) having an acid group and a polymerizable unsaturated group, which were obtained in the following synthesis examples, examples, etc., and filtered through a microfilter with a solid content conversion of 1.0% by mass in tetrahydrofuran, were used.

[0139] <FD-MS spectrum measurement> The FD-MS spectrum was measured using the following measuring apparatus and measuring conditions. From this result, mass peaks corresponding to the target products (polyindene compounds (A-1) to (A-4), hydrocarbon resin (C-1)) were confirmed. Measuring apparatus: JMS-T100GC AccuTOF Measuring conditions Measuring range: m / z = 4.00 to 2000.00 Rate of change: 51.2 mA / min Final current value: 45 mA Cathode voltage: -10 kV Recording interval: 0.07 sec

[0140] < 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.

[0141] <Preparation of test specimens, measurement of linear expansion coefficient and peel strength (evaluation of adhesion)> -Preparation of test specimens- The curable compositions obtained in each example and comparative example were applied to a copper foil (electrolytic copper foil "F2-WS" 18 μm, manufactured by Furukawa Sangyo Co., Ltd.) using a 50 μm applicator and dried at 80° C. for 30 minutes. Then, a metal halide lamp was used to apply 1000 mJ / cm 2 After irradiating the coating with ultraviolet light, it was heated at 160°C for 1 hour to obtain test piece 1. - Linear expansion coefficient measurement - The thermomechanical analysis of the test piece 1 was carried out in a tensile mode under a nitrogen atmosphere using a thermomechanical analyzer (TMA: "TMA-60" manufactured by Shimadzu Corporation) under the following measurement conditions. The measurement was carried out twice for the same sample, and the average linear expansion coefficient in the temperature range of 40°C to 60°C in the second measurement was recorded as the linear expansion coefficient (10 -6 The temperature was evaluated as a function of temperature (°C). Measurement conditions: Measurement load 50mN, temperature rise rate 10℃ / min, twice, measurement temperature range (first time) 25℃ to 220℃, (second time) -40℃ to 220℃ -Peel strength measurement (evaluation of adhesion)- The adhesion was evaluated by measuring the peel strength as described below. The above 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).

[0142] <Dielectric constant and dielectric loss tangent measurement (evaluation of dielectric properties)> 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 1000 mJ / cm 2 2 After irradiating the glass substrate with ultraviolet light, the glass substrate 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 cured product was then stored in a room at a temperature of 23°C and a humidity of 50% for 24 hours to obtain test piece 2. The dielectric constant and dielectric loss tangent of the test piece at 1 GHz were measured by the cavity resonance method using a network analyzer "4291B RF Impedance Material Analyzer, 16453A" manufactured by Agilent Technologies.

[0143] (Synthesis Example 1) Synthesis of polyindene compound (A-1) A flask equipped with a stirrer and a condenser was charged with 116.2 parts by mass of indene, 145.9 parts by mass of potassium tertiary butoxide (hereinafter, tBuOK), and 814.4 parts by mass of toluene, and the mixture was heated to 70°C to obtain a mixture. Next, 145.19 parts by mass of allyl bromide was added dropwise to the mixture while maintaining the temperature at 70-80°C, and stirring was continued at 70°C for 3 hours to obtain a reaction solution. The reaction solution was cooled to 80°C, neutralized, and washed three times with 156.2 parts by mass of water to remove catalyst residue from the reaction solution. The reaction solution from which the catalyst residue had been removed was then heated to 150°C and distilled under reduced pressure to remove volatiles, obtaining the target polyindene compound (A-1) (Mn: 293, Mw: 597). The repeating number of the structural unit of general formula (1) in the polyindene compound (A-1) was in the range of 1 to 3.

[0144] (Synthesis Example 2) Synthesis of polyindene compound (A-2) The same procedure as in Example 1 was carried out except that 814.4 parts by mass of toluene was replaced with 370.7 parts by mass of toluene, 145.19 parts by mass of allyl bromide was replaced with 108.7 parts by mass of 3-chloro-2-methyl-1-propene, and 156.2 parts by mass of water was replaced with 181.0 parts by mass of water, to obtain a polyindene compound (A-2) (Mn: 299, Mw: 582). The obtained polyindene compound (A-2) was analyzed by GPC, 13 The structure and molecular weight were identified by C-NMR and FD-MS measurements. The repeating number of the structural unit of general formula (1) in the polyindene compound (A-2) was in the range of 1 to 3.

[0145] (Synthesis Example 3) Synthesis of polyindene compound (A-3) A flask equipped with a stirrer, a Dean-Stark apparatus, and a condenser was charged with 75.7 parts by mass of indene, 131.2 parts by mass of cinnamyl alcohol, 206.9 parts by mass of toluene, and 4.14 parts by mass of p-toluenesulfonic acid monohydrate, and heated to obtain a reaction solution. The temperature was raised to reflux while removing water generated during the reaction using a Dean-Stark apparatus, and stirring was continued for 2 hours to obtain the reaction solution. The resulting reaction solution was cooled to 80°C and neutralized with 1.80 parts by mass of 49% by mass aqueous sodium hydroxide solution. The organic layer was then diluted with 189.3 parts by mass of methyl isobutyl ketone and washed three times with 189.3 parts by mass of water to remove catalyst residue. The reaction solution from which the catalyst residue had been removed was then heated to 150°C, and volatiles were distilled off under reduced pressure to obtain polyindene compound (A-3) (Mn: 370, Mw: 672 for polyindene compound (A-3)). The obtained polyindene compound (A-3) was analyzed by GPC, 13 The structure and molecular weight were identified by C-NMR and FD-MS measurements. The repeating number of the structural unit of general formula (1) in the polyindene compound (A-3) was in the range of 1 to 3.

[0146] (Synthesis Example 4) Synthesis of polyindene compound (A-4) In Example 3, 75.7 parts by mass of indene was replaced with 116.2 parts by mass of indene, 206.9 parts by mass of toluene was replaced with 245.4 parts by mass of toluene, 131.2 parts by mass of cinnamyl alcohol was replaced with 129.2 parts by mass of 3-methyl-2-buten-1-ol, 4.14 parts by mass of p-toluenesulfonic acid monohydrate was replaced with 4.91 parts by mass of p-toluenesulfonic acid monohydrate, 1.80 parts by mass of 49% by mass of aqueous sodium hydroxide was replaced with 2.13 parts by mass of 49% by mass of sodium hydroxide, methyl isobutyl ketone was omitted, and 189.3 parts by mass of water was replaced with 109.2 parts by mass of water. By performing the same operation as in Synthesis Example 3, a polyindene compound (A-4) was obtained (Mn: 297, Mw: 431). The obtained polyindene compound (A-4) was analyzed by GPC, 13The structure and molecular weight were identified by C-NMR and FD-MS measurements. The repeating number of the structural unit of general formula (1) in the polyindene compound (A-4) was in the range of 1 to 3.

[0147] (Synthesis Example 5): Synthesis of Compound (B-1) Having a Polymerizable Unsaturated Group A flask equipped with a thermometer, stirrer, and reflux condenser was charged with 346 parts by weight of bisphenol A epoxy resin (DIC Corporation's "EPICLON 850CRP," epoxy equivalent 173 g / eq; hereafter referred to as "bisphenol A epoxy resin (1)"), and 0.21 parts by weight of dibutylhydroxytoluene as an antioxidant and 0.21 parts by weight of methoquinone as a thermal polymerization inhibitor were added. Then, 72 parts by weight of acrylic acid and 0.21 parts by weight of triphenylphosphine were added, and the esterification reaction was carried out at 100 °C for 10 hours while blowing air into the mixture. After confirming that the acid value was 1 mg KOH / g or less, 0.21 parts by weight of oxalic acid was added and the mixture was stirred at 70 °C for 3 hours to obtain epoxy resin (B-1) having polymerizable unsaturated groups. The epoxy equivalent of this epoxy resin (B-1) having polymerizable unsaturated groups was 450 g / eq. The number of moles of acid groups in the acrylic acid relative to 1 mole of epoxy groups in the bisphenol A epoxy resin (1) was 0.5.

[0148] (Comparative Synthesis Example 1) Synthesis of fused ring compound (C1) A flask equipped with a thermometer, condenser, and stirrer was charged with 72.0 parts by mass of norbornene, 25.0 parts by mass of DVB-810 (manufactured by Nippon Steel Chemical & Material Co., Ltd., containing 81% by mass of divinylbenzene and 19% by mass of ethylstyrene), and 75.0 parts by mass of DVB-570 (manufactured by Nippon Steel Chemical & Material Co., Ltd., containing 57% by mass of divinylbenzene and 43% by mass of ethylstyrene). The ratio of divinylbenzene to ethylstyrene was adjusted to 0.63 moles and 0.37 moles per mole of norbornene. Subsequently, 35.6 parts by mass of butyl acetate and 114.7 parts by mass of toluene were added, and the mixture was heated to 70 °C with stirring. Trifluoroborane-diethyl ether complex was added and reacted at the same temperature for 6 hours to obtain a reaction solution. After completion of the reaction, the mixture was neutralized with aqueous sodium bicarbonate, washed with water to remove catalyst residue, and volatiles were removed under reduced pressure at 60 °C to obtain fused ring compound (C1).

[0149] Examples 1 to 8: Preparation and evaluation of resin compositions and curable compositions The polyindene compounds (A-1) to (A-4) obtained in the above synthesis examples and the compound (B-1) having a polymerizable unsaturated group were mixed in the composition ratios shown in Table 1 to obtain resin compositions (1) to (4). Next, the resin compositions (1) to (4) were mixed with methyl ethyl ketone (MEK) as a solvent, a photopolymerization initiator (Omnirad 907 manufactured by IGM Resins), and 2-ethyl-4-methylimidazole as a curing accelerator in the composition ratios shown in Table 1 to obtain curable compositions (1) to (4). Then, the linear expansion coefficient, peel strength (adhesion), dielectric constant, and dielectric loss tangent of the curable compositions (1) to (4) were evaluated according to the procedures of the evaluation methods described in the above (Evaluation Method) section. The results are shown in Table 1 below.

[0150] Comparative Example 1: Preparation and Evaluation of Composition As in Examples 1 to 4, the components were mixed in the composition ratios shown in Table 1 to obtain a composition (C1) of Comparative Example 1 and a comparative curable composition (C1). The comparative curable composition (C1) of Comparative Example 1 was then evaluated for linear expansion coefficient, peel strength (adhesion), dielectric constant, and dielectric loss tangent according to the procedures of the evaluation methods described in the above section (Evaluation Method). The results are shown in Table 1 below.

[0151] [Table 1]

[0152] From the results in Table 1, it was confirmed that the resin compositions of the examples and the curable compositions containing the resin compositions were able to exhibit excellent adhesion, low linear expansion, and low dielectric properties in the resulting cured products compared to the comparative examples. [Industrial Applicability]

[0153] According to the present disclosure, it is possible to provide a resin composition that can exhibit excellent adhesion, low linear expansion, and low dielectric properties in the resulting cured product, a curable composition containing the resin composition, and a cured product, insulating material, and resist material obtained using the curable composition.

Claims

1. a polyindene compound (A) using an indene compound and a chain olefin compound having 3 or more carbon atoms and a leaving group at its terminal, which may be substituted with an alkyl group or an aryl group, as reaction raw materials, the polyindene compound (A) having a structural unit derived from the indene compound represented by the following general formula (1) and a group having an unsaturated bond derived from the olefin compound represented by the following general formula (2); 【Chemistry 1】 (In the above general formula (1), each R i1 independently represents a hydrogen atom, an alkyl group, an allyl group, an aryl group, an aralkyl group, or R i2 ; each R i2 independently represents a group having an unsaturated hydrocarbon bond derived from the olefin compound represented by general formula (2) excluding the leaving group; each R i3 independently represents an indenyl group or an indanyl group; p i1 represents an integer of 1 to 3; p i2 represents an integer of 1 to 3; p i3 represents an integer of 0 to 2; p i2 +p i3 represents an integer of 1 to 3; and * represents a bond to another atom.) 【Chemistry 2】 (In the above general formula (2), R iia , R iib , and R iic each independently represent a hydrogen atom, an alkyl group, or an aryl group, p ii1 represents an integer of 1 or more and 6 or less, and * represents a bond to another atom.) A resin composition containing, as the compound (B) having a polymerizable unsaturated group, an epoxy(meth)acrylate resin obtained by reacting an epoxy resin with an unsaturated monobasic acid, or an epoxy(meth)acrylate resin obtained by reacting an epoxy resin with an unsaturated monobasic acid and a polybasic acid anhydride.

2. The resin composition described in Claim 1, wherein the weight average molecular weight (Mw) of the polyindene compound (A) is in the range of 100 to 30,000.

3. 3. The resin composition according to claim 1, wherein a mass ratio of solid contents of the polyindene compound (A) to the compound (B) having a polymerizable unsaturated group [(A) / (B)] is in the range of 1 / 100 to 100 / 1.

4. A curable composition comprising the resin composition according to claim 1 or 2 and a photopolymerization initiator.

5. The curable composition described in Claim 4, wherein the content of the polyindene compound (A) is in the range of 5 to 95 mass% in the solid content of the curable composition.

6. A cured product of the resin composition according to claim 1.

7. An article having a coating film comprising the cured product according to claim 1.

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