Composition, cured product, printed wiring board, semiconductor encapsulating material, and build-up film

Abstract

To provide a composition exhibiting excellent mechanical characteristics and high heat resistance when cured, and to provide a cured product thereof.SOLUTION: The present disclosure relates to a composition containing a maleimide-based resin, a propenyl-based resin, and a radical scavenger, a cured product of the composition, a printed wiring board using the composition, a semiconductor encapsulating material using the composition, and a build-up film using the composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a composition, a cured product, a printed wiring board, a semiconductor encapsulating material, and a build-up film. [Background technology]

[0002] In recent years, the trend toward energy conservation and CO2 emission reduction has led to the widespread adoption of power semiconductors in the fields of new energy power conversion and electric vehicles. Therefore, for various electrical materials applications, such as semiconductor encapsulation materials and printed circuit boards, particularly for advanced materials applications, there is a demand for materials and compositions that combine these performance characteristics, such as heat resistance and dielectric properties. In particular, the use of SiC-based devices is expanding in the power semiconductor field due to their high conversion efficiency and potential for miniaturization and weight reduction. Because these SiC-based devices can operate at high temperatures, next-generation power semiconductor encapsulation materials must have high heat resistance to ensure operational reliability at high temperatures. Conventional semiconductor encapsulation materials have used epoxy resins, which offer an excellent balance of physical properties such as heat resistance and moisture resistance. However, to achieve even higher heat resistance, the use of epoxy resins in combination with or as a replacement for resins with higher heat resistance (Tg), such as maleimide resins, benzoxazine resins, and cyanate resins, is being explored. For example, Patent Document 1 discloses a technique relating to a composition containing a maleimide compound having two or more maleimide groups in one molecule and a propenyl group-containing resin. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-019149 Summary of the Invention [Problem to be solved by the invention]

[0004] However, while the technology of Patent Document 1 examines heat resistance and curability (gel time), it does not consider mechanical properties at all. In particular, the reaction between a maleimide group and a propenyl group simultaneously undergoes radical polymerization, which results in a cured product with a different chemical structure than the Diels-Alder reaction or Alder-ene reaction. As a result, the chemical structure of the resulting cured product varies significantly depending on the curing conditions. In particular, it has been confirmed that cured products cured under conditions that favor radical polymerization do not exhibit the desired mechanical properties, particularly bending strength. Therefore, the technical problem to be solved by the present disclosure is to provide a composition that exhibits excellent heat resistance and excellent mechanical properties when cured, and a cured product thereof, a printed wiring board, a semiconductor encapsulating material, and a build-up film. [Means for solving the problem]

[0005] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have found that a composition containing a maleimide-based resin, a propenyl-based resin, and a radical scavenger can provide a composition, a cured product thereof, a printed wiring board, a semiconductor encapsulating material, and a build-up film that exhibit excellent heat resistance and mechanical properties when cured, and have completed the present invention. Furthermore, the composition of the present disclosure can also use a propenyl-based resin and / or a maleimide-based resin that uses plant-derived raw materials (biomass raw materials) as reaction raw materials. This provides a propenyl-based resin and composition that have moldability adaptable to conventional production processes and that are derived from biomass raw materials and have a low environmental impact.

[0006] [1] A composition containing a maleimide-based resin, a propenyl-based resin, and a radical scavenger.

[0007] [2] The maleimide resin is represented by the following general formula (1): [ka] (In the above general formula (1), R 11 and R12 each independently represents a hydroxyl group, an alkyl group, an alkoxy group, or an aryl group; M 11 represents a divalent linking group, m11 represents an integer of 0 to 4, m12 represents an integer between 0 and 3, n11 is the number of repeating units and represents a natural number.

[0008] [3] The composition according to [1] or [2], wherein the propenyl-based resin is one or more selected from the group consisting of resins represented by the following general formulas (i) and (ii): [ka] (In the above general formula (i), M i1 is n i represents a 2-valent organic group, M i2 represents a cyclic group having one or more unsaturated bonds, which may be substituted by a substituent R, and the carbon-carbon double bond at the -CH=CH-CH3 moiety in the general formula (i) and M i2 and the one or more unsaturated bonds in M ​​form a conjugated diene structure in s-cis configuration, or i2 It itself has a conjugated diene structure in s-cis configuration, L i1 and L i3 each independently represents a single bond, -O- or -S-; L i2 represents a divalent organic group, n i represents a natural number between 2 and 4.) [ka] (In the above general formula (ii), M ii1 and M ii2 each independently represents a cyclic group having one or more unsaturated bonds, which may be substituted by a substituent R, and the carbon-carbon double bond at the -CH=CH-CH3 moiety in the general formula (ii) and M ii1and M ii2 and the one or more unsaturated bonds in M ​​have a conjugated diene structure in s-cis configuration, or ii1 and M ii2 It itself has a conjugated diene structure in s-cis configuration, M ii3 each independently represents a divalent linking group, M ii4 represents a divalent organic group, M ii5 each independently represents a trivalent organic group, L ii1 and L ii3 represents a divalent organic group, L ii2 and L ii4 represents a single bond, -O- or -S-; L ii5 and L ii6 represents a single bond, -O- or -S-; n ii represents a natural number.)

[0009] [4] The composition according to any one of [1] to [3], wherein the radical scavenger is one or more selected from the group consisting of hindered phenol compounds, benzenediol compounds, nitroxyl radical compounds, nitrosamine compounds, and phenothiazine compounds.

[0010] [5] A cured product of the composition according to any one of [1] to [4].

[0011] [6] A printed wiring board made using the composition according to any one of [1] to [4].

[0012] [7] A semiconductor encapsulation material comprising the composition according to any one of [1] to [4].

[0013] [8] A build-up film obtained by using the composition according to any one of [1] to [4]. [Effects of the Invention]

[0014] The present disclosure provides a composition that exhibits excellent heat resistance and excellent mechanical properties upon curing. Such cured products are particularly useful in printed wiring boards, semiconductor encapsulation materials, build-up films, and the like. [Brief explanation of the drawings]

[0015] [Figure 1] 1 shows the FD-MS spectrum of the propenyl-based resin-containing mixture (1) synthesized in Synthesis Example 1. [Figure 2A] 1 shows a 1H-NMR chart of the propenyl-based resin-containing mixture (1) synthesized in Synthesis Example 1. [Figure 2B] 1 shows a 13C-NMR chart of the propenyl-based resin-containing mixture (1) synthesized in Synthesis Example 1. [Figure 3] 1 shows the FD-MS spectrum of the propenyl resin (3) synthesized in Synthesis Example 3. [Figure 4] 1 shows a GPC chart of the propenyl resin (3) synthesized in Synthesis Example 3. [Figure 5A] 1 shows a 1H-NMR chart of the propenyl resin (3) synthesized in Synthesis Example 3. [Figure 5B] 1 shows a 13C-NMR chart of the propenyl resin (3) synthesized in Synthesis Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0016] The following describes in detail an embodiment of the present invention (hereinafter referred to as the "present embodiment"); however, the present disclosure is not limited to the following description and can be implemented in various modifications within the scope of its gist.

[0017] [term] In this specification, the term "reaction raw material" refers to a compound that is used to obtain a target compound through a chemical reaction such as synthesis or decomposition and that partially constitutes the chemical structure of the target compound, and excludes substances that serve as chemical reaction auxiliaries, such as solvents and catalysts. In particular, in this specification, the term "reaction raw material" refers to a precursor for obtaining the target propenyl resin through a chemical reaction.

[0018] In this specification, the term "organic group" refers to a group whose chemical structure is formed by an organic compound containing one or more carbon atoms being in the form of a monovalent to tetravalent group. In other words, the term "organic group" refers to an atomic group formed by removing one to four hydrogen atoms from an organic compound containing one or more carbon atoms. Therefore, the organic group may contain, in addition to carbon atoms, one or more atoms selected from the group consisting of hydrogen atoms, nitrogen atoms, oxygen atoms, halogen atoms, sulfur atoms, phosphorus atoms, and the like. Furthermore, the term "organic group" encompasses the term "cyclic group" described below. Specific examples of the organic group are preferably groups having a hydrocarbon group, more preferably groups having a linear or branched aliphatic hydrocarbon group or a cyclic hydrocarbon group, and even more preferably groups having a linear or branched saturated aliphatic hydrocarbon group, a cyclic hydrocarbon group having one or more unsaturated bonds, or a group having an aromatic ring. The organic group preferably has 1 to 50 carbon atoms, more preferably 6 to 40 carbon atoms, even more preferably 10 to 30 carbon atoms, and even more preferably 10 to 20 carbon atoms.

[0019] In the present specification, the term "aliphatic hydrocarbon group" refers to a group containing a hydrocarbon having one or more carbon atoms, and includes linear or branched hydrocarbon groups and monocyclic or polycyclic alicyclic hydrocarbon groups, such as alkyl groups, alkenyl groups, and alkynediyl groups. Unless otherwise specified, the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 50, more preferably 6 to 40, even more preferably 10 to 30, and even more preferably 10 to 20. Furthermore, one or more -CH2- groups in the alkyl group, the alkenyl group, and the alkynediyl group may be substituted with -O- or -C(=O)-. Therefore, the term "aliphatic hydrocarbon group" encompasses groups containing an ester bond, an ether bond, or a ketone bond.

[0020] As used herein, the term "cyclic group" refers to an atomic group in which constituent atoms are bonded in a ring, and includes a carbocyclic ring, a heterocyclic ring, a saturated or unsaturated cyclic structure, a monocyclic ring, a ring assembly, a polycyclic structure (e.g., a bicyclic structure), an aromatic ring, a non-aromatic ring, etc., and may be a group consisting of a combination of these. The cyclic group may also contain at least one heteroatom, and further, any one or more hydrogen atoms in the cyclic group may be substituted with at least one substituent (e.g., an electron-donating group). The cyclic group is preferably a group having an aromatic ring (including a heteroaromatic ring), a carbon ring, or a carbon ring having one or more unsaturated bonds. 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. Therefore, for example, M in the general formula (i) described below i2 In the case where M may have an aromatic ring as a divalent cyclic group, a preferred divalent cyclic group may be a group in which any two hydrogen atoms have been removed from any of the aromatic rings exemplified above or an alicyclic hydrocarbon described below. ii5 In the case where M may have an aromatic ring as a trivalent cyclic group, a preferred trivalent cyclic group may be a group in which any three hydrogen atoms have been removed from each of the aromatic rings exemplified above or an alicyclic hydrocarbon described below. i1When the tetravalent cyclic group may have an aromatic ring, a preferred tetravalent cyclic group may be a group in which any four hydrogen atoms have been removed from any of the aromatic rings exemplified above or the alicyclic hydrocarbons described below. Furthermore, one or more hydrogen atoms of the aromatic ring may be substituted with one or more substituents R. The substituent R is preferably an electron-donating group, and the substituent R is preferably, for example, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, an amino group, or an imino group having an alkyl group having 1 to 5 carbon atoms.

[0021] Examples of the carbocyclic ring include carbocyclic rings in alicyclic hydrocarbons, and the group having a carbocyclic ring with one or more unsaturated bonds may be a group in which one or more -CH2-CH2- in the alicyclic hydrocarbon group are substituted with an ethenylene group (-CH=CH-). Examples of the alicyclic hydrocarbon include cyclohexane, cyclooctane, cyclononane, cyclodecane, adamantane, norbornane, isobornane, etc. For example, examples of the divalent alicyclic hydrocarbon group include divalent monocyclic alicyclic hydrocarbon groups such as cyclohexanediyl group, cyclooctanediyl group, cyclononanediyl group, and cyclodecanediyl group; bicyclo[1.1.0]butanediyl group, tricyclo[2.2.1.0]heptanediyl group, bicyclo[3.2.1]octanediyl group, bicyclo[2.2.2]octanediyl group, adamantanediyl group, bicyclo[4.3.2]undecanediyl group, tricyclo[5.3.1.1]dodecanediyl group, tricyclo[5.2.1.0]octanediyl group, and the like. 2,6Divalent polycyclic alicyclic hydrocarbon groups such as a decanediyl group, an adamantanediyl group, a norbornane group, or an isobornane group are preferred. The alicyclic hydrocarbon group may have, as a substituent, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; or a hydroxy group. For example, a trivalent alicyclic hydrocarbon group may be a group obtained by removing any one hydrogen atom from the above-mentioned divalent alicyclic hydrocarbon group. Similarly, a tetravalent alicyclic hydrocarbon group may be a group obtained by removing any two hydrogen atoms from the above-mentioned divalent alicyclic hydrocarbon group. Therefore, examples of the carbocyclic ring having one or more unsaturated bonds include groups in which any one or more -CH2-CH2- in the above-exemplified alicyclic hydrocarbons or the above-exemplified alicyclic hydrocarbon groups are substituted with one or more ethenylene groups (-CH=CH-).

[0022] The cyclic group is preferably any one of the following groups (g) to (l), more preferably any one of the groups (h) to (l), even more preferably a group (h) or (j), and even more preferably a 1,4-phenylene group optionally substituted with one or more substituents R. (g) A 1,4-cyclohexylene group optionally substituted by a substituent R (in this group, one -CH- or two or more non-adjacent -CH- groups may be replaced by -O-, or one or more -CH-CH- groups in the 1,4-cyclohexylene group may be replaced by an ethenylene group (-CH=CH-).) (h) A 1,4-phenylene group optionally substituted by a substituent R (in which one -CH= or two or more non-adjacent -CH= groups may be replaced by -N=). (j) a 1,3-phenylene group optionally substituted by a substituent R (in which one -CH= or two or more non-adjacent -CH= groups may be replaced by -N=); (k) a 1,2-phenylene group optionally substituted by a substituent R (in which one -CH= or two or more non-adjacent -CH= groups may be replaced by -N=); and (l) A naphthalenediyl group optionally substituted by a substituent R (one -CH= or two or more non-adjacent -CH= groups in the naphthalenediyl group may be substituted by -N=). In the above groups (g), (h), (j), (k) and (l), the substituent R is preferably an electron-donating group, and specifically, is preferably one or more selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, an amino group and an imino group having an alkyl group having 1 to 5 carbon atoms.

[0023] The term "linking group" as used herein refers to a bond or an atomic group for linking structural units together, and is a divalent organic group, a single bond, -O-, -S-, -CO-, or -N(R 0 )- are mentioned. In addition, the above R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0024] The "alkyl group" in this specification may be linear, branched, or cyclic, and examples thereof include a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n-)decyl group, (n-)undecyl group, (n-)dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclononyl group. The "alkyl group" includes a "cycloalkyl group", and examples of the "cycloalkyl group" include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, and an adamantyl group. Examples of the "alkenyl group" in this specification include a vinyl group, a 1-propenyl group (hereinafter also simply referred to as a propenyl group), a 2-propenyl group (hereinafter also simply referred to as an allyl group), an isopropenyl group, and a 2-methylpropenyl group (methallyl 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 "aryl group" includes, for example, a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. As used herein, the term "aralkyl group" refers to a group in which one of the hydrogen atoms of an alkyl group has been substituted with a monovalent group obtained by removing one of the hydrogen atoms of the above-mentioned aromatic ring (for example, benzene, naphthalene, or biphenyl), and examples thereof include a benzyl group, a phenethyl group (1-phenylethyl group, 2-phenylethyl group), a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, a naphthylbutyl group, a naphthylpentyl group, and a naphthylhexyl group. As used herein, the term "alkylene group" refers to, for example, a group in which any one hydrogen atom has been removed from the above-mentioned exemplary groups of "alkyl group" or "cycloalkyl group." Specific examples of the "alkylene group" include linear alkylene groups such as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl, and dodecane-1,12-diyl; and Examples of branched alkylene groups include an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a pentane-2,4-diyl group, a 2-methylpropane-1,3-diyl group, a 2-methylpropane-1,2-diyl group, a pentane-1,4-diyl group, and a 2-methylbutane-1,4-diyl group. As used herein, the "alkenylene group" may, for example, be a group in which any one hydrogen atom has been removed from the above-mentioned exemplary "alkenyl group." Specific examples of the "alkenylene group" include linear or branched alkenylene groups such as vinylene, vinylidene, propenediyl, isopropenediyl, butenediyl, isobutenediyl, tert-butenediyl, pentenediyl, hexenediyl, heptenediyl, octenediyl, isooctenediyl, and nonenediyl, as well as cyclobutenediyl, cyclopentenediyl, cyclohexenediyl, cycloheptenediyl, cyclooctenediyl, and cyclononenediyl. Examples of the "alkynediyl group" in this specification include an ethynediyl group, a propynediyl group, an isopropynediyl group, a butynediyl group, an isobutynediyl group, a tert-butynediyl group, a pentynediyl group, a hexynediyl group, an octynediyl group, and a nonynediyl 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. The term "structural unit" as used herein refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization; in other words, it refers to a partial structure other than the structure of the chemical bonds involved in the reaction or polymerization in a product compound formed through a reaction or polymerization, and is a so-called residue.

[0025] [Composition] The present disclosure relates to a composition containing a maleimide-based resin, a propenyl-based resin, and a radical scavenger. The presence of a radical scavenger inhibits the progress of radical polymerization in the system, resulting in a cured product through the Diels-Alder reaction between the maleimide group and the propenyl group, which exhibits excellent heat resistance and mechanical properties upon curing. The composition of the present embodiment contains a maleimide-based resin, a propenyl-based resin, a radical scavenger, and additives described below that are added as needed. In the composition of the present embodiment, the content of the maleimide resin is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, even more preferably 30% by mass to 70% by mass, still more preferably 35% by mass to 65% by mass, and particularly preferably 40% by mass to 60% by mass, relative to the total amount (100% by mass) of the composition. In the composition of the present embodiment, the content of the propenyl resin is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, even more preferably 30% by mass to 70% by mass, still more preferably 35% by mass to 65% by mass, and particularly preferably 40% by mass to 60% by mass, relative to the total amount (100% by mass) of the composition. In the composition of the present embodiment, the content of the radical scavenger is, relative to the total amount (100% by mass) of the composition, preferably 0.01% by mass to 5.00% by mass, more preferably 0.03% by mass to 3.00% by mass, even more preferably 0.05% by mass to 2.00% by mass, still more preferably 0.05% by mass to 1.50% by mass, and particularly preferably 0.05% by mass to 1.00% by mass. In the composition of the present embodiment, the total content of the maleimide resin, propenyl resin, radical scavenger, and additives is preferably 10% by mass to 100% by mass, more preferably 20% by mass to 100% by mass, even more preferably 30% by mass to 100% by mass, still more preferably 40% by mass to 100% by mass, and particularly preferably 50% by mass to 100% by mass, relative to the total amount (100% by mass) of the composition. When the composition of the present embodiment contains a maleimide-based resin, a propenyl-based resin, a radical scavenger, and a filler (inorganic filler), the total content of the maleimide-based resin, the propenyl-based resin, the radical scavenger, the filler (inorganic filler), and additives other than the filler is preferably 10% by mass to 100% by mass, more preferably 20% by mass to 100% by mass, even more preferably 30% by mass to 100% by mass, still more preferably 40% by mass to 100% by mass, and particularly preferably 50% by mass to 100% by mass, relative to the total amount (100% by mass) of the composition. On the other hand, when the composition of the present embodiment contains a maleimide-based resin, a propenyl-based resin, and a radical scavenger, but does not contain a filler (inorganic filler), the total content of the maleimide-based resin, the propenyl-based resin, the radical scavenger, and additives other than the filler is preferably 10% by mass to 100% by mass, more preferably 20% by mass to 100% by mass, even more preferably 30% by mass to 100% by mass, still more preferably 40% by mass to 100% by mass, and particularly preferably 50% by mass to 100% by mass, relative to the total amount (100% by mass) of the composition. The components of the composition of this embodiment, namely the maleimide resin, the propenyl resin, the radical scavenger, and the additives that may be added as needed, will be described in detail below.

[0026] (Maleimide resin) The maleimide resin of this embodiment is a compound having two or more maleimide groups in the molecule. Examples of the maleimide resin include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, and other maleimide-based resins. Examples of the other maleimide-based resins include the maleimides described in WO 2020 / 217679, the maleimide-based resins described in Japanese Patent Application Publication No. 7140307, ​​the maleimide-based resin (A) described in JP 2023-146886 A, the acid-modified maleimide-based resin (A) described in WO 2020 / 166212 A, the first maleimide compound (A1) and / or the second maleimide compound (A2) described in JP 2023-152757 A, and the polymaleimide compound (A) described in JP 2023-152755 A. The maleimide resins may be used alone or in combination of two or more. Of the maleimide resins exemplified above, the maleimide resin of this embodiment is preferably an aromatic maleimide resin having two or more maleimide groups in the molecule, which makes it easier to obtain a cured product with high heat resistance.

[0027] The maleimide resin of this embodiment may also be a polymer adduct obtained by polymerizing an aromatic maleimide resin having two or more maleimide groups in the molecule with an aromatic polyamine. In other words, the maleimide resin of this embodiment may be an aromatic maleimide resin having two or more maleimide groups in the molecule, or a compound produced by reacting an aromatic maleimide resin having two or more maleimide groups in the molecule with an aromatic polyamine as reaction raw materials.

[0028] When forming a polymer adduct by polymerizing the aromatic maleimide resin having two or more maleimide groups in the molecule with an aromatic polyamine, examples of the aromatic polyamine include m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 2,6-diaminopyridine, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diamino-3-methyldiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, and bis(4-aminophenyl)phenyl. amines, m-xylylenediamine, p-xylylenediamine, 1,3-bis[4-aminophenoxy]benzene, 3-methyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2',5,5'-tetrachloro-4,4'-diaminodiphenylmethane, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-ethyl-4-aminophenyl)propane, 2,2-bis(2,3-dichloro-4-aminophenyl)propane, bis(2,3-dimethyl-4-aminophenyl)phenylethane, ethylenediamine, and hexamethylenediamine.

[0029] The maleimide resin of this embodiment is preferably a compound represented by the following general formula (1). [ka] (In the above general formula (1), R 11 and R 12 each independently represents a hydroxyl group, an alkyl group, or an alkoxy group; M 11 represents a divalent linking group, m11 represents an integer of 0 to 4, m12 represents an integer between 0 and 3, n11 is the number of repeating units and represents a natural number. This allows the maleimide resin to have an aromatic ring, making it easier to obtain a cured product with even higher heat resistance upon curing.

[0030] In the above general formula (1), R 11 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms. In the above general formula (1), R 12 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms.

[0031] In the above general formula (1), M 11 is preferably an alkylene group having 1 to 10 carbon atoms or a divalent aromatic ring hydrocarbon group having 7 to 16 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms. The divalent aromatic ring hydrocarbon group may be any hydrocarbon group having an aromatic ring, and may be a group in which one arbitrary hydrogen atom has been removed from an aryl group or an aralkyl group. The divalent aromatic ring hydrocarbon group may preferably be a group in which one arbitrary hydrogen atom has been removed from an aralkyl group.

[0032] In general formula (1), m11 is preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, and even more preferably 0. In general formula (1), m12 is preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, and even more preferably 0. In the general formula (1), n11 is preferably a natural number of 1 to 20, more preferably a natural number of 1 to 10, and even more preferably a natural number of 1 to 5.

[0033] A preferred maleimide resin in this embodiment may be one or more compounds selected from the group consisting of 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, and 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane. In the composition of the present embodiment, the content of the maleimide resin represented by general formula (1) is preferably 10 to 80 mass %, more preferably 15 to 75 mass %, even more preferably 20 to 70 mass %, and particularly preferably 25 to 65 mass %, relative to the total amount (100 mass %) of the composition. When the content of the maleimide resin is within the above range, it is possible to achieve an effect of achieving a high level of moldability, heat resistance (particularly a high glass transition temperature), and mechanical properties (particularly bending strength). The upper and lower limits of the content of the maleimide resin can be appropriately adjusted.

[0034] The number average molecular weight (Mn) of the maleimide resin of this embodiment is preferably in the range of 300 to 2,000, and more preferably in the range of 300 to 1,000. The number average molecular weight (Mn) of the maleimide resin of this embodiment is measured using gel permeation chromatography (hereinafter abbreviated as "GPC") under the measurement conditions described in the examples described later.

[0035] (Propenyl resin) The propenyl resin of this embodiment is a substance having one or more 1-propenyl groups and one or more unsaturated bonds in the molecule, and having a conjugated diene structure in s-cis conformation. The propenyl resin is preferably a compound capable of forming a conjugated diene structure in s-cis conformation with the 1-propenyl groups and the unsaturated bonds. Examples of the propenyl-based resin of the present embodiment include one or more compounds selected from the group consisting of compounds represented by the following general formula (i) and compounds represented by the following general formula (ii): [ka] (In the above general formula (i), M i1 is n i represents a 2-valent organic group, L i1 and L i3 each independently represents a single bond, -O- or -S-; L i2 represents a divalent organic group, M i2 represents a cyclic group having one or more unsaturated bonds, which may be substituted by a substituent R, and the carbon-carbon double bond at the -CH=CH-CH3 moiety in the general formula (i) and M i2 and the one or more unsaturated bonds in M ​​form a conjugated diene structure in s-cis configuration, or i2 It itself has a conjugated diene structure in s-cis configuration, ni represents a natural number between 2 and 4.) [ka] (In the above general formula (ii), M ii1 and M ii2 each independently represents a cyclic group having one or more unsaturated bonds, which may be substituted by a substituent R, and the carbon-carbon double bond at the -CH=CH-CH3 moiety in the general formula (ii) and M ii1 and M ii2 and the one or more unsaturated bonds in M ​​have a conjugated diene structure in s-cis configuration, or ii1 and M ii2 It itself has a conjugated diene structure in s-cis configuration, M ii3 each independently represents a divalent linking group, preferably a divalent organic group; M ii4 each independently represents a divalent organic group; Mii5 represents a trivalent organic group, L ii1 and L ii3 represents a divalent organic group, L ii2 and L ii4 represents a single bond, -O- or -S-; L ii5 and L ii6 represents a single bond, -O- or -S-; nii represents a natural number.)

[0036] The propenyl resin represented by the general formula (i) and the propenyl resin represented by the general formula (ii) will be described in detail below. <Propenyl-based resin represented by general formula (i)> By using the propenyl-based resin of this embodiment as the propenyl-based resin represented by the above general formula (i), the effect of exhibiting superior curability and an excellent appearance with reduced voids or unevenness upon curing is achieved. Furthermore, in a composition containing both a propenyl resin represented by general formula (i) and a maleimide resin having a maleimide group, the gel time is short, and the curing reaction with the compound or resin having a maleimide group can be completed at a conventional curing temperature (e.g., 175°C or lower).

[0037] "M i1 " In general formula (i), M i1 is n i The organic group is an aryl group. The organic group is defined by the definition of "organic group" in the above [Terminology] section. i1 is preferably a divalent to tetravalent organic group. Preferred M in formula (i) i1 The compound preferably has a chemical structure having a rigid portion (a so-called mesogenic structure, such as a cyclic group), and preferably has a cyclic group having 6 to 30 carbon atoms. In addition, M in the above general formula (i) i1In the divalent organic group, one or more hydrogen atoms of the organic group may be substituted with one or more substituents R. The substituents R are as explained in the above section [Terminology]. M in general formula (i) i1 Preferred examples of the group include groups represented by the following formulae (I) to (VI). [ka] (In the above formulas (I) to (VI), R f , R e , R g , R h , R j , R k and R l each independently represents a hydroxyl group, an amino group, a cyano group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; R 1a and R 2b each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n f , n e , n g and n h each independently represents an integer of 0 to 4, n j represents an integer between 0 and 6, n k and n l each independently represents an integer of 0 or more and 5 or less.) In the groups represented by the above formulae (I) to (IV), the bond -* is preferably bonded to the carbon atom at the para position (4th position) of each benzene ring. In the group represented by the above formula (V), the bond -* is preferably bonded to one of the carbon atoms at positions 1 to 4 and one of the carbon atoms at positions 5 to 8 of the naphthalene ring. In the group represented by the above formula (VI), the bond -* is preferably bonded to one of the carbon atoms at positions 1 to 4 and one of the carbon atoms at positions 5 to 8 of each naphthalene ring. In addition, R in the above formulas (I) to (IV) f , R e , Rg , R h , R j , R k and R l corresponds to the substituent R.

[0038] In the chemical structure of the propenyl-based resin of this embodiment, M in general formula (i) i1 By having a cyclic group, especially an aromatic ring, a rigid mesogenic structure can be formed within the molecule, which provides the effect of high heat resistance.

[0039] M in the above general formula (i) i1 is particularly preferably one or more types selected from groups represented by the following formulas (a) to (f). [ka] (In the above formulas (a) to (f), "*" indicates a bond to another atom.) In the groups represented by the above formulae (a) to (f), the linking group -* is preferably bonded to the carbon atom at the para position (4th position) of each benzene ring. In the group represented by the above formula (e), the linking group -* is preferably bonded to one of the carbon atoms at positions 1 to 4 and one of the carbon atoms at positions 5 to 8 of the naphthalene ring. In the group represented by the above formula (f), the linking group -* is preferably bonded to one of the carbon atoms at positions 1 to 4 and one of the carbon atoms at positions 5 to 8 of each naphthalene ring. Of the groups represented by the above formulae (a) to (f), the groups represented by the above formulae (a), (b), (d) and (e) are preferred from the viewpoint of low viscosity. In addition, M in the general formula (i) i1 is included in the group (so-called residue) derived from a hydrocarbon-containing compound having a first reactive functional group, such as the epoxy compound (1) described below.

[0040] "M i2 " In the above general formula (1), M i2represents a cyclic group having one or more unsaturated bonds, which may be substituted by a substituent R, and the carbon-carbon double bond at the -CH=CH-CH3 moiety in the general formula (i) and M i2 and the one or more unsaturated bonds in M ​​form a conjugated diene structure in s-cis configuration, or i2 It itself has a conjugated diene structure in s-cis configuration. This allows the cyclic group to serve as a substrate for the Diels-Alder reaction with the maleimide group, which is a dienophile (so-called dienophile). Therefore, in addition to the Alder-ene reaction, a faster Diels-Alder reaction is likely to proceed, resulting in superior curability. As a result, the curing temperature of the composition containing the propenyl resin and the maleimide resin of this embodiment can be set relatively low (for example, 200°C or lower (preferably 175°C or lower)). The cyclic group having one or more unsaturated bonds is defined by the terms "cyclic group" and "group containing a carbocyclic ring having one or more unsaturated bonds" described above. i2 may be the same as or different from each other. In addition, M in the above general formula (i) i2 In the cyclic group having one or more unsaturated bonds, one or more hydrogen atoms of the cyclic group may be substituted with one or more substituents R. The substituents R are as explained in the above section of [Terminology].

[0041] In the above general formula (1), M i2 The number of carbon atoms is preferably 5 to 14, more preferably 6 to 12, more preferably 6 to 10, and more preferably 6. M in the above general formula (i) i2When the divalent cyclic group has an aromatic ring, examples of the aromatic ring include a monocyclic aromatic ring, a fused aromatic ring, and a ring assembly aromatic ring. Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of the fused aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Examples of the ring assembly aromatic ring include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. Therefore, M in the above general formula (i) i2 A preferred divalent cyclic group may be a group in which any two hydrogen atoms have been removed from each of the aromatic rings exemplified above. When the cyclic group has an aromatic ring, a diene structure can be formed, which facilitates the Diels-Alder reaction with the maleimide group, thereby providing the effect of achieving superior curability. Furthermore, the Diels-Alder reaction is highly reactive, making it possible to cure at low temperatures with compounds having unsaturated groups such as maleimide groups. In addition, M in the above general formula (i) i2 When has an aromatic ring as a divalent cyclic group, one or more hydrogen atoms of the aromatic ring may be substituted with one or more substituents R.

[0042] M in the above general formula (i) i2When the cyclic group is any of the groups (g) to (l) above, the alkenyl group adopts a planar conformation, reducing steric hindrance and facilitating the pericyclic reaction with the bulky maleimide group, resulting in superior curability. Furthermore, when the cyclic group is any of the groups (h) to (l), an electron-rich diene structure is formed, facilitating the Diels-Alder reaction with the maleimide group, resulting in superior curability. Furthermore, when the cyclic group is a group (h) or (j), the two ortho positions of the alkenyl group can serve as reaction sites, facilitating the Diels-Alder reaction with the maleimide group, resulting in superior curability. Furthermore, the high reactivity of the Diels-Alder reaction allows for low-temperature curing with compounds having unsaturated groups such as maleimide groups.

[0043] In the general formula (i), preferred M i2 may be substituted with a substituent R, and it is even more preferred that the substituent R is an electron-donating group. As defined by the Woodward-Hoffmann rule, in the cycloaddition of two molecules, the reaction is regulated by the HOMO of the diene (the diene structure in general formula (i), for example, the cyclic group and the propenyl group) and the LUMO of the dienophile (the maleimide group) in the thermal reaction, while the reaction is regulated by the LUMO of both in the photoreaction. Therefore, electron-rich dienes with strong electron-donating groups have a smaller energy difference between the HOMO of the diene and the LUMO of the maleimide group, so the reaction is more likely to proceed at lower temperatures. In other words, the substituent R i3 is an electron donating group, then the substituent R i3 This increases the HOMO of the bonded diene, which increases the Diels-Alder reactivity with the maleimide group. As a result, the reaction proceeds more easily at low temperatures, which is thought to improve curability. In the propenyl resin having a 1-propenylbenzene (β-methylstyrene) skeleton shown in the Examples (for example, Synthesis Example 1) which are examples of this embodiment, an electron-donating substituent R i3It has been confirmed that the introduction of a methoxy group as a substituted alkoxy group can enhance the Diels-Alder reactivity with the maleimide group. Furthermore, it has been found that the propenyl resin described in the synthesis examples is substituted with two alkoxy groups, and therefore has higher reactivity with the maleimide group than an unsubstituted or monosubstituted 1-propenylbenzene skeleton. In the above general formula (i), M i2 A specific example of the group is preferably a phenylene group having an alkoxy group as the electron-donating substituent R. In addition, M in the general formula (i) i2 is included in the group (so-called residue) derived from a cyclic compound having an alkenyl group and a second reactive functional group (for example, an aromatic hydrocarbon-containing compound having an alkenyl group and a second reactive functional group, particularly an alkenylphenol compound) described below.

[0044] "L i1 , L i2 and L i3 " In the above general formula (i), L i1 preferably represents a single bond or —O—. In the above general formula (i), L i3 preferably represents a single bond or —O—. In general formula (i), L i2 represents a divalent organic group. The organic group is defined by the same definition as in the "organic group" section above. i2 is preferably an organic group that serves as a linking group. Preferred L in formula (i) i2 is a group having a linear or branched saturated aliphatic hydrocarbon group, and more preferably represents an alkylene group having 1 to 10 carbon atoms, provided that one or more -CH2- in the alkylene group may be substituted with -CH(-OH)-, -O-, or -C(=O)-. L in the above general formula (i) i2 The number of carbon atoms in the group L in the general formula (i) is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 6. i2 is preferably linear or branched. L in the above general formula (i) i2 is an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 9 carbon atoms (-[(CH2) n -(CH2O) m ] p -(CH2) k -), -[(CH2) n -(CH(OH)) m -(CH2) k ] p -or-[(CH2) n -(CH(OH)) m -(CH2) k ] p -OC(=O)-(CH2) l -C(=O)- is preferred, where n is an integer of 0 or more and 8 or less, m is an integer of 1 or more and 9 or less, k is an integer of 0 or more and 8 or less, l is an integer of 2 or more and 4 or less, and p is an integer of 1 or more and 3 or less, and n+m+k+l=an integer of 1 or more and 10 or less. In general formula (i), L i2 By having an alkylene group of a predetermined length, the melting point of the propenyl compound (the softening point of the resin) can be lowered, and therefore the propenyl compound is compatible with the maleimide resin under conventional kneading conditions, making it possible to prepare a uniform composition and a cured product. As a result, L i2 By having a molecular chain of a predetermined length, it is possible to provide a composition that exhibits an excellent appearance with reduced voids or unevenness when cured. This is believed to improve compatibility with maleimide resins, which in turn allows for the preparation of uniform compositions and cured products, which are believed to exhibit excellent appearance with reduced voids or unevenness upon curing. In addition, L in the general formula (i) i2 and L i3 corresponds to a group (so-called residue) derived from a hydrocarbon-containing compound having a first reactive functional group, such as the epoxy compound (1) described below. i1corresponds to, for example, a group (so-called residue) derived from a cyclic compound having an alkenyl group and a second reactive functional group (an aromatic hydrocarbon-containing compound having an alkenyl group and a second reactive functional group, particularly an alkenylphenol compound).

[0045] "ni" In the above general formula (i), ni represents a natural number of 2 or more and 4 or less, with 2 or 3 being preferred, and 2 being more preferred. In the above general formula (i), the substituent R is more preferably a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, from the viewpoint of increasing the HOMO of the cyclic group to which the substituent R is bonded.

[0046] (Preferred form of propenyl resin represented by general formula (i)) The propenyl-based resin of the present embodiment is more preferably represented by the following general formula (i-1). [ka] (In the above general formula (i-1), M i1 represents a nivalent organic group, M i2 represents a cyclic group optionally substituted by a substituent R; ni represents a natural number between 2 and 4.) This results in a lower melting point (or softening point) due to the presence of flexible and polar 2-hydroxypropylene groups, and improved compatibility with maleimide-based resins, etc., making it easier to prepare a uniform composition, resulting in an excellent appearance with fewer voids or unevenness upon curing. Furthermore, hydrogen bonding occurs between the OH groups and the metal surface, resulting in higher adhesion upon curing. "M" in the general formula (i-1) i1 ,ni,M i2 and the substituent R" is the same as "M" in the general formula (i) above. i1 ,ni,M i2 and substituent R" and therefore "M i1 ,ni,M i2and substituent R" are incorporated herein by reference.

[0047] The propenyl resin of this embodiment is preferably one or more compounds selected from the group consisting of the following general formulas (i.1) to (i.9). [ka] (In the above general formulas (i.1) to (i.3), M i3 represents a group selected from the group consisting of the above formulas (I), (IV) and (V), and R i each independently represents an electron-donating group, each nx independently represents an integer of 0 or more and 4 or less, each ny independently represents an integer of 0 or more and 6 or less, and each nz independently represents an integer of 0 or more and 4 or less. [ka] (In the above general formulas (i.4) to (i.6), M i4 each independently represents the above formula (II), and R i each independently represents an electron-donating group, each nx independently represents an integer of 0 or more and 4 or less, each ny independently represents an integer of 0 or more and 6 or less, and each nz independently represents an integer of 0 or more and 4 or less. [ka] (In the above general formulas (i.7) to (i.9), M i5 represents a group selected from the group consisting of formulas (III) and (VI), and R i each independently represents an electron-donating group, each nx independently represents an integer of 0 or more and 4 or less, each ny independently represents an integer of 0 or more and 6 or less, and each nz independently represents an integer of 0 or more and 4 or less. In addition, the substituent R in the above formulas (i.1) to (i.9) i Examples of the substituent R include the same groups as those of the substituent R described in the general formula (i) above. The general formulas (i.1) to (i.9) all have a diene structure formed by the terminal propenyl group and the unsaturated bond in the cyclic group in the molecule, and therefore, a Diels-Alder reaction with the maleimide group can proceed. i The HOMO of the bonded diene increases, which can enhance the Diels-Alder reactivity with the maleimide group. As a result, the reaction proceeds more easily at low temperatures, which can improve the curability and moldability, such as appearance. In the propenyl resin represented by general formula (i), M i2 is a benzene ring, L i1 is preferably bonded to the 1-position of the benzene ring, and the 1-propenyl group is preferably bonded to the 3- or 4-position of the benzene ring. i2 is a naphthalene ring, L i1 is preferably bonded to the 1- or 2-position of the naphthalene ring, and the 1-propenyl group is preferably bonded to the 4-, 5-, 6-, 7- or 8-position of the naphthalene ring.

[0048] <Propenyl-based resin represented by general formula (ii)> By using the propenyl-based resin of this embodiment as a propenyl-based resin represented by the above general formula (ii), the propenyl-based resin exhibits superior heat resistance and mechanical properties when cured.

[0049] "M ii1 and M ii2 " In the above general formula (ii), M ii1 and M ii2 Each independently represents a cyclic group which may be substituted by a substituent R, and is preferably a divalent cyclic group. The cyclic group is defined by the "cyclic group" explained in the above [Terminology] section. In addition, when there are nii M ii1 may be the same as or different from each other. In the above general formula (ii), M ii1 and M ii2 The cyclic group preferably has 5 to 14 carbon atoms, more preferably 6 to 12, more preferably 6 to 10, and even more preferably 6 carbon atoms.

[0050] In the above general formula (ii), M ii1 and M ii2 The cyclic group represented by the formula (ii) preferably has one or more unsaturated bonds, and more preferably the double bond of the propenyl group (the -CH=CH-CH3 moiety) in general formula (ii) and the one or more unsaturated bonds in the cyclic group have a diene structure (=conjugated diene), or the cyclic group itself has a diene structure (=conjugated diene). This facilitates the progress of a faster Diels-Alder reaction in addition to the Alder-ene reaction, resulting in an effect of superior curability. In addition, the propenyl resin represented by general formula (ii) requires a -CH=CH-CH3 moiety. ii1 and / or M ii2 The relative positional relationship between one or more unsaturated bonds in the cyclic group and the double bond in the -CH=CH-CH3 moiety makes it easier to form a so-called 1,3-butadiene skeleton. In general formula (ii), the divalent cyclic group preferably has a ring structure having a diene structure, and more preferably has a diene structure fixed in an s-cis configuration. This allows the cyclic group to serve as a substrate for the Diels-Alder reaction with the maleimide group, which is a dienophile (so-called dienophile).As a result, the curing temperature of the composition containing the propenyl resin of this embodiment and a compound or resin having an unsaturated group such as a maleimide group can be set relatively low (for example, 200°C or lower (preferably 175°C or lower)).

[0051] In the general formula (ii), preferred M ii1 and M ii2is a divalent cyclic group having one or more unsaturated bonds, which may be substituted with a substituent R, and the carbon-carbon double bond at the -CH=CH-CH3 site in general formula (ii) and the one or more unsaturated bonds in the divalent cyclic group have a diene structure (=conjugated diene), or the divalent cyclic group itself has a diene structure (=conjugated diene).Moreover, it is more preferable that the diene structure (=conjugated diene) is a diene structure fixed in an s-cis conformation, and it is even more preferable that the substituent R is an electron-donating group. M in general formula (ii) ii1 The carbon-carbon double bond at the -CH=CH-CH3 site bonded to M ii1 and the one or more unsaturated bonds in the divalent cyclic group satisfy the relationship of a diene structure (=conjugated diene), whereby a Diels-Alder reaction between the maleimide group and the diene structure due to heat can proceed, thereby improving curability. Similarly, when the divalent cyclic group itself has a diene structure (=conjugated diene), a Diels-Alder reaction between the maleimide group and the diene structure due to heat can proceed, thereby improving curability. Furthermore, these diene structures (=conjugated dienes) satisfy the s-cis conformational relationship, making them more likely to serve as substrates for the Diels-Alder reaction with maleimide groups. As defined by the Woodward-Hoffmann rule, in the cycloaddition of two molecules, the thermal reaction is governed by the HOMO of the diene (the diene structure in general formula (ii), e.g., the cyclic group and the propenyl group) and the LUMO of the dienophile (the maleimide group), while the photoreaction is governed by the LUMO of both. Therefore, electron-rich dienes with strong electron-donating groups have a smaller energy difference between the HOMO of the diene and the LUMO of the maleimide group, making the reaction more likely to proceed at lower temperatures. In other words, if the substituent R is an electron-donating group, the HOMO of the diene to which the substituent R is bonded increases, enhancing the Diels-Alder reactivity with the maleimide group. As a result, the reaction is more likely to proceed at lower temperatures, which is thought to improve curability. Therefore, in a propenyl resin represented by general formula (ii) having a 1-propenylbenzene (β-methylstyrene) skeleton shown in an example (e.g., Synthesis Example 3) that is an example of this embodiment, it has been confirmed that the Diels-Alder reactivity with a maleimide group can be enhanced by introducing a methoxy group as an electron-donating substituent R into the aromatic ring. Furthermore, it has been found that the propenyl resin described in the Synthesis Example is substituted with two alkoxy groups, and therefore has higher reactivity with a maleimide group than unsubstituted or monosubstituted 1-propenylbenzene. Therefore, M in the above general formula (ii) ii1 and M ii2 Preferably, each independently has an aromatic ring as a divalent cyclic group, which makes it easier to serve as a substrate for the Diels-Alder reaction.

[0052] M in the above general formula (ii) ii1 and M ii2 When each independently has an aromatic ring as a divalent cyclic group, examples of the aromatic ring include a monocyclic aromatic ring, a fused aromatic ring, and a ring assembly aromatic ring. Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of the fused aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Examples of the ring assembly aromatic ring include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. Therefore, M in the above general formula (ii) ii1 and M ii2 A preferred divalent cyclic group may be a group in which any two hydrogen atoms have been removed from each of the aromatic rings exemplified above. When the cyclic group has an aromatic ring, a diene structure can be formed, which facilitates the Diels-Alder reaction with the maleimide group, thereby providing the effect of achieving superior curability. Furthermore, the Diels-Alder reaction is highly reactive, making it possible to cure at low temperatures with compounds having unsaturated groups such as maleimide groups. In addition, M in the above general formula (ii) ii1 and M ii2 When has an aromatic ring as a divalent cyclic group, one or more hydrogen atoms of the aromatic ring may be substituted with one or more substituents R. The substituents R are as explained in the above section [Terminology].

[0053] The cyclic group in the general formula (ii) is more preferably any one of the groups (g) to (l) above, even more preferably any one of the groups (h) to (l), still more preferably a group (h) or (j), and even more preferably a 1,4-phenylene group optionally substituted by one or more substituents R. In the above general formula (ii), M ii1 and M ii2 A specific example of the above is a phenylene group having an alkoxy group bonded as the electron-donating substituent R. In addition, M in the general formula (ii) ii1 and M ii2 is included in the group (so-called residue) derived from the alkenylphenol compound described below.

[0054] In the above general formula (ii), the substituent R is preferably an electron-donating group, and specifically, is preferably one or more selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, an amino group, and an imino group having an alkyl group having 1 to 5 carbon atoms. From the viewpoint of increasing the HOMO of the cyclic group to which the substituent R is bonded, the substituent R is more preferably a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. In addition, M in the general formula (ii) ii1 and Mii2 is encompassed, for example, in groups (so-called residues) derived from cyclic compounds (particularly the above alkenylphenol compounds) having an alkenyl group and a second reactive functional group, which will be described later.

[0055] "M ii3 " In general formula (ii), M ii3 represents a divalent organic group. The organic group is the same as that described in the "Terminology" section above. ii3 may be the same as or different from each other. In the above general formula (ii), M ii3 The number of carbon atoms is preferably 1 to 20, more preferably 6 to 20, even more preferably 7 to 16, even more preferably 8 to 15, and particularly preferably 8 to 14. M ii3 When the number of carbon atoms in the organic group is 6 or more, the distance between crosslinking points becomes longer, making it easier to suppress cracks that occur during curing, and when the number of carbon atoms in the organic group is 20 or less, the viscosity becomes low, making it easier to load a high amount of filler. In the above general formula (ii), M ii3 preferably represents a divalent organic group having from 1 to 20 carbon atoms, more preferably a linear or branched alkylene group or a divalent cyclic group having from 1 to 6 carbon atoms, and even more preferably a group having an aromatic ring or a carbon ring which may be substituted with a substituent R. In addition, M in the above general formula (ii) ii3 In the organic group represented by the formula: one or more hydrogen atoms of the organic group may be substituted with one or more substituents R. The substituents R are as explained in the above section [Terminology]. In the above general formula (ii), preferred M ii3Examples of the group having a carbocyclic ring as the carbon ring include divalent monocyclic alicyclic hydrocarbon groups such as a cyclohexanediyl group, a cyclooctanediyl group, a cyclononanediyl group, and a cyclodecanediyl group; a bicyclo[1.1.0]butanediyl group, a tricyclo[2.2.1.0]heptanediyl group, a bicyclo[3.2.1]octanediyl group, a bicyclo[2.2.2]octanediyl group, an adamantanediyl group, a bicyclo[4.3.2]undecanediyl group, a tricyclo[5.3.1.1]dodecanediyl group, and a tricyclo[5.2.1.0] 2,6 Divalent polycyclic alicyclic hydrocarbon groups such as a decanediyl group, an adamantanediyl group, a norbornane group, or an isobornane group are preferred. The alicyclic hydrocarbon group may have, as a substituent, an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; or a hydroxy group. Separately, one or more hydrogen atoms of the alicyclic hydrocarbon group may be substituted with one or more of the substituents R. On the other hand, M ii3 When is a group having an aromatic ring, the aromatic ring is preferably a divalent aromatic hydrocarbon group having 8 to 14 carbon atoms. The divalent aromatic ring hydrocarbon group may be any hydrocarbon group having a divalent aromatic ring, and may be a group in which one hydrogen atom has been removed from an aryl group or an aralkyl group. The divalent aromatic ring hydrocarbon group may preferably be a group in which one hydrogen atom has been removed from an aralkyl group.

[0056] M in general formula (ii) ii3 Examples of R are preferably groups represented by the following formulae (M-1) to (M-5). 2r corresponds to the substituent R. [ka] (In the above formulas (M-1) to (M-5), R 2r each independently represents a hydroxyl group, an amino group, an alkyl group, or an alkoxy group; L 1r and L 2r each independently represents a single bond or a linear or branched alkylene group having 1 to 15 carbon atoms; R 3r each independently represents a hydroxyl group, an amino group, an alkyl group, or an alkoxy group, n2 represents an integer of 0 or more and 6 or less, n3 represents an integer of 0 or more and 4 or less, n4 represents an integer of 0 or more and 3 or less, and n5 represents an integer of 0 or more and 5 or less. In the groups represented by the above formulae (M-1) to (M-5), * represents a bond to another atom.

[0057] In addition, the above-mentioned M ii3 is more preferably a group represented by formulae (Mi) to (M-ix), and further preferably a group represented by formulae (Mi-1) to (M.ix-1). In addition, R in the following formulas (Mi) to (M-ix) 2r corresponds to the substituent R. [ka] (In the above formulas (Mi) to (M-ix), R 2r each independently represents a hydroxyl group, an amino group, an alkyl group, or an alkoxy group; R 1r , R 3r , R 4r , R 5r and R 6r each independently represents a hydroxyl group, an amino group, an alkyl group, or an alkoxy group; R 7r , R 8r , R 9r and R 10r each independently represents a hydrogen atom, a hydroxyl group, an amino group, an alkyl group, or an alkoxy group, n 2 represents an integer between 0 and 6, and n 3 represents an integer of 0 or more and 4 or less. In the groups represented by the above formulae (Mi) to (M-ix), * represents a bond to another atom. [ka] (In the above formulae (Mi-1) to (M.ix-1), "*" indicates a bond to another atom.) Also, M ii3 In the various formulas above, it is preferable that the two bonds "*" are spaced apart from each other. For example, M ii3 When M has a benzene ring, it is preferable that a group having a bond "*" is bonded to the ortho-position (1st and 3rd positions) or the para-position (1st and 4th positions). ii3 When M has a biphenyl ring, it is preferable that a group having a bond "*" is bonded to 4,4' or 3,5' (or 3',5). ii3 is a cyclodecane ring (e.g., tricyclo[5.3.1.1]dodecanediyl group, tricyclo[5.2.1.0 2,6 ]decane), it is preferred that a group having a bond "*" is bonded to the 2-position or 3-position and the 5-position, 6-position or 7-position. In addition, M in the general formula (ii) ii3 is included in groups (so-called residues) derived from, for example, epoxy resins (particularly, epoxy resin (A)) described below.

[0058] "M ii4 " In general formula (ii), M ii4 represents a divalent organic group. The organic group is defined by the definition of "organic group" explained in the "Terminology" section above. Preferred M in formula (ii) ii4 The alkyl group preferably has a chemical structure having a rigid portion (a so-called mesogenic structure, for example, a divalent cyclic group), and is preferably a cyclic group having 6 to 30 carbon atoms. In the above general formula (ii), M ii4 The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 3 to 12, even more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6 to 7. In addition, M in the above general formula (ii) ii4In the divalent organic group, one or more hydrogen atoms of the organic group may be substituted with one or more substituents R. The substituents R are as explained in the above section [Terminology]. M in general formula (ii) ii4 Preferred examples of the group include groups represented by the following formulae (VII) to (X). [ka] (In the above formulas (VII) to (X), R f each independently represents a hydroxyl group, an amino group, a cyano group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms; n f each independently represents an integer of 0 to 4, n p each independently represents an integer of 0 to 3, n q each independently represents an integer of 0 to 5, n g represents an integer between 0 and 6.) In addition, R in the above formulas (VII) to (X) f corresponds to the substituent R. In addition, M in the general formula (ii) ii4 is included in groups (so-called residues) derived from, for example, epoxy resins (particularly, epoxy resin (A)) described below.

[0059] "M ii5 " In general formula (ii), M ii5 represents a trivalent organic group. The organic group is the same as that described in the "Terminology" section above. ii5 may be the same as or different from each other. Preferred M in formula (ii) ii5 It is preferable that the compound has a rigid portion (a so-called mesogenic structure, for example, a trivalent cyclic group). In the above general formula (ii), M ii5The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 3 to 12, even more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6 to 7. In addition, M in the above general formula (ii) ii5 In the trivalent organic group, one or more hydrogen atoms of the organic group may be substituted with one or more substituents R. The substituents R are as explained in the above section [Terminology]. M in general formula (ii) ii5 As examples thereof, groups represented by the following formulae (XI) to (XIV) are preferred, and groups represented by formulae (XI-1) and (XI-2) are more preferred. [ka] (In the above formulas (XI) to (XIV), R f each independently represents a hydroxyl group, an amino group, a cyano group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms, n x each independently represents an integer of 0 to 3, n p and n y each independently represents an integer of 0 to 5, n z each independently represents an integer of 0 or more and 2 or less.) In addition, R in the above formulas (XI) to (XIV) f corresponds to the substituent R. [ka] In addition, M in the general formula (ii) ii5 is included in groups (so-called residues) derived from, for example, epoxy resins (particularly, epoxy resin (A)) described below.

[0060] "L ii1 and L ii3 " In general formula (ii), L ii1 and L ii3Each independently represents a divalent organic group. The organic group is defined by the same definition as in the "organic group" section above. ii1 and L ii3 is preferably an organic group that serves as a linking group. Preferred L in formula (ii) ii1 and L ii3 is a group having a linear or branched saturated aliphatic hydrocarbon group, and more preferably represents an alkylene group having 1 to 10 carbon atoms, provided that one or more -CH2- in the alkylene group may be substituted with -CH(-OH)-, -O-, or -C(=O)-. In the above general formula (ii), L ii1 and L ii3 may each independently preferably have 1 to 10 carbon atoms, more preferably have 2 to 8 carbon atoms, and even more preferably have 3 to 6 carbon atoms. ii1 and L ii3 are each independently preferably linear or branched. L in the above general formula (ii) ii1 and L ii3 are each independently an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 1 to 9 carbon atoms (-[(CH2) n -(CH2O) m ] p -(CH2) k -), -[(CH2) n -(CH(OH)) m -(CH2) k ] p -or-[(CH2) n -(CH(OH)) m -(CH2) k ] p -OC(=O)-(CH2) l -C(=O)- is preferred, where n is an integer of 0 or more and 8 or less, m is an integer of 1 or more and 9 or less, k is an integer of 0 or more and 8 or less, l is an integer of 2 or more and 4 or less, and p is an integer of 1 or more and 3 or less, and n+m+k+l=an integer of 1 or more and 10 or less. In general formula (ii), L ii1 and / or Lii3 By having an alkylene group of a predetermined length, the melting point of the propenyl resin (the softening point of the resin) can be lowered, and therefore the propenyl resin is compatible with the maleimide resin under conventional kneading conditions, making it possible to prepare a uniform composition and a cured product. As a result, L ii1 and L ii2 By having an alkylene group of a predetermined length, it is possible to provide a composition that exhibits an excellent appearance with reduced voids or unevenness when cured. This is believed to improve compatibility with maleimide resins, which in turn allows for the preparation of uniform compositions and cured products, which are believed to exhibit excellent appearance with reduced voids or unevenness upon curing. Among them, L in the above general formula (ii) ii1 and L ii2 -[(CH2) n -(CH(OH)) m -(CH2) k ] p -, since it has a 2-hydroxypropylene ether skeleton similar to that of cured epoxy resins, hydrogen bonding occurs between the OH group and the metal surface, resulting in higher adhesion when cured. In addition, L in general formula (ii) ii1 and / or L ii3 corresponds to, for example, a group (so-called residue) derived from an epoxy resin (particularly, epoxy resin (A)) described below.

[0061] "L ii2 and L ii4 , L ii5 and L ii6 " In the above general formula (ii), L ii2 and L ii4 are each independently preferably a single bond or —O—. In the above general formula (ii), L ii5 and L ii6 are each independently preferably a single bond or —O—. In the above general formula (ii), L ii2 and L ii4corresponds to, for example, a group (residue) derived from a cyclic compound (particularly, an alkenylphenol compound) having an alkenyl group and a second reactive functional group, which will be described later. ii5 and L ii6 corresponds to, for example, a group (so-called residue) derived from an epoxy resin (particularly, epoxy resin (A)) described below.

[0062] "n ii " In the above general formula (ii), n ii represents a natural number of 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.

[0063] (Preferred form of propenyl resin represented by general formula (ii)) The propenyl-based resin of the present embodiment is more preferably represented by the following general formula (ii-1). [ka] (In the above general formula (ii-1), M ii1 and M ii2 each independently represents a cyclic group having one or more unsaturated bonds, which may be substituted by a substituent R, and the carbon-carbon double bond at the -CH=CH-CH3 moiety in the general formula (ii-1) and M ii1 and M ii2 and the one or more unsaturated bonds in M ​​have a conjugated diene structure in s-cis configuration, or ii1 and M ii2 It itself has a conjugated diene structure in s-cis configuration, M ii3 each independently represents a divalent linking group, M ii4 represents a divalent organic group, preferably a divalent aromatic hydrocarbon group; M ii5 each independently represents a trivalent organic group, preferably a trivalent aromatic hydrocarbon group; n ii represents a natural number.) This results in a lower melting point (or softening point) due to the presence of flexible and polar 2-hydroxypropylene groups, and improved compatibility with maleimide-based resins, etc., making it easier to prepare a uniform composition, resulting in an excellent appearance with fewer voids or unevenness upon curing. Furthermore, hydrogen bonding occurs between the OH groups and the metal surface, resulting in higher adhesion upon curing. "M" in the general formula (ii-1) ii1 , M ii2 , n ii , M ii3 , substituents R, M ii4 and M ii5 " is the same as "M" in the general formula (ii) above. ii1 , M ii2 , n ii , M ii3 , substituents R, M ii4 and M ii5 ", so "M" in the above general formula (ii) ii1 , M ii2 , n ii , M ii3 , substituents R, M ii4 and M ii5 "The contents of this document are incorporated herein by reference.

[0064] The propenyl resin of this embodiment is preferably one or more compounds selected from the group consisting of the following general formulas (ii.1) to (ii.3). [ka] [ka] (In the above general formulas (ii.1) to (ii.3), M ii3 represents a group selected from the group consisting of the above formulae (Mi) to (M-ix), and R iieach independently represents an electron-donating group, and is selected from the group consisting of an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms); an alkoxy group having 1 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group; a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; and a hydroxy group; each independently represents an integer of 0 to 3; each independently represents an integer of 0 to 4; and each independently represents an integer of 0 to 6.) Note that R in the above general formulae (ii.1) to (ii.3) ii corresponds to the substituent R. The general formulas (ii.1) to (ii.3) all have a diene structure formed by the terminal propenyl group and the unsaturated bond in the cyclic group in the molecule, and therefore, a Diels-Alder reaction with the maleimide group can proceed. ii5 The HOMO of the bonded diene increases, enhancing the Diels-Alder reactivity with the maleimide group. In the propenyl resin represented by general formula (ii), M ii1 and / or M ii2 is a benzene ring, L ii1 and / or L ii2 is preferably bonded to the 1-position of the benzene ring, and the 1-propenyl group is preferably bonded to the 3- or 4-position of the benzene ring. ii1 and / or M ii2 is a naphthalene ring, L ii1 and / or L ii2 is preferably bonded to the 1- or 2-position of the naphthalene ring, and the 1-propenyl group is preferably bonded to the 4-, 5-, 6-, 7- or 8-position of the naphthalene ring.

[0065] (Another preferred form of propenyl-based resin) Another preferred embodiment of the propenyl resin of this embodiment is a compound having a partial structure represented by the following general formula (iii) and having a molecular weight in the range of 300 to 10,000. [ka] (In the above general formula (iii), R iii5 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and miii represents an integer of 0 to 4. When a propenyl resin having a partial structure represented by the above general formula (iii) and a maleimide resin are present together, the Diels-Alder reaction proceeds more easily, and as a result, the curing temperature of a composition containing a maleimide resin and a radical scavenger can be made relatively low (for example, 200°C or lower (preferably 175°C or lower)).

[0066] The propenyl resin of the present embodiment is more preferably one or more compounds selected from the group consisting of compounds represented by the following general formulas (2) and (3). [ka] (In the above general formula (2), R 21 each independently represents an alkyl group, an alkoxy group, or an aryl group, M 21 represents an n21-valent organic group, L 21 each independently represents an alkylene group having 1 to 10 carbon atoms, provided that one or more -CH- in the alkylene group may be replaced by -CH(-OH)-, -O-, or -C(=O)-; L 22 represents a single bond or -O-; m21 represents an integer between 0 and 4, n21 represents an integer between 2 and 4.) [ka] (In the above general formula (3), R 31 and R 32 each independently represents an alkyl group, an alkoxy group, or an aryl group, M 31 represents a divalent organic group, M 32 each independently represents a trivalent organic group, M 33 each independently represents a divalent linking group, L 32 and L 33 each independently represents an alkylene group having 1 to 10 carbon atoms, provided that one or more -CH- in the alkylene group may be replaced by -CH(-OH)-, -O-, or -C(=O)-; L 34 and L 35 each independently represents a single bond or -O-; m31 and m32 each independently represent an integer of 0 to 4, n31 is the number of repeating units and represents a natural number.)

[0067] The propenyl resin represented by the general formula (2) is included in the propenyl resin represented by the general formula (i). In the above general formula (2), M 21 represents a divalent to tetravalent organic group. In this case, the divalent to tetravalent organic group described in the section above regarding <Propenyl-based resin represented by general formula (i)> is used by reference. In addition, M in the above general formula (2) 21 represents M in the above general formula (i). i1 In order to correspond to the above, M in the general formula (i) i1 The contents of the above are cited. Preferred M 21 is a group represented by the above formulas (I) to (VI), and among these, it is particularly preferable that it is one or more types selected from the groups represented by formulas (a) to (f).

[0068] In the above general formula (2), L 21 each independently represents an alkylene group having 1 to 10 carbon atoms, provided that one or more -CH2- in the alkylene group may be substituted with -CH(-OH)-, -O-, or -C(=O)-. 21 represents L in the above general formula (i). i1 In order to correspond to the above, L in the general formula (i) i1 The contents of the following are cited. 21is an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 2 to 9 carbon atoms (-[(CH2) n -(CH2O) m ] p -), -[(CH2) n -(CH(OH)) m -(CH2) k ] p -or-[(CH2) n -(CH(OH)) m -(CH2) k ] p -OC(=O)- is preferred, where n is an integer of 0 to 8, m is an integer of 1 to 9, k is an integer of 0 to 8, p is an integer of 1 to 3, and n+m+k=an integer of 2 to 9. In the above general formula (2), m21 is preferably an integer of 0 or more and 2 or less, and 1 or 2 is more preferable. In the above general formula (2), n21 is preferably an integer of 2 or more and 3 or less, and 2 is more preferable.

[0069] The propenyl resin represented by the general formula (3) is included in the propenyl resin represented by the general formula (ii). In the above general formula (3), M 31 represents a divalent organic group. In this case, the divalent organic group described in the section <Propenyl-based resin represented by general formula (ii)> above can be used as the divalent organic group. In addition, M in the general formula (3) above 31 represents M in the above general formula (ii). ii4 In order to correspond to the above, M in the general formula (ii) ii4 The contents of the above are cited. Preferred M 31 is a group represented by the above formulas (XI) to (XIV), and among these, it is particularly preferable that it is one or more types selected from the groups represented by formula (XI-1) and formula (XI-2). In the above general formula (3), M 32represents a trivalent organic group. In this case, the trivalent organic group described in the section "Propenyl-based resin represented by general formula (ii)" above can be used as the trivalent organic group. In addition, M in the general formula (3) above 32 represents M in the above general formula (ii). ii5 In order to correspond to the above, M in the general formula (ii) ii5 The contents of the above are cited. Preferred M 32 is a group represented by the above formulas (VII) to (X), and among these, it is particularly preferable that it is one or more types selected from the groups represented by formula (XI-1) and formula (XI-2).

[0070] In the above general formula (3), L 32 and L 33 are preferably each independently an alkylene group having 1 to 10 carbon atoms, provided that one or more -CH2- in the alkylene group may be substituted with -CH(-OH)-, -O- or -C(=O)-. 32 and L 33 are each independently L in the general formula (ii). ii1 and L ii3 In order to correspond to the above, L in the general formula (i) ii1 and L ii3 The contents of each of these will be cited. 32 and L 33 are each independently an alkylene group having 1 to 10 carbon atoms, an alkyleneoxy group having 2 to 9 carbon atoms (-[(CH2) n -(CH2O) m ] p -), -[(CH2) n -(CH(OH)) m -(CH2) k ] p -or-[(CH2) n -(CH(OH)) m -(CH2) k ] p-OC(=O)- is preferred, where n is an integer of 0 to 8, m is an integer of 1 to 9, k is an integer of 0 to 8, p is an integer of 1 to 3, and n+m+k=an integer of 2 to 9.

[0071] In the above general formula (3), M 33 Each independently represents a divalent linking group. In this case, the divalent linking group described in the section "Propenyl-based resin represented by general formula (ii)" above can be used as the divalent linking group. In addition, M in general formula (3) 33 represents M in the above general formula (ii). ii3 In order to correspond to the above, M in the general formula (ii) ii3 The contents of M are cited. 33 is preferably a group represented by any of the above formulas (M-1) to (M-5). In the above general formula (3), m31 and m32 each independently preferably represent an integer of 0 or more and 3 or less, and more preferably 0 or 1. n31 is the number of repeating units and represents a natural number of preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 5.

[0072] (Properties of propenyl resin) <Amount of double bonds in propenyl resin (g / mol)> The double bond equivalent (g / mol) of the propenyl resin of this embodiment is preferably 100 g / mol or more and 1000 g / mol or less, more preferably 200 g / mol or more and 800 g / mol or less, and even more preferably 300 g / mol or more and 600 g / mol or less. The "double bond equivalent (g / mol)" in this specification is an index of the amount of double bonds contained in a molecule, and for compounds of the same molecular weight, the smaller the double bond equivalent value, the greater the amount of double bonds introduced. The "double bond equivalent (g / mol)" is a calculated value calculated by the method described below and the method described in the Examples section. The preferred range of the double bond equivalent (g / mol) can be determined by appropriately rearranging the upper and lower limits. - Calculation method for double bond equivalent of propenyl resin - The double bond equivalent, which is the content of carbon-carbon double bonds in the propenyl resin of the present embodiment, is calculated using the iodine value method in accordance with JIS K0070:1992.

[0073] <Molecular weight of propenyl resin> The molecular weight (number average molecular weight) of the propenyl resin of this embodiment is preferably in the range of 300 to 10,000, and more preferably in the range of 300 to 3,000. For example, the molecular weight of the propenyl resin represented by general formula (i) or general formula (2) of this embodiment is preferably in the range of 300 to 2,000, more preferably in the range of 400 to 1,500, and even more preferably in the range of 500 to 1,000. On the other hand, the number average molecular weight (Mn) of the propenyl resin represented by general formula (ii) or general formula (3) of this embodiment is preferably in the range of 600 to 3000, more preferably in the range of 800 to 2500, and even more preferably in the range of 1000 to 2000. Furthermore, the weight average molecular weight (Mw) of the propenyl resin represented by general formula (ii) or general formula (3) is preferably in the range of 600 to 5000, more preferably in the range of 800 to 4000, and even more preferably in the range of 1000 to 3000. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the propenyl resin represented by general formula (ii) or general formula (3) of this embodiment is preferably in the range of 1.0 to 2.0, more preferably 1.0 to 1.3. The molecular weight of the propenyl resin of this embodiment is measured by FD-MS or GPC, as described in the examples below.

[0074] (Another embodiment of the propenyl resin represented by general formula (i)) The propenyl-based resin represented by general formula (i) of this embodiment is preferably prepared using, as reaction raw materials, a hydrocarbon-containing compound having a first reactive functional group and a cyclic compound having an alkenyl group (preferably a 1-propenyl group) and a second reactive functional group. Examples of the first reactive functional group in the hydrocarbon-containing compound having the first reactive functional group include a glycidyl group, a halogenated alkyl group, a hydroxyl group, a carboxylic acid group, and (-C(=O)-X (X is a halogen atom). Examples of the second reactive functional group in the cyclic compound having an alkenyl group and a second reactive functional group include a halogen atom, a hydroxyl group, a mercapto group, and a glycidyl group.

[0075] "Hydrocarbon-containing compound having a first reactive functional group" As the hydrocarbon-containing compound having the first reactive functional group, for example, a compound having a structure represented by the following general formula (4) is preferred. [ka] (In the above general formula (4), M 6 represents an n4-valent organic group, preferably an n4-valent aliphatic or aromatic hydrocarbon group, more preferably an n4-valent group having an aromatic ring, L 3 each independently represents a divalent linking group, preferably a single bond or an alkylene group having 1 to 6 carbon atoms, with the proviso that one or more -CH- in the alkylene group may be substituted with -O- or -C(=O)-; Y 1 each independently represents a first reactive functional group, which is one selected from the group consisting of a halogen atom, a hydroxyl group, a glycidyl group, a carboxylic acid group, and —C(═O)—X (X is a halogen atom), and n4 represents an integer of 2 or more and 4 or less.

[0076] In general formula (4), M 6 represents an n-tetravalent organic group. The organic group is defined by the same definition as in the "organic group" section above. M in general formula (4) 6is preferably an organic group that serves as a linking group. In the above general formula (4), preferred M 6 represents a divalent to tetravalent aliphatic hydrocarbon group or a divalent to tetravalent aromatic hydrocarbon group. The aliphatic hydrocarbon group is preferably a divalent to tetravalent acyclic aliphatic hydrocarbon group, and may be either linear or branched. The aliphatic hydrocarbon group may be a saturated or unsaturated hydrocarbon, but is preferably a saturated hydrocarbon group, and more preferably a linear saturated hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 13 carbon atoms. For example, examples of divalent acyclic aliphatic hydrocarbon groups having 1 to 13 carbon atoms, which may have a substituent, include alkanediyl groups such as methanediyl, ethanediyl, n-propanediyl, i-propanediyl, n-butanediyl, n-pentanediyl, n-hexanediyl, n-heptanediyl, n-octanediyl, n-nonanediyl, and n-decanediyl. Similarly, an optionally substituted trivalent acyclic aliphatic hydrocarbon group refers to a group obtained by removing one arbitrary hydrogen atom from the aforementioned divalent acyclic aliphatic hydrocarbon group. Furthermore, an optionally substituted tetravalent acyclic aliphatic hydrocarbon group refers to a group obtained by removing two arbitrary hydrogen atoms from the aforementioned divalent acyclic aliphatic hydrocarbon group.

[0077] The divalent to tetravalent aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, even more preferably 6 to 12 carbon atoms, and even more preferably 6 to 10 carbon atoms. The divalent to tetravalent aromatic hydrocarbon group may be a divalent to tetravalent group having an aromatic ring. 6 is M in the above general formula (i) i1 Therefore, the aromatic ring corresponds to M in the above general formula (i). i1 The contents of the exemplary aromatic rings in The divalent to tetravalent aliphatic hydrocarbon group or the divalent to tetravalent aromatic hydrocarbon group may have a substituent R, and preferred examples of the substituent R include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms); an alkoxy group having 1 to 10 carbon atoms; an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group or a naphthyl group; a halogen atom; and a hydroxyl group.

[0078] The hydrocarbon-containing compound having the first reactive functional group is preferably an aliphatic or aromatic hydrocarbon-containing compound having the first reactive functional group, and preferred embodiments of the aliphatic or aromatic hydrocarbon-containing compound include epoxy compound (1) (e.g., epoxy compound (1) having an aromatic ring), divalent to tetravalent alkyl halide compounds (e.g., aromatic compounds having 2 to 4 halogenated alkyl groups), divalent to tetravalent carboxylic acid halides (e.g., aromatic compounds having 2 to 4 -C(=O)-X (X is a halogen atom)), and divalent to tetravalent phenol compounds or alcohol compounds (e.g., aromatic compounds having 2 to 4 hydroxyl groups).

[0079] "Cyclic compounds having an alkenyl group and a second reactive functional group" The cyclic compound having an alkenyl group and a second reactive functional group is preferably an aromatic hydrocarbon-containing compound having an alkenyl group and a second reactive functional group. As the cyclic compound having an alkenyl group and a second reactive functional group, for example, a compound having a structure represented by the following general formula (5) is preferred. [ka] (In the above general formula (5), M 51 represents an (n51+n52+1)-valent cyclic group, preferably an (n51+n52+1)-valent aromatic ring; R 51 represents an alkenyl group, preferably an allyl group or a propenyl group, R 52 each independently represents an electron-donating group, preferably an alkoxy group having 1 to 5 carbon atoms; L5 each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms, provided that one or more -CH2- groups in the alkylene group may be replaced with -O- or -C(=O)-; Y 2 represents a second reactive functional group, each independently being one selected from the group consisting of a halogen atom, a hydroxyl group, a mercapto group, and a glycidyl group; n51 represents an integer between 1 and 4, n52 represents an integer between 0 and 4, n51+n52 represents an integer between 1 and 5.) In the above general formula (5), the cyclic group M 51 The meaning of "cyclic group" is as defined in the above [Terminology] section. Furthermore, the cyclic compound having an alkenyl group and a second reactive functional group is more preferably an aromatic hydrocarbon-containing compound having an alkenyl group and a second reactive functional group, and examples thereof include alkenylphenol compounds, alkenylthiophenol compounds, and alkenylnaphthol compounds, each having one alkenyl group, and alkenylphenyl glycidyl ether compounds, each having one alkenyl group.

[0080] The propenyl-based resin represented by general formula (i) of this embodiment is preferably used as a reaction raw material for any of the following (Z1) to (Z4), more preferably as a reaction raw material for either (Z1) or (Z4), and even more preferably as a reaction raw material for (Z1). (Z1) The propenyl resin represented by general formula (i) of this embodiment is prepared using, as reaction raw materials, an epoxy compound (1) (preferably a divalent to tetravalent epoxy compound (1)) as a hydrocarbon-containing compound having a first reactive functional group, and a cyclic compound having an alkenyl group and a second reactive functional group. The cyclic compound having an alkenyl group and a second reactive functional group includes, for example, an alkenylphenol compound, an alkenylthiophenol compound, an alkenylnaphthol compound, and an alkenylphenyl glycidyl ether compound. (Z2) The propenyl resin represented by general formula (i) of this embodiment is prepared using, as reaction raw materials, a divalent to tetravalent alkyl halide compound as a hydrocarbon-containing compound having a first reactive functional group, and the cyclic compound having the alkenyl group and a second reactive functional group. (Z3) The propenyl resin represented by general formula (i) of this embodiment is prepared using, as reaction raw materials, a divalent to tetravalent carboxylic acid halide as a hydrocarbon-containing compound having a first reactive functional group and a cyclic compound having an alkenyl group and a second reactive functional group. (Z4) The propenyl resin represented by general formula (i) of this embodiment is prepared using, as reaction raw materials, a dihydric to tetrahydric phenol compound or alcohol compound as a hydrocarbon-containing compound having a first reactive functional group, and a cyclic compound having an alkenyl group and a second reactive functional group (for example, an alkenylphenyl glycidyl ether compound having one alkenyl group). In particular, the propenyl resin represented by general formula (i) of the present embodiment is more preferably produced using, as reaction raw materials, epoxy compound (1) and a cyclic compound having an alkenyl group and a second reactive functional group (preferably an alkenylphenol compound), and particularly preferably produced using, as reaction raw materials, epoxy compound (1) and eugenol or isoeugenol. Eugenol is a component generally found in spices such as cloves and bay leaves, and is a naturally occurring biomass compound classified as a monophenylpropanoid. Therefore, using eugenol or isoeugenol obtained by the isomerization of eugenol as a reaction raw material can reduce the environmental impact.

[0081] <Epoxy compound (1)> The propenyl resin represented by general formula (i) of this embodiment preferably uses an epoxy compound (1) as a reaction raw material. The epoxy compound (1) of this embodiment is not particularly limited as long as it is a compound having 2 to 4 glycidyl groups in one molecule. Hereinafter, a compound having 2 to 4 epoxy groups in one molecule will be simply referred to as an epoxy compound (1). Various epoxy compounds (1) can be used, but polyvalent epoxy compounds (1) having 2 to 4 epoxy groups in one molecule are preferred. In addition, the epoxy compound (1) is a compound having a structure represented by general formula (4), and Y in general formula (4) 1 is preferably a compound in which: is a glycidyl group.

[0082] Specific examples of polyepoxy compounds are those obtained by condensation of epichlorohydrin with polyhydric phenols such as bisphenols or polyhydric alcohols, and include glycidyl ether epoxy resins such as bisphenol A, brominated bisphenol A, hydrogenated bisphenol A, bisphenol F, bisphenol S, bisphenol AF, biphenyl, naphthalene, fluorene, tris(hydroxyphenyl)methane, tetraphenylolethane, phenylaralkyl, biphenylaralkyl, and dicyclopentadienephenol. Other examples include glycidyl ester epoxy resins obtained by condensation of epichlorohydrin with carboxylic acids such as phthalic acid derivatives or fatty acids, glycidyl amine epoxy resins obtained by reaction of epichlorohydrin with amines, cyanuric acids, or hydantoins, and epoxy resins modified by various methods, but are not limited to these. In this embodiment, the molecular weight of the epoxy compound (1) is preferably from 100 to 600, more preferably from 200 to 500, and even more preferably from 250 to 350. This provides excellent curability and excellent appearance. The molecular weight of the epoxy compound (1) is calculated by FD-MS measurement as described in the Examples below.

[0083] The epoxy compound (1) of the present embodiment is preferably represented by the following general formula (6). [ka] (In the above general formula (6), M 7 represents M in general formula (i). i1 and preferably represents a group selected from the group consisting of the above formulas (I) to (VI), n61 represents an integer between 2 and 4.)

[0084] <Alkenylphenol compounds> A suitable form of the cyclic compound having an alkenyl group and a second reactive functional group of this embodiment may be a compound having an alkenyl group (allyl group or propenyl group), a second reactive functional group (e.g., a glycidyl group, a hydroxyl group, or a mercapto group), and a cyclic group having an unsaturated bond and to which the alkenyl group (allyl group or propenyl group) and the second reactive functional group are bonded. The cyclic compound having an alkenyl group and a second reactive functional group is preferably an alkenylphenol compound.

[0085] <<Alkenylphenol compounds>> The alkenylphenol compound is a general term for compounds having an alkenyl group (allyl or propenyl), a hydroxyl group or a mercapto group, and a cyclic group to which the alkenyl group (allyl or propenyl) and the hydroxyl group or the mercapto group are bonded and which has an unsaturated bond, and is not particularly limited as long as it is an alkenylphenol compound represented by the following general formula (3A) or (3B): Hereinafter, the compound represented by the following general formula (3A) or (3B) will be simply referred to as an alkenylphenol compound.

[0086] The alkenylphenol compound of this embodiment is more preferably represented by general formula (3A-1) or (3B-1), and examples thereof include 2-allylphenol, 4-allylphenol, 2-(1-propenyl)phenol, 4-(1-propenyl)phenol, eugenol, isoeugenol, hydroxychavicol, and propenylguaetol. Of these alkenylphenol compounds, eugenol and isoeugenol are more preferred, with isoeugenol being even more preferred. [ka] (In the above general formulas (3A) and (3B), M 2’ represents a cyclic group having one or more unsaturated bonds, which may be substituted by a substituent R; Z 1 represents a hydroxyl group or a mercapto group. [ka] (In the above general formulas (3A-1) and (3B-1), R 3a each independently represents a substituent, Z 1 represents a hydroxyl group or a mercapto group, n3a represents an integer between 0 and 4.)

[0087] In the above general formulas (3A) and (3B), M 2’ represents M in the above general formula (i). i2 Corresponds to. In the above general formulas (3A), (3B), (3A-1) and (3B-1), Z 1 represents a hydroxyl group or a mercapto group, and is preferably a hydroxyl group from the viewpoint of suppressing corrosion degradation of the Cu wire.

[0088] When the alkenylphenol compound of this embodiment is eugenol, that is, when R 3a is a substituted methoxy group at the 2-position, and Z 1is a hydroxyl group at the 1-position and n3a is 1, plant-derived eugenol can be incorporated into the chemical structure of the target propenyl resin represented by general formula (i), thereby providing a compound that reduces environmental impact. When the alkenylphenol compound of this embodiment is isoeugenol, that is, in the above general formula (3B-1), R 3a is a substituted methoxy group at the 2-position, and Z 1 is a hydroxyl group at the 1-position and n3 is 1, plant-derived isoeugenol can be incorporated into the chemical structure of the target propenyl resin represented by general formula (i), thereby providing a compound that reduces environmental impact.

[0089] The propenyl-based resin represented by general formula (i) of this embodiment is preferably produced using an alkenylphenol compound as a reaction raw material, and the alkenylphenol compound is preferably eugenol or isoeugenol, more preferably isoeugenol. The alkenylphenol compound is preferably an alkenyl group, a phenolic hydroxyl group, and an aromatic compound to which the alkenyl group and the hydroxyl group are bonded. The alkenylphenol compound is a compound having a structure represented by general formula (5), and L in general formula (5) 5 is a single bond and Y 2 is preferably a compound in which: is a hydroxyl group. When the cyclic compound having an alkenyl group and a second reactive functional group of this embodiment is isoeugenol, that is, when M 51 is a benzene ring, and R 51 is a propenyl group (1-propenyl group), and R 52 is a methoxy group, and L 5 is a single bond, and Y 2 In the case of a compound in which n51 is a hydroxyl group and n52 are each 1, plant-derived isoeugenol can be incorporated into the chemical structure of the target propenyl resin represented by general formula (i), thereby providing a compound that reduces the environmental load.

[0090] (Mixture containing propenyl resin represented by general formula (i)) The propenyl resin represented by general formula (i) of the present disclosure may be a propenyl resin-containing mixture containing the propenyl resin represented by general formula (i). The content of the propenyl resin represented by general formula (i) of this embodiment can be calculated in area % by GPC using the method described below, and may be preferably 20 area % or more, more preferably 40 area % to 100 area %, and even more preferably 60 area % to 100 area %, relative to the total amount (100 area %) of the propenyl resin-containing mixture. When the propenyl resin represented by general formula (i) is contained in the mixture at a content of 20 area % or more, the effect can be exhibited. Components other than the propenyl resin represented by general formula (i) contained in the mixture containing the propenyl resin represented by general formula (i) may be by-products and polymers generated in the production process of the reaction raw materials and the epoxidation process.

[0091] (Method for producing propenyl resin represented by general formula (i)) A method for producing the propenyl resin represented by general formula (i) of the present disclosure will be described below. The method for producing the propenyl resin represented by general formula (i) of this embodiment is not particularly limited as long as it can produce the chemical structure represented by general formula (i). For example, the raw materials used in the method for producing the propenyl resin represented by general formula (i) of the present disclosure can be an aliphatic or aromatic hydrocarbon-containing compound having a first reactive functional group represented by general formula (4) above, and an aromatic hydrocarbon-containing compound having an alkenyl group and a second reactive functional group represented by general formula (5) above. Furthermore, known synthesis conditions and methods can be used as reference for the method for producing the propenyl resin. For the sake of convenience, the following describes an example of a method for producing a propenyl resin represented by general formula (i) of the present disclosure, in which an epoxy compound (1) and an alkenylphenol compound are used as reaction raw materials. An example of a method for producing the propenyl-based resin represented by general formula (i) of the present disclosure includes a production method including the following step (i-1) and, optionally, steps (i-2) and (i-3): Step (i-1): A step of reacting an epoxy compound (1) with an alkenylphenol compound as reaction raw materials; step (i-2): purifying the reaction product from a mixture containing the reaction product of the epoxy compound (1) and the alkenylphenol compound; Step (i-3): When a compound having a structure represented by general formula (5) is used as the alkenylphenol compound as a reaction raw material, and R 51 is an allyl group, a step of isomerizing the carbon-carbon double bond. Specifically, the method for producing the propenyl resin represented by general formula (i) of the present embodiment preferably includes a step (i-1) of reacting an epoxy compound (1) with an alkenylphenol compound in the presence of a basic compound, a step (i-2) of purifying the reaction product produced in the step (i-1) by using an acidic aqueous solution and an organic solvent, and an optional step (i-3) of isomerizing the carbon-carbon double bond. Hereinafter, each step of the method for producing the propenyl resin represented by general formula (i) of the present disclosure will be described in order.

[0092] <Process (i-1)> Considering the balance of the physical properties of moldability and curability of the resulting propenyl resin represented by general formula (i), the blending ratio of the epoxy compound (i-1) and the alkenylphenol compound is preferably 0.1 to 2.0 mol, more preferably 0.5 to 1.5 mol, and more preferably 0.8 to 1.3 mol, in terms of the molar ratio of hydroxyl groups of the alkenylphenol compound per 1 mol of glycidyl groups of the epoxy compound. The specific method for carrying out the above reaction is generally to charge all the raw materials at once and react them at a predetermined temperature, or to charge an alkenylphenol compound and a basic compound and react them while maintaining the temperature at a predetermined level and adding the epoxy compound (1) dropwise. In this case, the dropwise addition time is usually 0.5 to 24 hours, preferably 0.5 to 4 hours.

[0093] The basic compound usable in step (i-1) of this embodiment may be an inorganic basic compound, an organic basic compound, or the like. Examples of inorganic basic compounds include hydroxides of alkali metals such as potassium and sodium; carbonates of alkali metals such as potassium and sodium; hydroxides of alkaline earth metals such as calcium and barium; and carbonates of calcium and barium. On the other hand, examples of organic basic compounds include phosphines such as triphenylphosphine. From the viewpoint of ease of purification by washing with water, the basic compound of this embodiment is preferably an alkali metal hydroxide (e.g., potassium hydroxide, sodium hydroxide, lithium hydroxide, or the like), and more preferably potassium hydroxide or sodium hydroxide. The basic compound is preferably used in an amount of 0.01 to 10 parts by mass, more preferably 1 to 5% by mass, relative to 100 parts by mass of the epoxy compound (1) and the alkenylphenol compound combined.

[0094] In step (i-1) of this embodiment, a phase transfer catalyst may be used. Specific examples of phase transfer catalysts that can be used in step (i-1) of this embodiment include quaternary ammonium salts, quaternary phosphonium salts, and crown ethers. Quaternary ammonium salts and quaternary phosphonium salts are preferred because of their particularly excellent catalytic activity, and specific examples include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, and tetrabutylphosphonium bromide. When used, these phase transfer catalysts may be used in the form of an aqueous solution of about 10% to 55% by mass, or in the form of a solid. The amount of the phase transfer catalyst to be added is in the range of 0.01 to 1.00 parts by mass relative to 100 parts by mass of the total amount of the raw materials to be charged (= the total amount of reaction raw materials such as, for example, the epoxy compound (1) and the alkenylphenol compound), but from the viewpoints of handleability and economy, it is preferably 0.05 to 0.20 parts by mass. In step (i-1) of this embodiment, an organic solvent may be used. Examples of the organic solvent include ketones such as methyl isobutyl ketone, acetone, methyl ethyl ketone (MEK), cyclohexanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; and aromatic solvents such as benzene, toluene, and xylene. These may be used alone or in combination.

[0095] In step (i-1) of the present embodiment, the reaction temperature between the epoxy compound (i-1) and the alkenylphenol compound is usually in the range of 50 to 170°C, but is preferably 100 to 140°C in order to avoid side reactions such as the formation of polymers and hydrolysis of glycidyl groups. In step (i-1) of the present embodiment, the reaction time between the epoxy compound and the alkenylphenol compound is usually in the range of 0.5 to 24 hours in total under the reaction temperature conditions, preferably 1 to 6 hours in total, because the reaction does not proceed completely if it is short and side reactions such as thermal decomposition of the product occur if it is long. Therefore, in step (i-1) of this embodiment, it is more preferable to carry out the reaction at a temperature in the range of 100 to 140° C. for 1 to 6 hours while stirring. In addition, the reaction in step (i-1) is preferably carried out in an inert gas atmosphere such as nitrogen, helium, or argon.

[0096] <Process (i-2)> Step (i-2) in this embodiment is performed as needed to recover the reaction product (= the target propenyl resin represented by general formula (i)) obtained in step (i-1). An acidic aqueous solution is added to a solution containing the reaction product (= the target propenyl resin represented by general formula (i)) obtained in step (i-1) and an organic solvent. The solution is neutralized with the acidic aqueous solution, washed with water, or the like to remove salts of basic compounds and impurities. This is followed by azeotropic dehydration, followed by microfiltration, whereby the solvent and unreacted compounds are distilled off under reduced pressure to obtain the target propenyl resin represented by general formula (i). A dehydrating agent may also be used during the reaction, if necessary.

[0097] The reaction product can be washed with an acidic aqueous solution to improve the stability of the resulting compound. Specific examples of acids that can be used in the acidic aqueous solution include nitric acid, hydrochloric acid, sulfuric acid, boric acid, arsenic acid, phosphoric acid, hydrocyanic acid, acetic acid, peracetic acid, thioacetic acid, oxalic acid, tartaric acid, succinic acid, and maleic acid, as well as salts thereof (e.g., alkali metal or alkaline earth metal salts). These acids may be used alone or in combination. Examples of the dehydrating agent used in step (i-2) of this embodiment include inorganic acids such as sulfuric acid, and porous ceramics such as molecular sieves.

[0098] <Process (i-3)> After step (i-1) or (i-2) of this embodiment, step (i-3) of isomerizing the carbon-carbon double bond may be carried out, if necessary. Specifically, in the alkenylphenol compound represented by the general formula (5), R 51 is an allyl group and Y 2 is a hydroxyl group (i.e., when an alkenylphenol compound having an allyl group and a hydroxyl group is used as a reaction raw material), a step (i-3) may be further provided in which the reaction product obtained by reacting an epoxy compound with the alkenylphenol compound having the allyl group and the hydroxyl group is isomerized to isomerize the allyl group to a 1-propenyl group, thereby synthesizing a propenyl resin represented by general formula (i). As a method for isomerizing the allyl group to a 1-propenyl group, a known method can be adopted, and examples thereof include an isomerization reaction of a carbon-carbon bond using a palladium acetate catalyst or the like (see [J. Am. Chem. Soc., 91, pp. 6707-6714 (1969)]), or an isomerization reaction of a carbon-carbon bond using an alkali metal hydroxide or the like (potassium hydroxide) as a base catalyst (see [J. Am. Chem. Soc., 78, pp. 1709-1715 (1956)]). This allows the propenyl resin represented by the general formula (i) to be easily synthesized.

[0099] (Another preferred embodiment of the propenyl resin represented by formula (ii)) One preferred embodiment of the propenyl resin represented by general formula (ii) of the present embodiment is one in which an epoxy resin and a cyclic compound having an alkenyl group and a second reactive functional group (particularly the alkenylphenol compound) are used as reaction raw materials. Furthermore, it is more preferable to use eugenol or isoeugenol as the reaction raw material as the cyclic compound having an alkenyl group and a second reactive functional group.

[0100] <Epoxy resin> In this embodiment, the epoxy resin that is the reaction raw material for the propenyl resin represented by general formula (ii) is not particularly limited as long as it is an epoxy resin having a partial structure represented by the following general formula (7). Note that the epoxy resin having the partial structure represented by general formula (7) will be simply referred to as epoxy resin (A). [ka] (In the above general formula (7), M 72 are each independently M in the general formula (ii) ii5 and preferably represents a trivalent aromatic hydrocarbon group, M 71 are each independently M in the general formula (ii) ii3 and preferably represents a divalent organic group, more preferably a divalent organic group having from 6 to 20 carbon atoms, n71 represents an integer between 1 and 10.)

[0101] Specific examples of the epoxy resin (A) include those obtained by condensation of epichlorohydrin with polyhydric phenols such as phenol resins, and include glycidyl ether epoxy resins of polyhydric phenols such as novolac type, phenylaralkyl type, biphenylaralkyl type, cycloalkylene type, alkylene type, cycloalkylidene type, benzylidene type, and fluorenylidene type.Other examples include epoxy resins modified by various methods, but are not limited to these. The epoxy resin (A) is not particularly limited, but is preferably, for example, a curable resin that contains two or more glycidyl groups in the molecule and can be cured by forming a crosslinked network with the glycidyl groups.

[0102] The epoxy resin (A) of the present embodiment is preferably a resin having two or more glycidyl groups in the molecule, for example, Novolac epoxy resins such as phenol novolac epoxy resins and orthocresol novolac epoxy resins; aralkyl-type epoxy resins such as phenol phenyl aralkyl-type epoxy resins, cresol phenyl aralkyl-type epoxy resins, naphthol phenyl aralkyl-type epoxy resins, and phenol biphenyl aralkyl-type epoxy resins; cycloalkylene-type epoxy resins such as dicyclopentadiene phenol-type epoxy resins; Alkylene-type epoxy resins such as 1,3-dimethylbutylene bisphenol-type epoxy resins; cycloalkylidene epoxy resins such as cyclohexylidene bisphenol epoxy resins, 3,3,5-trimethylcyclohexylidene bisphenol epoxy resins, and cyclododecylidene bisphenol epoxy resins; benzylidene-type epoxy resins such as benzylidene bisphenol-type epoxy resins and α-methylbenzylidene bisphenol-type epoxy resins; fluorenylidene epoxy resins such as 9-fluorenylidene bisphenol epoxy resins; Of these epoxy resins (A), aralkyl type epoxy resins, cycloalkylene type epoxy resins and cycloalkylidene type epoxy resins are more preferred from the viewpoint of moisture absorption and heat resistance. The above-mentioned epoxy resins (A) may be used alone or in combination of two or more kinds.

[0103] In this embodiment, the epoxy equivalent of the epoxy resin (A) is preferably 140 g / mol or more, more preferably 180 g / mol or more, and even more preferably 220 g / mol to 400 g / mol. When the epoxy equivalent of the polyfunctional epoxy resin (A) is 180 g / mol or more, the resulting cured product has excellent adhesion and low moisture absorption, which is preferable. On the other hand, when the epoxy equivalent of the epoxy resin (A) is 400 g / mol or less, the resulting cured product has excellent heat resistance, which is preferable.

[0104] The functional group equivalent ratio of the amount of the alkenylphenol compound used to the amount of the epoxy resin (A) used (hydroxyl group or mercapto group of the alkenylphenol compound / glycidyl group of the epoxy resin (A)) is preferably 0.5 to 1.5, more preferably 0.8 to 1.3. When the functional group equivalent ratio is 0.5 or more, the resulting propenyl resin represented by general formula (ii) exhibits excellent low viscosity and curability, which is preferable.

[0105] The number-average molecular weight (Mn) of the epoxy resin (A) is preferably 300 to 3,000, more preferably 350 to 2,000. When the number-average molecular weight of the epoxy resin (A) is 300 or more, the resulting cured product exhibits superior mechanical properties, particularly superior bending strength, which is preferable. On the other hand, when the weight-average molecular weight of the epoxy resin (A) is 3,000 or less, the resulting propenyl resin represented by general formula (ii) exhibits low viscosity, which is preferable. The molecular weight of the epoxy resin of this embodiment was measured using GPC, as described in the Examples below.

[0106] (Method for producing propenyl resin represented by general formula (ii)) A method for producing the propenyl resin represented by general formula (ii) of the present disclosure will be described below. The method for producing the propenyl resin represented by general formula (ii) of the present embodiment is not particularly limited as long as it can produce the compound represented by general formula (ii).

[0107] For ease of explanation, the method for producing the propenyl resin represented by general formula (ii) of the present disclosure will be described below by taking as an example a case in which an epoxy resin (A), which is an example of an aromatic hydrocarbon-containing compound having a reactive functional group, and an alkenylphenol compound are used as reaction raw materials. An example of a method for producing the propenyl resin represented by general formula (ii) of the present disclosure includes a production method including the following step (ii-1) and, optionally, step (ii-2): Step (ii-1): A step of reacting an epoxy resin (A) with an alkenylphenol compound as a reaction raw material; Step (ii-2): A step of purifying the reaction product from a mixture containing the reaction product of the epoxy resin (A) and the alkenylphenol compound; Step (ii-3): When a compound having a structure represented by general formula (5) is used as the alkenylphenol compound as a reaction raw material, and R 51 is an allyl group, a step of isomerizing the carbon-carbon double bond. Specifically, the method for producing the propenyl resin represented by general formula (ii) of the present embodiment preferably includes: a step (ii-1) of reacting an epoxy resin (A) with an alkenylphenol compound in the presence of a basic compound; a step (ii-2) of purifying the reaction product produced in the step (ii-1) using an aqueous solvent and an organic solvent; and an optional step (ii-3) of isomerizing the carbon-carbon double bond. Hereinafter, each step of the method for producing the propenyl resin represented by general formula (ii) of the present disclosure will be described in order.

[0108] <Process (ii-1)> The blending ratio of the epoxy resin (A) and the alkenylphenol compound is appropriately selected in consideration of the balance of the physical properties of the moldability and curability of the resulting propenyl-based resin represented by general formula (ii), the raw materials to be used, etc. For example, when an epoxy resin (A) is used as the aromatic hydrocarbon-containing compound having a reactive functional group and an alkenylphenol compound is used as the alkenyl group-containing compound, the molar ratio of hydroxyl groups or mercapto groups of the alkenylphenol compound relative to 1 mole of glycidyl groups of the epoxy resin (A) is preferably 0.1 to 2.0 moles, more preferably 0.5 to 1.5 moles, and more preferably 0.8 to 1.3 moles. The specific method for carrying out the above reaction is generally to charge all raw materials at once and react them at a predetermined temperature, or to charge an alkenylphenol compound and a basic compound and react them while maintaining the temperature at a predetermined level and adding the epoxy resin (A) dropwise. In this case, the dropwise addition time is usually 0.5 to 24 hours, preferably 0.5 to 4 hours.

[0109] The basic compounds that can be used in step (ii-1) of this embodiment are the same as those that can be used in step (i-1) above. The basic compound is preferably used in an amount of 0.01 to 10 parts by mass, more preferably 1 to 5% by mass, relative to 100 parts by mass of the epoxy resin (A) and the alkenylphenol compound combined.

[0110] In step (ii-1) of this embodiment, a phase transfer catalyst may be used. The types of the phase transfer catalyst are the same as those described above for the phase transfer catalyst that can be used in step (i-1). In step (ii-1), the phase transfer catalyst may be used in the form of an aqueous solution of about 10% by mass to 55% by mass, or in the form of a solid. The amount of the phase transfer catalyst to be added is in the range of 0.01 to 1.00 parts by mass per 100 parts by mass of the total amount of raw materials to be charged (= the total amount of reaction raw materials such as, for example, the epoxy resin (A) and the alkenylphenol compound), but from the viewpoints of handleability and economy, it is preferably 0.05 to 0.20 parts by mass. In step (ii-1) of this embodiment, an organic solvent may be used. The types of the organic solvent are the same as those described above for the organic solvent used in step (i-1).

[0111] In step (ii-1) of the present embodiment, the reaction temperature between the epoxy resin (A) and the alkenylphenol compound is usually in the range of 50 to 170° C. However, in order to avoid side reactions such as the formation of polymers or hydrolysis of the glycidyl group, a temperature of 100 to 140° C. is preferred. In step (ii-1) of the present embodiment, the reaction time between the epoxy resin (A) and the alkenylphenol compound is usually in the range of 0.5 to 24 hours in total under the reaction temperature conditions, preferably 1 to 6 hours in total, because the reaction does not proceed completely if it is short and side reactions such as thermal decomposition of the product occur if it is long. Therefore, in step (ii-1) of this embodiment, it is more preferable to carry out the reaction at a temperature in the range of 100 to 140° C. for 1 to 6 hours while stirring. In addition, the reaction in step (ii-1) is preferably carried out in an inert gas atmosphere such as nitrogen, helium, or argon.

[0112] <Process (ii-2)> Step (ii-2) in this embodiment is performed as needed to recover the reaction product (= the target propenyl resin represented by general formula (ii)) obtained in step (ii-1). A known acidic aqueous solvent is added to a solution containing the reaction product (= the target propenyl resin represented by general formula (ii)) obtained in step (ii-1) and an organic solvent. The solution is neutralized using the acidic aqueous solvent, washed with water, or the like to remove salts of basic compounds and impurities. Then, an azeotropic dehydration operation is performed, and after microfiltration, the solvent and unreacted compounds are distilled off under reduced pressure to obtain the target propenyl resin represented by general formula (ii). A dehydrating agent may also be used during the reaction, if necessary.

[0113] The reaction product in the step (ii-2) can also be washed with an acidic aqueous solution to improve the stability of the resulting compound. As the acidic aqueous solution, the same applies as for the acidic aqueous solution that can be used in the step (i-1). Examples of the dehydrating agent used in step (ii-2) of this embodiment include inorganic acids such as sulfuric acid, and porous ceramics such as molecular sieves.

[0114] <Process (ii-3)> After step (ii-1) or (ii-2) of this embodiment, step (ii-3) of isomerizing the carbon-carbon double bond may be performed as needed. Specifically, in the alkenylphenol compound represented by the general formula (5), R 51 is an allyl group and Y 2 is a hydroxyl group (i.e., when an alkenylphenol compound having an allyl group and a hydroxyl group is used as a reaction raw material), a step (ii-3) may be further provided in which the reaction product obtained by reacting the epoxy resin (A) with the alkenylphenol compound having the allyl group and the hydroxyl group is isomerized to isomerize the allyl group to a 1-propenyl group, thereby synthesizing a propenyl resin represented by general formula (ii). As a method for isomerizing the allyl group to a 1-propenyl group, a known method can be adopted, and examples thereof include an isomerization reaction of a carbon-carbon bond using a palladium acetate catalyst or the like (see [J. Am. Chem. Soc., 91, pp. 6707-6714 (1969)]), or an isomerization reaction of a carbon-carbon bond using an alkali metal hydroxide or the like (potassium hydroxide) as a base catalyst (see [J. Am. Chem. Soc., 78, pp. 1709-1715 (1956)]). This allows the propenyl resin represented by the general formula (ii) to be easily synthesized.

[0115] (radical scavenger) The composition of this embodiment contains a radical scavenger. By including a radical scavenger in the composition, the radical polymerization reaction is suppressed and the Diels-Alder reaction is facilitated. As a result, the molecules in the composition tend to undergo a uniform curing reaction (Diels-Alder reaction), which improves the uniformity of the curing reaction throughout the composition and allows the resulting cured product to achieve both high heat resistance (particularly glass transition temperature) and high mechanical properties (particularly flexural strength). The radical scavenger of this embodiment is not particularly limited as long as it is a compound that interacts with radicals to inactivate them, but is preferably one or more selected from the group consisting of hindered phenol compounds, benzenediol compounds, nitroxyl radical compounds, nitrosamine compounds, and phenothiazine compounds. This more efficiently inhibits radical polymerization reactions and facilitates the progress of the Diels-Alder reaction. As a result, the curability of the composition is improved uniformly, resulting in improved heat resistance (particularly the glass transition temperature) and mechanical properties (particularly the flexural strength) of the resulting cured product.

[0116] <Hindered phenol compounds> The hindered phenol compound of the present embodiment is not particularly limited as long as it is a compound having a hindered phenol group. The term "hindered phenol group" as used herein refers to a group in which at least one of the two carbon atoms (or two ortho-position carbon atoms) adjacent to the carbon atom in a benzene ring to which a hydroxyl group is bonded is substituted with a t-butyl group at the ortho position. Therefore, the hindered phenol compound of this embodiment includes compounds having the chemical structures of the following formulae (h1) to (h3). [ka] (In the above formula (h2), R b represents an alkyl group having 1 to 8 carbon atoms. c represents an alkyl group having 1 to 8 carbon atoms. In addition, one or more hydrogen atoms of the benzene ring in the above formulas (h1) to (h3) may be substituted with a substituent, and examples of the substituent include a hydroxyl group, an amino group, an alkyl group, or an alkoxy group. In formulas (h1) to (h3), * represents a bond to another atom.

[0117] Specific examples of the hindered phenol compound of this embodiment include the following: Examples of the hindered phenol compound represented by the above formula (h1) include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, hexamethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(-3,5-tert-butyl-4-hydroxyphenyl)propionate], N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0118] Examples of the semi-hindered phenol compound represented by the above formula (h2) include 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, and triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate].

[0119] Examples of the less hindered type hindered phenol compound represented by the above formula (h3) include bis[(3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyric acid)glycol ester, 4,4'-thiobis(3-methyl-6-tert-butyl)phenol, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)-butane, and 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol).

[0120] In the composition of the present embodiment, the radical scavenger may be used alone or in combination of two or more. When a hindered phenol compound is used as the radical scavenger contained in the composition of the present embodiment, the content of the hindered phenol compound is preferably 0.01% by mass to 5.00% by mass, more preferably 0.03% by mass to 3.00% by mass, even more preferably 0.05% by mass to 2.00% by mass, still more preferably 0.05% by mass to 1.50% by mass, and particularly preferably 0.05% by mass to 1.00% by mass, relative to the total amount (100% by mass) of the composition.

[0121] <Benzenediol compounds> The benzenediol compound of this embodiment is not particularly limited as long as it is an aromatic compound having two or more phenolic hydroxyl groups. Examples of the benzenediol compound include unsubstituted hydroquinone, a hydroquinone compound having a substituent bonded to an aromatic ring, unsubstituted resorcinol, a resorcinol compound having a substituent bonded to an aromatic ring, and unsubstituted catechol, or a catechol compound having a substituent bonded to an aromatic ring. Only one type of benzenediol compound may be used, or two or more types may be used in combination. The substituent of the benzenediol compound is not particularly limited, and examples thereof include hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups, and aralkyl groups. The hydrocarbon group has, for example, 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. Among these, the substituent is preferably an alkyl group, more preferably a t-butyl group or a methyl group, and particularly preferably a t-butyl group. The most preferred benzenediol compound is t-butylhydroquinone or 4-t-butylcatechol. When a benzenediol compound is used as the radical scavenger contained in the composition of the present embodiment, the content of the benzenediol compound is preferably 0.01% by mass to 5.00% by mass, more preferably 0.03% by mass to 3.00% by mass, even more preferably 0.05% by mass to 2.00% by mass, still more preferably 0.05% by mass to 1.50% by mass, and particularly preferably 0.05% by mass to 1.00% by mass, relative to the total amount (100% by mass) of the composition.

[0122] <Nitroxyl radical compounds> The nitroxyl radical compound of this embodiment refers to a secondary amine oxide compound containing an N,N-disubstituted NO· atomic group (N-oxyl group) having an unpaired electron. Examples of the nitroxyl radical compound include piperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and 3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical. When a nitroxyl radical compound is used as the radical scavenger contained in the composition of the present embodiment, the content of the nitroxyl radical compound is preferably 0.01 mass% to 5.00 mass%, more preferably 0.03 mass% to 3.00 mass%, even more preferably 0.05 mass% to 2.00 mass%, still more preferably 0.05 mass% to 1.50 mass%, and particularly preferably 0.05 mass% to 1.00 mass%, relative to the total amount of the composition (100 mass%).

[0123] <Nitrosamine compounds> The nitrosamine compound of the present embodiment is not particularly limited as long as it is a compound having a =NN=O chemical structure in its molecule. Examples of the nitrosamine compound include N-nitroso-N-phenylhydroxylamine, N-nitroso-N-phenylhydroxylamine ammonium, and N-nitroso-N-phenylhydroxylamine aluminum salt. When a nitrosamine compound is used as the radical scavenger contained in the composition of the present embodiment, the content of the nitrosamine compound is preferably 0.01% by mass to 5.00% by mass, more preferably 0.03% by mass to 3.00% by mass, even more preferably 0.05% by mass to 2.00% by mass, still more preferably 0.05% by mass to 1.50% by mass, and particularly preferably 0.05% by mass to 1.00% by mass, relative to the total amount (100% by mass) of the composition.

[0124] <Phenothiazine compounds> The phenothiazine compound of the present embodiment is not particularly limited as long as it has a structure in which a benzene ring is fused to both ends of a thiazine ring, and examples of the phenothiazine compound include phenothiazine, bis(α-methylbenzyl)phenothiazine, 3,7-dioctylphenothiazine, and bis(α,α-dimethylbenzyl)phenothiazine. When a phenothiazine compound is used as the radical scavenger contained in the composition of the present embodiment, the content of the phenothiazine compound is preferably 0.01% by mass to 5.00% by mass, more preferably 0.03% by mass to 3.00% by mass, even more preferably 0.05% by mass to 2.00% by mass, still more preferably 0.05% by mass to 1.50% by mass, and particularly preferably 0.05% by mass to 1.00% by mass, relative to the total amount (100% by mass) of the composition.

[0125] (Optional added ingredients) The composition of the present disclosure may contain a curing agent in addition to the propenyl-based resin or the maleimide-based resin, and further, if necessary, various compounding agents such as a curing accelerator, a silane coupling agent, a release agent, a pigment, an emulsifier, a non-halogen-based flame retardant, an inorganic filler (also referred to as a filler), a flame retardant (for example, an inorganic phosphorus-based flame retardant, an organic phosphorus-based flame retardant, or a halogen-based flame retardant), and a solvent may be added. Furthermore, as long as the object of the present disclosure is not impaired, known resin components may be contained in addition to the propenyl resin and the maleimide resin, such as epoxy resin, phenol resin, active ester resin, cyanate resin, polyphenylene ether resin, benzoxazine resin, styrene-maleic anhydride copolymer, polybutadiene and its modified products, polyacetal resin, polyvinyl alcohol resin, liquid crystal polymer, fluororesin, polystyrene, polyethylene, polyimide resin, silicone gel, silicone oil, etc.

[0126] [Method of producing the composition] The method for producing the composition of this embodiment is not particularly limited. For example, melt kneading is a preferred method for producing the composition. Examples of devices used for melt kneading include an extruder, a Banbury mixer, a roller, a kneader, and the like, which are operated batchwise or continuously. In general, when producing the composition, it is preferred to melt and mix the composition thoroughly at a temperature equal to or higher than the melting point thereof using an extruder, kneader, rolls or the like until the composition is homogeneous.

[0127] [Cured product] The cured product of the present disclosure is preferably obtained from the composition of this embodiment. The cured product can be obtained by subjecting the composition to a curing reaction. Therefore, the cured product of the present disclosure reflects the properties of the composition, and can therefore achieve a high degree of compatibility between mechanical properties, particularly excellent flexural strength, and heat resistance, particularly a high glass transition temperature. The composition can be obtained by uniformly mixing the above-mentioned components (e.g., curing agent, compounding agent), and can be easily formed into a cured product using a method similar to that known in the art. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coatings, and films.

[0128] [Semiconductor encapsulation materials] The present disclosure relates to a semiconductor encapsulation material containing the composition or cured product of the present embodiment. The semiconductor encapsulation material obtained using the composition of the present embodiment has improved mechanical properties, particularly flexural strength, of the resulting cured product, which suppresses molding defects such as cracks during the manufacturing process, making it a preferred embodiment.

[0129] The composition of this embodiment used in the semiconductor encapsulation material may contain an inorganic filler. The inorganic filler may be used in an amount of, for example, 0.5 to 1,200 parts by mass per 100 parts by mass of the combined total of the propenyl resin and maleimide resin of this embodiment. Examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride.

[0130] Examples of a method for obtaining the semiconductor encapsulating material include a method in which the composition of the present embodiment and optional additives are further melt-mixed, as necessary, using an extruder, kneader, roll, or the like until the mixture becomes homogeneous.

[0131] [Semiconductor Devices] The present disclosure relates to a semiconductor device including a cured product of the semiconductor encapsulation material. The semiconductor device obtained using the semiconductor encapsulation material obtained using the composition of the present embodiment has improved bending strength and a high glass transition temperature, and therefore has excellent mold releasability and reflow resistance during the manufacturing process, which is a preferred embodiment.

[0132] The semiconductor device can be obtained by molding the semiconductor encapsulating material using a casting machine, a transfer molding machine, an injection molding machine, or the like, and then heat-curing the material at a temperature ranging from room temperature (20°C) to 250°C.

[0133] [Prepreg] The present disclosure provides a prepreg having a reinforcing substrate and a semi-cured product of the composition of the present embodiment impregnated into the reinforcing substrate. The resulting semi-cured product exhibits excellent mechanical properties, particularly flexural strength, and heat resistance, particularly a high glass transition temperature. A method for obtaining a prepreg from the above composition includes blending an organic solvent (described below) to form a varnish, impregnating a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.) with the varnished composition, and then heating the composition at a temperature appropriate for the type of solvent used, preferably 50 to 170°C, to semi-cure (or uncure) the composition to obtain a prepreg. The mass ratio of the composition to the reinforcing substrate used in this case is not particularly limited, but it is usually preferable to prepare the prepreg so that the resin content is 20 to 60 mass%. In this embodiment, the semi-cured product of the composition can be obtained by adjusting the heating temperature and heating time to stop the curing reaction before it is completed. For example, the semi-cured product may have a degree of cure of, for example, 5% or more and 85% or less. Meanwhile, the cured product in this embodiment may have a higher degree of cure than the semi-cured product. The degree of cure of the semi-cured product can be calculated from the following formula by measuring the amount of heat generated during curing when the composition is heated and the amount of heat generated during curing of the semi-cured product by DSC. Degree of cure (%) = [1 - (heat generated from curing of semi-cured product / heat generated from curing of composition)] x 100

[0134] Examples of organic solvents used in producing the prepreg include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The selection and appropriate amount of the organic solvent can be determined appropriately depending on the application. For example, when a printed circuit board is further produced from the prepreg as described below, it is preferable to use a polar solvent with a boiling point of 160°C or less, such as methyl ethyl ketone, acetone, or dimethylformamide, and it is also preferable to use it in a proportion such that the non-volatile content is 40 to 80% by mass.

[0135] [Circuit board] The present disclosure relates to a circuit board that is a laminate of the prepreg and copper foil. A method for obtaining a printed circuit board from the composition of this embodiment includes laminating the prepreg by a conventional method, overlaying copper foil as appropriate, and subjecting the laminate to heat-pressure bonding at 170 to 300°C under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0136] [Build-up film] The present disclosure relates to a build-up film containing the composition of the present embodiment. A method for producing the build-up film of the present embodiment includes applying the composition to a support film to form a composition layer, thereby producing an adhesive film for a multilayer printed wiring board. The build-up film thus obtained exhibits excellent mechanical properties, particularly bending strength, and heat resistance, particularly a high glass transition temperature.

[0137] When a build-up film is produced from the composition, it is essential that the film softens under the lamination temperature conditions (usually 70 to 140°C) in the vacuum lamination method, and exhibits fluidity (resin flow) that allows resin to fill via holes or through holes present in the circuit board simultaneously with lamination of the circuit board. It is preferable to blend the above-mentioned components so as to exhibit such properties.

[0138] Here, the diameter of the through-holes in the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to make it possible to fill the resin within this range. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes.

[0139] Specifically, the adhesive film can be produced by preparing the above-mentioned composition in a varnish form, applying the varnish-like composition to the surface of the support film (Y), and then drying the organic solvent by heating or blowing hot air, etc., to form a composition layer (X) made of the composition.

[0140] The thickness of the composition layer (X) to be formed is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 μm, the thickness of the composition layer is preferably 10 to 100 μm.

[0141] The composition layer (X) in this embodiment may be protected with a protective film, which will be described later. By protecting the composition layer with a protective film, adhesion of dust and the like to the surface of the composition layer and scratches can be prevented.

[0142] Examples of the support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be subjected to a mud treatment, a corona treatment, or a release treatment.

[0143] The thickness of the support film is not particularly limited, but is usually in the range of 10 to 150 μm, preferably 25 to 50 μm, and the thickness of the protective film is preferably 1 to 40 μm.

[0144] The support film (Y) is peeled off after laminating it onto the circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat cured, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is usually subjected to a release treatment in advance.

[0145] [Heat-resistant materials and electronic materials] The cured products obtained from the propenyl-based resin composition of the present disclosure exhibit excellent mechanical properties, particularly flexural strength, and heat resistance, particularly a high glass transition temperature, making them suitable for use in heat-resistant or electronic components. They are particularly suitable for use in prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up boards, adhesives using conductive pastes, and resist materials. They are also suitable for use as matrix resins for fiber-reinforced resins, making them particularly suitable for prepregs with high heat resistance or excellent appearance. Furthermore, the propenyl-based resin contained in the composition exhibits excellent solubility in various solvents, making it possible to form it into a paint. The heat-resistant or electronic components thus obtained can be used in a variety of applications, including, but not limited to, industrial machine parts, general machine parts, automobile, railway, and vehicle parts, aerospace and aviation-related parts, electronic and electrical components, building materials, containers and packaging materials, household goods, sports and leisure goods, and housing materials for wind power generation. [Example]

[0146] The present invention will be described in more detail with reference to examples and comparative examples. In the following, "parts" and "%" are by mass unless otherwise specified. The physical properties of the synthesized propenyl-based resins were measured as follows, and the results are shown in Table 1.

[0147] (1) Measurement of double bond equivalent (iodine value) The double bond equivalent weight of the propenyl resin-containing mixture obtained in the synthesis examples was calculated in accordance with JIS K 0070.

[0148] (2) GPC measurement The content (area %) of the propenyl resin in the propenyl resin-containing mixture obtained in the synthesis examples was calculated using the following measuring device and measurement conditions. "Measuring device" Tosoh Corporation's "HLC-8320 GPC" "Measurement conditions" Column: Tosoh Corporation guard column "HXL-L" +Tosoh Corporation's "TSK-GEL G4000HXL" +Tosoh Corporation's "TSK-GEL G3000HXL" +Tosoh Corporation "TSK-GEL G2000HXL" +Tosoh Corporation "TSK-GEL G2000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Column temperature: 40℃ Developing solvent: tetrahydrofuran Flow rate: 1.0ml / min Sample: A tetrahydrofuran solution (50 μl) of 1.0 mass % (solid content equivalent) of the propenyl-based resin-containing mixture obtained in Synthesis Example was filtered through a microfilter.

[0149] (3) FD-MS measurement The FD-MS spectrum of the propenyl-based resin-containing mixture obtained in the synthesis example was measured using the following measuring device and measurement conditions. "Measuring device" JEOL Ltd. "JMS-T100GC AccuTOF" "Measurement conditions" Measurement range: m / z = 4.00 to 2000.00 Rate of change: 51.2mA / min Final current value: 45mA Cathode voltage: -10kV Recording interval: 0.07 sec

[0150] (4)NMR measurement The propenyl resin-containing mixture obtained in the synthesis example1 H-NMR spectrum and 13 The C-NMR spectrum was measured using the following measuring device and under the following measuring conditions. "Measuring device" JEOL RESONANCE "JNM-ECA500" "Measurement conditions" 1 H-NMR spectrum Resonance frequency: 500MHz Accumulation count: 16 times Solvent: chloroform-d Sample concentration: 4% by mass 13 C-NMR spectrum Resonance frequency: 125MHz Accumulation count: 2000 times Solvent: chloroform-d Sample concentration: 30% by mass

[0151] (Synthesis Example 1) A flask equipped with a thermometer, a fractionating column, and a stirrer was charged with 300 g (1.83 mol) of isoeugenol as an alkenylphenol compound, 15 g (0.18 mol) of 49% sodium hydroxide, 285 g of an epoxy resin (EXA-850CRP (number of moles of glycidyl groups: 1.65 mol, see formula (X-1) below) whose main component is an epoxy compound (molecular weight: 340) represented by chemical formula (X-1), 0.50 g of tetrabutylammonium bromide, and 600 g of methyl isobutyl ketone. The system was heated to 120°C while purging with nitrogen gas, and stirring was continued for 3 hours. After the reaction was completed, the temperature in the system was lowered to 80°C, and 300 g of a 12% aqueous solution of sodium phosphate monobasic was added. The mixture was stirred and mixed for 15 minutes, and then allowed to stand for liquid separation to remove the aqueous layer. Water was then added to the methyl isobutyl ketone layer containing the dissolved reaction product, and the mixture was stirred and mixed for 15 minutes. The mixture was then allowed to stand for liquid separation to remove the aqueous layer. Azeotropic dehydration was performed, and after microfiltration, the solvent was distilled off under reduced pressure to obtain a propenyl-based resin-containing mixture (1) containing 89 area % of the propenyl-based resin (1) represented by the following chemical formula (2-1.1). The softening point of the propenyl-based resin-containing mixture (1) was 60°C. The double bond equivalent of the propenyl-based resin-containing mixture (1) was 341 g / mol. The FD-MS spectrum of the propenyl-based resin-containing mixture (1) is shown in Figure 1, and the FD-MS spectrum of the propenyl-based resin-containing mixture (1) is shown in Figure 2. 1 H-NMR spectrum and 13 The C-NMR spectra are shown in Figures 2A and 2B. [ka] Chemical formula (2-1.1): [ka]

[0152] (Synthesis Example 2) The same procedure as in Synthesis Example 1 was carried out, except that the type of epoxy compound was changed to an epoxy resin (HP-4032D (number of moles of glycidyl groups: 1.65 mol)) whose main component was an epoxy compound (molecular weight: 272) represented by chemical formula (X-2). A propenyl-based resin-containing mixture (2) containing 88 area % of propenyl-based resin (2) represented by the following chemical formula (2-1.2) was obtained. The softening point of the propenyl-based resin-containing mixture (2) was 71°C. The double bond equivalent of the propenyl-based resin-containing mixture (2) was 310 g / mol. [ka] Chemical formula (2-1.2): [ka] The chemical structure, molecular weight, and the like of the obtained propenyl-based resin-containing mixture (2) represented by the chemical formula (2-1.2) were determined by FD-MS spectrum, 1 H-NMR spectrum and 13 This was confirmed by C-NMR spectroscopy.

[0153] (Synthesis Example 3) The same operations as in Synthesis Example 1 were carried out, except that the type of epoxy resin was changed to HP-7200L (dicyclopentadiene-type epoxy resin (manufactured by DIC Corporation), epoxy equivalent: 249 g / mol, Mn=430, Mw=566, Mw / Mn=1.315, number of moles of glycidyl groups: 1.65 mol, see formula (S1) below) as the epoxy resin represented by chemical formula (X-1), to obtain propenyl-based resin (3) represented by the following chemical formula (3-1.1). [ka] The softening point of the propenyl resin (3) was 83° C. The double bond equivalent of the propenyl resin (3) was 385 g / mol. The Mn of the propenyl resin (3) was 1113, the Mw was 1331, and the Mw / Mn was 1.196. Chemical formula (3-1.1): [ka] The FD-MS spectrum of the obtained propenyl-based resin (3) is shown in Figure 3, the GPC chart is shown in Figure 4, 1 The H-NMR spectrum is shown in Figure 5A. 13 The C-NMR spectrum is shown in Figure 5B.

[0154] <Examples 1 to 5 and Comparative Examples 1 to 3> <<Preparation of composition and production of cured product>> The components were blended according to the formulation shown in Table 1 below, and melt-kneaded using a two-roll mill at 90°C for 5 minutes to prepare the compositions of Examples 1 to 5 and Comparative Examples 1 to 3. Details of the components other than the propenyl resin used in Examples 1 to 5 and Comparative Examples 1 to 3 are as follows: Maleimide resin: Polyphenylmethane type maleimide resin (manufactured by Daiwa Chemical Industry Co., Ltd., "BMI-2300") represented by the following formula (1.1): [ka] Maleimide resin (8) represented by Radical scavenger (1): Phenothiazine (Fujifilm Wako Pure Chemical Industries, Ltd.) Radical scavenger (2): N-nitroso-N-phenylhydroxylamine aluminum (Q-1301, Fujifilm Wako Pure Chemical Industries, Ltd.) Radical scavenger (3): 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO, Fujifilm Wako Pure Chemical Industries, Ltd.) Radical scavenger (4): pentaerythritol tetrakis[3-(-3,5-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010, manufactured by BASF Japan Ltd.) Radical scavenger (5): 4-tert-butylcatechol (DIC Corporation)

[0155] Next, the compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were cured according to the procedure described in the section "Preparation of Cured Products" below to prepare cured products corresponding to Examples 1 to 5 and Comparative Examples 1 to 3, respectively. Then, the glass transition temperatures and flexural strengths were evaluated according to the following methods. The results are shown in Table 1. Ta.

[0156] <<Measurement of glass transition temperature (℃)>> -Preparation of hardened product- Each composition prepared as shown in Table 1 below was poured into a mold measuring 11 cm × 9 cm × 2.4 mm and molded in a press at 175°C for 10 minutes. The molded product was then removed from the mold and post-cured at 175°C for 5 hours to obtain cured products (2.4 mm thick) from the compositions of Examples 1 to 5 and Comparative Examples 1 to 3. -Measurement of the glass transition temperature (℃) of the cured product- Next, each of the 2.4 mm thick cured products prepared above was cut into a size of 5 mm wide and 54 mm long, which was used as test piece 1. Test piece 1 was then measured for its glass transition temperature (°C) using a viscoelasticity measuring device (DMA: Rheometrics solid viscoelasticity measuring device "RSAII", rectangular tension method: frequency 1 Hz, heating rate 3°C / min) to determine the temperature at which the change in elastic modulus was greatest (the rate of change in tan δ was greatest). A higher glass transition temperature (°C) indicates better heat resistance.

[0157] <<Bending strength measurement>> -Preparation of hardened product- Each resin composition prepared as shown in Table 1 below was poured into a mold measuring 11 cm x 9 cm x 4.0 mm and molded using a press at 175°C for 10 minutes. The molded product was then removed from the mold and post-cured at 175°C for 5 hours to obtain cured products (4.0 mm thick) from the compositions of Examples 1 to 5 and Comparative Examples 1 to 3. -Measurement of the glass transition temperature (℃) of the cured product- Next, each of the 4.0 mm thick cured products prepared above was cut into a size of 10 mm wide and 80 mm long, which was used as test piece 2. Then, the bending strength (MPa) of test piece 2 was measured according to JIS K7171. A higher bending strength (MPa) indicates better mechanical properties.

[0158] [Table 1]

[0159] From the results shown in Table 1 above, when comparing Examples 1 to 5 with Comparative Examples 1 to 3, it can be seen that by using the compositions of Examples 1 to 5, both excellent bending strength and heat resistance were achieved during curing. [Industrial Applicability]

[0160] According to the present disclosure, it is possible to provide a composition that exhibits both excellent flexural strength and heat resistance when cured, and a cured product thereof.

Claims

1. A composition comprising a maleimide-based resin, a propenyl-based resin, and a radical scavenger.

2. The maleimide resin is represented by the following general formula (1): 【Chemistry 1】 (In the above general formula (1), R １１ and R １２ each independently represents a hydroxyl group, an alkyl group, an alkoxy group, or an aryl group; M １１ represents a divalent linking group, m11 represents an integer of 0 to 4, m12 represents an integer of 0 to 3, The composition according to claim 1 , wherein n11 is the number of repeating units and represents a natural number.

3. The composition according to claim 1, wherein the propenyl-based resin is one or more selected from the group consisting of resins represented by the following general formulas (i) and (ii): 【Chemistry 2】 (In the above general formula (i), M ｉ１ is n ｉ represents a 2-valent organic group, M ｉ２ represents a cyclic group having one or more unsaturated bonds which may be substituted by a substituent R, and -CH=CH-CH in the above general formula (i) ３ the carbon-carbon double bond of the M ｉ２ and the one or more unsaturated bonds in M ​​form a conjugated diene structure in s-cis configuration, or ｉ２ It itself has a conjugated diene structure in s-cis configuration, L ｉ１ and L ｉ３ each independently represents a single bond, —O—, or —S—; L ｉ２ represents a divalent organic group, n ｉ represents a natural number between 2 and 4.) 【Transformation 3】 (In the above general formula (ii), M ｉｉ１ and M ｉｉ２ each independently represents a cyclic group having one or more unsaturated bonds which may be substituted by a substituent R, and -CH=CH-CH in the above general formula (ii) ３ the carbon-carbon double bond of the M ｉｉ１ and M ｉｉ２ and the one or more unsaturated bonds in M ​​have a conjugated diene structure in s-cis configuration, or ｉｉ１ and M ｉｉ２ It itself has a conjugated diene structure in s-cis configuration, M ｉｉ３ each independently represents a divalent linking group, M ｉｉ４ represents a divalent organic group, M ｉｉ５ each independently represents a trivalent organic group, L ｉｉ１ and L ｉｉ３ represents a divalent organic group, L ｉｉ２ and L ｉｉ４ represents a single bond, —O—, or —S—; L ｉｉ５ and L ｉｉ６ represents a single bond, —O—, or —S—; n ｉｉ represents a natural number.)

4. 2. The composition according to claim 1, wherein the radical scavenger is one or more selected from the group consisting of hindered phenol compounds, benzenediol compounds, nitroxyl radical compounds, nitrosamine compounds, and phenothiazine compounds.

5. A cured product of the composition according to any one of claims 1 to 4.

6. A printed wiring board made using the composition according to any one of claims 1 to 4.

7. A semiconductor encapsulation material comprising the composition according to any one of claims 1 to 4.

8. A build-up film obtained by using the composition according to any one of claims 1 to 4.

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