resin composition

Abstract

To provide a resin composition from which a cured product with low dielectric characteristics, high adhesion to a conductor layer, and excellent mechanical strength can be obtained.SOLUTION: A resin composition contains (A) a polyphenylene ether resin having the number of terminal functional groups of 2 or more, (B) an epoxy resin, (C) a curing agent, and (D) an inorganic filler.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a resin composition. Furthermore, it relates to a resin sheet, a printed circuit board, and a semiconductor device obtained using the resin composition. [Background technology]

[0002] One known manufacturing technique for printed circuit boards is the build-up method, in which insulating layers and conductive layers are stacked alternately.

[0003] As insulating materials for printed circuit boards used in such insulating layers, for example, resin compositions are disclosed in Patent Documents 1 and 2. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2022-60800 [Patent Document 2] Japanese Patent Publication No. 2013-181132 [Overview of the project] [Problems that the invention aims to solve]

[0005] In recent years, with the increasing sophistication of printed circuit boards, there has been a demand for further improvements in the dielectric loss tangent and dielectric constant of the insulating layer, as well as improved adhesion between the insulating layer and the plating. Furthermore, to enhance the mechanical strength of printed circuit boards, there is a demand for further improvements in the maximum point stress and elongation at break of the insulating layer. Hereinafter, dielectric loss tangent and dielectric constant will be collectively referred to as dielectric properties, and maximum point stress and elongation at break will be collectively referred to as mechanical strength.

[0006] The object of the present invention, which was devised in view of the above-mentioned object, is to provide a resin composition that can produce a cured product with low dielectric properties, high adhesion (peel strength) to a conductor layer, and excellent mechanical strength; a resin sheet containing the resin composition; a printed circuit board having an insulating layer formed using the resin composition; and a semiconductor device. [Means for solving the problem]

[0007] As a result of diligent research into the above-mentioned problems, the inventors have found that the above-mentioned problems can be solved by combining (A) a polyphenylene ether resin with a terminal functional group number greater than 2, (B) an epoxy resin, (C) a curing agent, and (D) an inorganic filler, and have completed the present invention.

[0008] In other words, the present invention includes the following: [1] (A) Polyphenylene ether resins having more than 2 terminal functional groups, (B) Epoxy resin, (C) Hardener, and (D) A resin composition containing an inorganic filler. [2] The resin composition according to [1], wherein component (A) has a structure represented by the following formula (A-1). [ka] In formula (A-1), X represents a valence linking group, and Z independently represents a hydrogen atom or a group represented by formula (A-3), and R 11 Each of these independently represents a hydrogen atom or a group represented by formula (A-2), and R 21 , and R 23 Each of these independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have substituents, or a halogen atom, R 22 , and R 24 Each of these independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have substituents, a group represented by formula (A-2), or a halogen atom. However, R 22 , and R 24When it represents a hydrogen atom, and R 22 and R 24 are excluded when one of them is a group represented by the formula (A-2) and the other represents a hydrogen atom, a methyl group, or an ethyl group. a and b each independently represent an integer of 2 to 6, k each independently represents an integer of 1 to 4, and n each independently represents an integer of 0 to 200.

Chemical formula

Chemical formula

[0009] According to the present invention, it is possible to provide a resin composition that can produce a cured product with low dielectric properties, high adhesion (peel strength) to the conductive layer, and excellent mechanical strength, as well as a resin sheet, a printed circuit board, and a semiconductor device using the resin composition. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below with reference to its preferred embodiments. However, the present invention is not limited to the embodiments and examples described below, and can be implemented with modifications as appropriate without departing from the scope of the claims and equivalents of the present invention.

[0011] [Resin composition] The resin composition of the present invention contains (A) a polyphenylene ether resin with a terminal functional group number greater than 2, (B) an epoxy resin, (C) a curing agent, and (D) an inorganic filler. In the present invention, by combining components (A), (B), (C), and (D), a cured product can be obtained that has a low dielectric loss tangent, high adhesion to the conductive layer, and excellent mechanical strength.

[0012] The resin composition of the present invention may further contain any components in combination with components (A) to (D). Examples of optional components include (E) radical polymerizable compounds, (F) thermoplastic resins, (G) curing accelerators, (H) organic fillers, (I) other additives, and (J) solvents. The components contained in the resin composition of the present invention will be described in detail below.

[0013] <(A) Polyphenylene ether resins with more than 2 terminal functional groups> The resin composition contains a polyphenylene ether resin as component (A), with a number of (A)-terminal functional groups greater than 2. By including component (A) in the resin composition, a cured product with excellent dielectric properties, high adhesion to the conductive layer, and excellent mechanical strength can be obtained. Component (A) may be used alone or in combination of two or more types.

[0014] Component (A) can be a resin having a polyphenylene ether skeleton with more than 2 terminal functional groups. The polyphenylene ether skeleton refers to a skeleton having repeating units represented by the following formula (a), or repeating units in which hydrogen atoms in the phenylene group of formula (a) are replaced by substituents, etc. In the formula, * represents a bond. [ka]

[0015] Component (A) has a terminal functional group number greater than 2, preferably 2.1 or more, more preferably 2.2 or more. The upper limit is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. By using a polyphenylene ether resin with a terminal functional group number within this range, a cured product with excellent dielectric properties, high adhesion to the conductive layer, and excellent mechanical strength can be obtained. The terminal functional group number is a numerical value representing the average value of functional groups present at the ends per molecule of component (A). The method for measuring terminal functional groups differs depending on the type of functional group, but for example, if the terminal functional group is a hydroxyl group, it can be determined by adding tetraethylammonium hydroxide, which associates with the hydroxyl group in component (A), to prepare a mixed solution and measuring the absorbance of the prepared mixed solution. If the terminal functional group is not a hydroxyl group, component (A) and a standard sample such as 1,3,5-trimethoxybenzene are dissolved in a deuterated solvent. 1 1H-NMR is measured. 1The number of terminal functional groups can be determined by 1H-NMR from the integral value of the peak originating from the terminal functional group, the integral value of the peak of the functional group in the standard sample, the mass of component (A), and the mass of the standard sample. Further details can be measured by the method described in the examples below.

[0016] (A) The number of terminal functional groups per gram of component is preferably 100 μmol / g or more, more preferably 500 μmol / g or more, even more preferably 1000 μmol / g or more, preferably 5000 μmol / g or less, more preferably 3000 μmol / g or less, and even more preferably 2000 μmol / g or less, from the viewpoint of obtaining the effects of the present invention to be clearly realized. (A) The number of terminal functional groups per gram of component can be measured by the method described in the examples below.

[0017] (A) The functional groups at the terminal end of component (A) include hydroxyl groups, acryloyl groups, methacryloyl groups, and styryl groups. In particular, from the viewpoint of obtaining the effects of the present invention in a remarkable manner, the functional group is preferably either a hydroxyl group or a methacryloyl group, and more preferably a hydroxyl group.

[0018] (A) The number-average molecular weight of component (A) is 100 or more, more preferably 500 or more, even more preferably 1000 or more, preferably 5000 or less, more preferably 3000 or less, and even more preferably 2000 or less, from the viewpoint of obtaining the effects of the present invention to be clearly demonstrated. The number-average molecular weight (Mn) of the resin can be measured by gel permeation chromatography (GPC), and the details can be measured by the method described in the examples below.

[0019] (A) The glass transition temperature (Tg) of component (A) is preferably 120°C or higher, more preferably 130°C or higher, even more preferably 140°C or higher, 150°C or higher, or 160°C or higher, and preferably 300°C or lower, more preferably 250°C or lower, even more preferably 200°C or lower, or 190°C or lower, from the viewpoint of obtaining the effects of the present invention to be clearly demonstrated. The glass transition temperature (Tg) can be measured by the method described in the examples below.

[0020] Component (A) preferably has a structure represented by the following formula (A-1). [ka] In formula (A-1), X represents a valence linking group, and Z independently represents a hydrogen atom or a group represented by formula (A-3), and R 11 Each of these independently represents a hydrogen atom or a group represented by formula (A-2), and R 21 , and R 23 Each of these independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have substituents, or a halogen atom, R 22 , and R 24 Each of these independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have substituents, a group represented by formula (A-2), or a halogen atom. However, R 22 , and R 24 When represents a hydrogen atom, and R 22 and R 24 This excludes the case where one of the elements is a group represented by formula (A-2) and the other is a hydrogen atom, a methyl group, or an ethyl group. a and b each independently represent an integer from 2 to 6, k each independently represent an integer from 1 to 4, and n each independently represent an integer from 0 to 200. [ka] In formula (A-2), R 31 , and R 34 Each of these independently represents an alkylene group with 1 to 8 carbon atoms, and R 32 , and R 33 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, and R 35 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group. * represents a bond. d and e each independently represent 0 or 1. [ka] In formula (A-3), R 41Each of these independently represents a divalent hydrocarbon group with 1 to 30 carbon atoms, and R 42 , R 43 , and R 44 Each of these independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group with 1 to 30 carbon atoms, an alkoxy group with 1 to 30 carbon atoms, an aryloxy group with 6 to 30 carbon atoms, an alkylamino group, or a hydroxyalkyl group with 1 to 30 carbon atoms. s represents an integer from 0 to 5. * represents a bond.

[0021] In formula (A-1), a and b each independently represent integers between 2 and 6, preferably between 2 and 4. It is preferable that a and b represent the same integer.

[0022] In equation (A-1), n ​​represents an integer between 0 and 200, preferably between 0 and 180.

[0023] In formula (A-1), X represents an α-valent linking group. Examples of α-valent linking groups include α-valent hydrocarbon groups, α-valent groups consisting of an ester bond and a hydrocarbon group, oxygen atoms, nitrogen atoms, phosphorus atoms, silicon atoms, etc.

[0024] Examples of α-valent hydrocarbon groups include α-valent aliphatic hydrocarbon groups, α-valent aromatic hydrocarbon groups, and groups consisting of combinations thereof, with α-valent aliphatic hydrocarbon groups being preferred. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, with saturated aliphatic hydrocarbon groups being preferred. The aliphatic hydrocarbon group may be a linear hydrocarbon group or a cyclic hydrocarbon group (i.e., an alicyclic hydrocarbon group), or a combination thereof. Furthermore, the linear hydrocarbon group may be either linear or branched, with branched being preferred. The α-valent aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 30 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and even more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0025] The aromatic hydrocarbon group of a valency is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and even more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.

[0026] Specific examples of the hydrocarbon group of a valency include the groups shown in the following formulas (a1) to (a2). In the formulas, * represents a bond.

Chemical formula

[0027] The hydrocarbon group of a valency may have a substituent. The substituent is not particularly limited. For example, a halogen atom, -OH, -O-C 1-6 alkyl group, -N(C 1-10 alkyl group)2, C 1-10 alkyl group, C 6-10 aryl group, -NH2, -CN, -C(O)O-C 1-10 alkyl group, -COOH, -C(O)H, -NO2, etc. may be mentioned. Here, the term "C p-q "(p and q are positive integers and satisfy p < q.) represents that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, the expression "C 1-10 alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure includes a spiro ring and a condensed ring.

[0028] [[ID=3​​​​Examples of alpha-valent groups consisting of an ester bond and a hydrocarbon group include alpha-valent groups consisting of an ester bond and an alkylene group, alpha-valent groups consisting of an ester bond and an arylene group, alpha-valent groups consisting of an ester bond, an alkylene group and an alpha-valent hydrocarbon group, and alpha-valent groups consisting of an ester bond, an arylene group and an alpha-valent hydrocarbon group, with alpha-valent groups consisting of an ester bond, an alkylene group and an alpha-valent hydrocarbon group being preferred.

[0030] The alkylene group is preferably one having 1 to 30 carbon atoms, more preferably one having 1 to 20 carbon atoms, and even more preferably one having 1 to 10 carbon atoms. Examples of alkylene groups include methylene, ethylene, trimethylene, 1,2-propylene, tetramethylene, 2-methyl-1,3-trimethylene, 1,1-dimethylethylene, pentamethylene, 1-ethyl-1,3-propylene, 1-methyl-1,4-butylene, 2-methyl-1,4-butylene, 3-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,2-cyclopentylene, 1,3-cyclopentylene, and 2,2-dimethyl-1,3-propylene 1,1-dimethyl-1,3-propylene group, 3,3-dimethyl-1,3-propylene group, hexamethylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, 1-ethyl-1,4-butylene group, 2-ethyl-1,4-butylene group, 3-ethyl-1,4-butylene group, 1-methyl-1,5-pentylene group, 2-methyl-1,5-pentylene group, 3-methyl-1,5-pentylene group, 4-methylpentylene group, 1,1-dimethyl-1,4-butylene group, 2,2 -dimethyl-1,4-butylene group, 3,3-dimethyl-1,4-butylene group, 1,2-dimethyl-1,4-butylene group, 1,3-dimethyl-1,4-butylene group, 2,3-dimethyl-1,4-butylene group, heptamethylene group, 1-methyl-1,6-hexylene group, 2-methyl-1,6-hexylene group, 3-methyl-1,6-hexylene group, 4-methyl-1,6-hexylene group, 5-methyl-1,6-hexylene group, 1-ethyl-1,5-pentylene group, 2-ethyl-1,5-pentylene group, 3-ethyl-1 ,5-pentylene group, 1,1-dimethyl-1,5-pentylene group, 2,2-dimethyl-1,5-pentylene group, 3,3-dimethyl-1,5-pentylene group, 4,4-dimethyl-1,5-pentylene group, 1,2-dimethyl-1,5-pentylene group, 1,3-dimethyl-1,5-pentylene group, 1,4-dimethyl-1,5-pentylene group, 2,3-dimethyl-1,5-pentylene group, 2,4-dimethyl-1,5-pentylene group, 3,4-dimethyl-1,5-pentylene group, 2-methyl-3,3-dimethyl-1,4-butylene group, 1-methyl-3,3-dimethyl-1,4-butylene group, 1,2,3-trimethyl-1,4-butylene group, 1,3-dimethyl-1,4-pentylene group, 2-isopropyl-1,4-butylene group, 2-methyl-1,4-cyclohexylene group, 3-methyl-1,4-cyclohexylene group, 4-methyl-1,4-cyclohexylene group, 1-cyclohexylmethylene group, 2-ethyl-1,3-cyclopentylene group, 3-ethyl-1,3-cyclopentylene group, 2,3-dimethyl-1,3-cyclopentylene group, 2,4-dimethyl-1,3-cyclopene Tylene group, 2-methyl-1,3-cyclopentylmethylene group, 2-cyclopentylethylene group, 1-cyclopentylethylene group, octamethylene group, 1-methyl-1,7-heptylene group, 1-ethyl-1,6-hexylene group, 1-propyl-1,5-pentylene group, 2-methyl-1,7-heptylene group, 3-methyl-1,7-heptylene group, 4-methyl-1,7-heptylene group, 5-methyl-1,7-heptylene group, 6-methyl-1,7-heptylene group, 2-ethyl-1,6-hexylene group, 3-ethyl-1,6-hexylene group, 4-ethyl-1,6-hexylene 1,1-dimethyl-1,6-hexylene group, 2,2-dimethyl-1,6-hexylene group, 3,3-dimethyl-1,6-hexylene group, 4,4-dimethyl-1,6-hexylene group, 5,5-dimethyl-1,6-hexylene group, 1,2-dimethyl-1,6-hexylene group, 1,3-dimethyl-1,6-hexylene group, 1,4-dimethyl-1,6-hexylene group, 1,5-dimethyl-1,6-hexylene group, 2,3-dimethyl-1,6-hexylene group, 2,4-dimethyl-1,6-hexylene group, 2,5-dimethyl-1 ,6-hexylene group, 1,1-ethylmethyl-1,5-pentylene group, 2,2-ethylmethyl-1,5-pentylene group, 3,3-ethylmethyl-1,5-pentylene group, 4,4-ethylmethyl-1,5-pentylene group, 1-ethyl-2-methyl-1,5-pentylene group, 1-ethyl-3-methyl-1,5-pentylene group, 1-ethyl-4-methyl-1,5-pentylene group, 2-ethyl-1-methyl-1,5-pentylene group, 3-ethyl-1-methyl-1,5-pentylene group, 4-ethyl-1-methyl-1,5-pentylene group, 2-ethyl-3-methyl-1,5-pentylene group, 2-ethyl-4-methyl-1,5-pentylene group, 3-ethyl-2-methyl-1,5-pentylene group, 4-ethyl-3-methyl-1,5-pentylene group, 3-ethyl-4-methyl-1,5-pentylene group, 4-ethyl-3-methyl-1,5-pentylene group, 1-(2-methylpropyl)-1,4-butylene group, 1-(2-methylpropyl)-2-methyl-1,4-butylene group, 1,1-(2-methylpropyl)ethylene group, 1,1-(2-methylpropyl (Propylene) ethyl-1,3-propylene group, 1,1-diethyl-1,3-propylene group, 2,2-diethyl-1,3-propylene group, 1,1-ethylmethyl-2,2-dimethyl-1,3-propylene group, 2,2-ethylmethyl-1,1-dimethyl-1,3-propylene group, 2-ethyl-1,1-dimethyl-1,4-butylene group, 2,3-dimethyl-1,4-cyclohexylene group, 2,3-dimethyl-1,4-cyclohexylene group, 2,5-dimethyl-1,4-cyclohex Silene group, 2,6-dimethyl-1,4-cyclohexylene group, 3,5-dimethyl-1,4-cyclohexylene group, 2-methyl-1,4-cyclohexyl-1-methylene group, 3-methyl-1,4-cyclohexyl-1-methylene group, 4-methyl-1,4-cyclohexyl-1-methylene group, 2-ethyl-1,4-cyclohexylene group, 3-ethyl-1,4-cyclohexylene group, 4-ethyl-1,4-cyclohexylene group, 2-cyclohexylethylene group, 1-cyclohex Examples include xylethylene group, 1-cyclohexyl-2-ethylene group, nonylmethylene group, 1-methyl-1,8-octylene group, decylmethylene group, 1-methyl-1,8-nonylene group, undecylmethylene group, dodecylmethylene group, 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, methylene-1,4-phenylene-methylene group, and ethylene-1,4-phenylene-ethylene group, with methylene and ethylene groups being preferred, and ethylene groups being more preferred.

[0031] The arylene group is preferably one having 6 to 20 carbon atoms, more preferably one having 6 to 15 carbon atoms, and even more preferably one having 6 to 12 carbon atoms. Specific examples of arylene groups include phenylene, naphthylene, and anthracenylene.

[0032] A specific example of an α-valent group consisting of an ester bond and a hydrocarbon group is the group shown in formula (a3) ​​below. In the formula, * represents a bond. [ka]

[0033] The alkylene group and the arylene group may have substituents. The substituents are the same as those that may be present on the α-valent linking group represented by X in formula (A-1).

[0034] In formula (A-1), X preferably represents an α-valent hydrocarbon group or an α-valent group consisting of an ester bond, an alkylene group and an α-valent hydrocarbon group; more preferably represents an α-valent aliphatic hydrocarbon group or an α-valent group consisting of an ester bond, an alkylene group and an α-valent hydrocarbon group; and even more preferably represents the group shown in formula (a1) or formula (a3).

[0035] In formula (A-1), Z independently represents either a hydrogen atom or a group represented by formula (A-3).

[0036] In equation (A-3), R 41 Each of these independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms. Examples of divalent hydrocarbon groups include divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon groups, with divalent aliphatic hydrocarbon groups being preferred.

[0037] The divalent aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, with saturated aliphatic hydrocarbon groups being preferred. The divalent aliphatic hydrocarbon group may be a linear hydrocarbon group or a cyclic hydrocarbon group (i.e., an alicyclic hydrocarbon group), or a combination thereof. Furthermore, the linear hydrocarbon group may be either linear or branched, with branched being preferred. The divalent aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 30 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and even more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Specific examples of divalent aliphatic hydrocarbon groups include alkylene groups, alkenylene groups, and alkylylene groups, with alkylene groups being preferred.

[0038] The divalent aromatic hydrocarbon group is preferably a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and even more preferably a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Specific examples of divalent aromatic hydrocarbon groups include arylene groups.

[0039] The alkylene group is the same as the alkylene group in the α-valent group, which is a combination of an ester bond and an alkylene group that can be represented by X in formula (A-1).

[0040] Examples of alkenylene groups include etenylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octenylene, nonerine, and decenylene.

[0041] Examples of alkylylene groups include ethynylene, pyropinylene, butynylene, pentynylene, hexynylene, heptynylene, octynylene, noninylene, and desynylene. Examples of allylene groups include phenylene and naphthylene.

[0042] Examples of arylene groups include phenylene groups, naphthylene groups, and anthracenylene groups.

[0043] The alkylene group, alkenylene group, alkynylene group, and arylene group may have substituents. The substituents are the same as those that may be present on the α-valent linking group represented by X in formula (A-1).

[0044] In equation (A-3), R 42 , R 43 , and R 44 Each of these independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylamino group, or a hydroxyalkyl group having 1 to 30 carbon atoms.

[0045] Monovalent hydrocarbon groups having 1 to 30 carbon atoms include monovalent aliphatic hydrocarbon groups, monovalent aromatic hydrocarbon groups, and groups consisting of combinations thereof, with monovalent aliphatic hydrocarbon groups being preferred. Monovalent aliphatic hydrocarbon groups may be monovalent saturated aliphatic hydrocarbon groups or monovalent unsaturated aliphatic hydrocarbon groups, with monovalent saturated aliphatic hydrocarbon groups being preferred. Monovalent aliphatic hydrocarbon groups may be linear hydrocarbon groups, cyclic hydrocarbon groups (i.e., alicyclic hydrocarbon groups), or combinations thereof. Furthermore, linear hydrocarbon groups may be linear or branched, with branched being preferred. Monovalent aliphatic hydrocarbon groups having 1 to 30 carbon atoms are preferred, aliphatic hydrocarbon groups having 1 to 20 carbon atoms are more preferred, and aliphatic hydrocarbon groups having 1 to 10 carbon atoms are even more preferred. Specific examples of monovalent aliphatic hydrocarbon groups include alkyl groups.

[0046] The monovalent aromatic hydrocarbon group is preferably a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and even more preferably a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Specific examples of monovalent aromatic hydrocarbon groups include aryl groups.

[0047] Examples of alkyl groups include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, 1-ethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, amyl group, cyclopentyl group, 2,2-dimethylpropyl group, 1,1-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentylene group, 4-methylpentylene group, 1,1- Dimethylbutylene group, 2,2-dimethylbutylene group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 3,3-dimethylpentyl group, 4,4-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylbutyl Lupentyl group, 1,4-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,4-dimethylpentyl group, 2-methyl-3,3-dimethylbutyl group, 1-methyl-3,3-dimethylbutyl group, 1,2,3-trimethylbutyl group, 1,3-dimethyl-2-pentyl group, 2-isopropylbutyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1-cyclohexylmethyl group, 2-ethylcyclopentyl group, 3-ethylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2 ,4-dimethylcyclopentyl group, 2-methylcyclopentylmethyl group, 2-cyclopentylethyl group, 1-cyclopentylethyl group, n-octyl group, 2-octyl group, 3-octyl group, 4-octyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 1,1-ethylmethylpentyl group, 2,2-ethylmethylpentyl group, 3,3-ethylmethylpentyl group, 4,4-ethylmethylpentyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1 -Ethyl-4-methylpentyl group, 2-ethyl-1-methylpentyl group, 3-ethyl-1-methylpentyl group, 4-ethyl-1-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-2-methylpentyl group, 4-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 4-ethyl-3-methylpentyl group, 1-(2-methylpropyl)butyl group, 1-(2-methylpropyl)-2-methylbutyl Group, 1,1-(2-methylpropyl)ethyl group, 1,1-(2-methylpropyl)ethylpropyl group, 1,1-diethylpropyl group, 2,2-diethylpropyl group, 1,1-ethylmethyl-2,2-dimethylpropyl group, 2,2-ethylmethyl-1,1-dimethylpropyl group, 2-ethyl-1,1-dimethylbutyl group, 2,3-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl Examples include the 3,5-dimethylcyclohexyl group, 2-methylcyclohexylmethyl group, 3-methylcyclohexylmethyl group, 4-methylcyclohexylmethyl group, 2-ethylcyclohexyl group, 3-ethylcyclohexyl group, 4-ethylcyclohexyl group, 2-cyclohexylethyl group, 1-cyclohexylethyl group, 1-cyclohexyl-2-ethylene group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, propargyl group, etc.

[0048] Examples of aryl groups include phenyl, naphthyl, and anthracenyl groups.

[0049] Examples of groups consisting of these combinations include the benzyl group and the 2-phenylethyl group.

[0050] The number of carbon atoms in the alkoxy group having 1 to 30 carbon atoms is preferably 1 to 20, and more preferably 1 to 10. Examples of alkoxy groups having 1 to 30 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, t-butoxy, 1-pentoxy, 2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, 2-ethylpropoxy, 3,3-dimethylpropoxy, 1,1-dimethylpropoxy, cyclopentoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 4-methylpentoxy, 3-methylpentoxy, and 2-methylpentoxy. Examples include the rupentoxy group, 1,1-dimethyl-1-butoxy group, 2,2-dimethyl-1-butoxy group, 3,3-dimethyl-1-butoxy group, 4,4-dimethyl-1-butoxy group, 1,2-dimethyl-1-butoxy group, 1,3-dimethyl-1-butoxy group, 2-ethyl-1-butoxy group, 3-ethyl-1-butoxy group, 3,3-ethylmethyl-1-propoxy group, cyclohexoxy group, 1-octoxy group, 2-octoxy group, 3-octoxy group, 4-octoxy group, 2-ethyl-1-hexoxy group, and phenylmethoxy group.

[0051] The number of carbon atoms in the aryloxy group having 6 to 30 carbon atoms is preferably 6 to 20, and more preferably 6 to 10. Examples of aryloxy groups having 6 to 30 carbon atoms include phenoxy, 4-methylphenoxy, 3-methylphenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,3-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-isopropylphenoxy, 2-isopropylphenoxy, 3-isopropylphenoxy, and 4-isobutylphenoxy. Examples include 2-isobutylphenoxy group, 3-isobutylphenoxy group, 4-t-butylphenoxy group, 2-t-butylphenoxy group, 3-t-butylphenoxy group, 2,6-di-t-butylphenoxy group, 2,4-di-t-butylphenoxy group, 2,3-di-t-butylphenoxy group, 2-methyl-4-t-butylphenoxy group, 2-methyl-6-t-butylphenoxy group, and 4-methyl-2-t-butylphenoxy group.

[0052] The alkylamino group may be a monoalkylamino group or a dialkylamino group, with the dialkylamino group being preferred. The alkylamino group is preferably an alkylamino group having 1 to 30 carbon atoms, more preferably an alkylamino group having 1 to 20 carbon atoms, and even more preferably an alkylamino group having 1 to 10 carbon atoms. Examples of alkylamino groups include dimethylamino group, ethylmethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-t-butylamino group, and dicyclohexylamino group.

[0053] The number of carbon atoms in a hydroxyalkyl group having 1 to 30 carbon atoms is preferably 1 to 20, and more preferably 1 to 10. Examples of hydroxyalkyl groups having 1 to 30 carbon atoms include hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxyisopropyl groups.

[0054] Monovalent hydrocarbon groups having 1 to 30 carbon atoms, alkoxy groups having 1 to 30 carbon atoms, aryloxy groups having 6 to 30 carbon atoms, alkylamino groups, and hydroxyalkyl groups having 1 to 30 carbon atoms may have substituents. The substituents are the same as those that may be present on the α-valent linking group represented by X in formula (A-1).

[0055] In particular, in equation (A-3), R 42 , R 43 , and R 44 Each of these preferably independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, R 42 , and R 43 represents a hydrogen atom, R 44 R more preferably represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. 42 , and R 43 represents a hydrogen atom, R 44 It is more preferable that this represents a hydrogen atom or a methyl group.

[0056] In formula (A-3), s represents an integer between 0 and 5, preferably an integer between 0 and 3, more preferably 0 or 1, and even more preferably 0.

[0057] In equation (A-1), R 11 Each of these independently represents either a hydrogen atom or a group represented by formula (A-2).

[0058] In equation (A-2), R 31 , and R 34 Each of these independently represents an alkylene group having 1 to 8 carbon atoms. The number of carbon atoms in the alkylene group having 1 to 8 carbon atoms is preferably 1 to 6, more preferably 1 to 3. Specifically, the alkylene group having 1 to 8 carbon atoms is the same as the alkylene group having 1 to 8 carbon atoms in the a-valent group consisting of a combination of an ester bond and an alkylene group that can be represented by X in formula (A-1).

[0059] In equation (A-2), R 32 , and R33 Each of these independently represents an alkyl group having 1 to 8 carbon atoms. The number of carbon atoms in the alkyl group having 1 to 8 carbon atoms is preferably 1 to 6, more preferably 1 to 3. A specific example of an alkyl group having 1 to 8 carbon atoms is R in formula (A-3). 42 Among the alkyl groups in hydrocarbon groups with 1 to 30 carbon atoms represented by , it is the same as alkyl groups with 1 to 8 carbon atoms. In particular, R 32 , and R 33 It is preferable that this represents a methyl group.

[0060] In equation (A-2), R 35 R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group. The alkyl group having 1 to 8 carbon atoms is R in formula (A-2). 32 This is the same as an alkyl group with 1 to 8 carbon atoms represented by R. 35 Preferably, the element is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0061] Alkyl groups having 1 to 8 carbon atoms may have substituents. These substituents are the same as those that may be present on the α-valent linking group represented by X in formula (A-1).

[0062] In formula (A-2), d and e each independently represent 0 or 1, with 0 being preferred.

[0063] In particular, in equation (A-2), d and e represent 0, and R 32 , R 33 , and R 35 It is preferable that the given element represents an alkyl group having 1 to 8 carbon atoms, and it is more preferable that formula (A-2) represents a t-butyl group.

[0064] In equation (A-1), k represents an integer between 1 and 4, preferably an integer between 1 and 3.

[0065] In equation (A-1), R 21 , and R 23Each of these independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms (which may have substituents), or a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, or iodine atoms.

[0066] Monovalent hydrocarbon groups having 1 to 12 carbon atoms include monovalent aliphatic hydrocarbon groups, monovalent aromatic hydrocarbon groups, and groups consisting of combinations thereof, with monovalent aliphatic hydrocarbon groups being preferred. Monovalent aliphatic hydrocarbon groups may be monovalent saturated aliphatic hydrocarbon groups or monovalent unsaturated aliphatic hydrocarbon groups, with monovalent saturated aliphatic hydrocarbon groups being preferred. Monovalent aliphatic hydrocarbon groups may be linear hydrocarbon groups, cyclic hydrocarbon groups (i.e., alicyclic hydrocarbon groups), or combinations thereof. Furthermore, linear hydrocarbon groups may be linear or branched, with branched being preferred. Monovalent aliphatic hydrocarbon groups having 1 to 12 carbon atoms are preferred, aliphatic hydrocarbon groups having 1 to 10 carbon atoms are more preferred, and aliphatic hydrocarbon groups having 1 to 6 carbon atoms are even more preferred. Specific examples of monovalent aliphatic hydrocarbon groups include alkyl groups.

[0067] The monovalent aromatic hydrocarbon group is preferably a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Specific examples of monovalent aromatic hydrocarbon groups include aryl groups. Examples of aryl groups include phenyl groups and naphthyl groups.

[0068] A specific example of an alkyl group having 1 to 12 carbon atoms is R in formula (A-3). 42 Among the alkyl groups in hydrocarbon groups with 1 to 30 carbon atoms represented by , it is the same as alkyl groups with 1 to 12 carbon atoms. In particular, R 21 , and R 23 Each of these groups is preferably independently of a methyl group, an ethyl group, an n-propyl group, a vinyl group, an aryl group, an ethynyl group, or a propargyl group, more preferably representing a methyl group or an ethyl group, and even more preferably representing a methyl group.

[0069] Alkyl groups having 1 to 12 carbon atoms may have substituents. These substituents are the same as those that may be present on the α-valent linking group represented by X in formula (A-1).

[0070] In equation (A-1), R 22 , and R 24 Each of these independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have substituents, a group represented by formula (A-2), or a halogen atom. However, R 22 , and R 24 When both represent a hydrogen atom, and R 21 and R 24 Cases where one of the groups is represented by formula (A-2) and the other represents a hydrogen atom, a methyl group, or an ethyl group are excluded. Monovalent hydrocarbon groups having 1 to 12 carbon atoms that may have substituents, groups represented by formula (A-2), and halogen atoms are as described above.

[0071] (A) Component can be synthesized by known methods. For example, it can be synthesized by the method described in International Publication No. 2022 / 190497.

[0072] (A) The content of component (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less, when the nonvolatile components in the resin composition are considered to be 100% by mass, from the viewpoint of obtaining a cured product with low dielectric properties, high adhesion, and excellent mechanical strength.

[0073] (A) The content of component (A) is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, preferably 45% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less, or 20% by mass or less, when the total resin component in the resin composition is 100% by mass.

[0074] In the present invention, unless otherwise specified, the content of each component in the resin composition is the value when the non-volatile components in the resin composition are taken as 100% by mass, and the non-volatile components refer to all non-volatile components in the resin composition excluding the solvent. Furthermore, the resin components in the resin composition refer to the components of the non-volatile components in the resin composition excluding (D) inorganic fillers.

[0075] <(B) Epoxy resin> The resin composition contains epoxy resin (B) as component (B). This epoxy resin (B) as component (B) does not include any of the components (A) mentioned above. By including epoxy resin (B) in the resin composition, a cured product exhibiting good mechanical strength and insulation reliability can be obtained. Epoxy resin (B) may be used alone or in combination of two or more types.

[0076] (B) Examples of epoxy resins include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, and glycidyl ester type epoxy resin. Examples include epoxy resins, glycidylcyclohexane type epoxy resins, alkyl diglycidyl ether type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiroring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, phenolphthaleimidine type epoxy resins, and the like. Epoxy resins may be used individually or in combination of two or more types.

[0077] The resin composition preferably contains an epoxy resin having two or more epoxy groups per molecule as component (B). From the viewpoint of significantly obtaining the desired effects of the present invention, the ratio of the epoxy resin having two or more epoxy groups per molecule to 100% by mass of epoxy resin (B) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0078] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only liquid epoxy resin as component (B), only solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin. In particular, from the viewpoint of obtaining the effects of the present invention in a remarkable manner, it is preferable to contain a combination of liquid epoxy resin and solid epoxy resin.

[0079] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0080] Preferred liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having a butadiene structure, glycidylcyclohexane type epoxy resin, phenolphthaleimidine type epoxy resin, and alkyl diglycidyl ether type epoxy resin; more preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, and alkyl diglycidyl ether type epoxy resin; and even more preferably naphthalene type epoxy resin, bisphenol A type epoxy resin, and bisphenol F type epoxy resin.

[0081] Specific examples of liquid epoxy resins include DIC's "HP4032," "HP4032D," and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US," "jER828EL," "825," and "Epicote 828EL" (bisphenol A-type epoxy resin); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F-type epoxy resin); Mitsubishi Chemical's "jER152" (phenol novolac-type epoxy resin); Mitsubishi Chemical's "630" and "630LSD" (glycidylamine-type epoxy resin); and Nippon Steel Chemical & Material's "ZX1 Examples include "059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) from Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin with an ester skeleton) from Daicel Corporation; "PB-3600" (epoxy resin with a butadiene structure) from Daicel Corporation; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) from Nippon Steel Chemical & Material Corporation; and "YED216D" (alkyl diglycidyl ether type epoxy resin) from Mitsubishi Chemical Corporation. These may be used individually or in combination of two or more types.

[0082] As for the solid epoxy resin, a solid epoxy resin having two or more epoxy groups per molecule is preferred, a solid epoxy resin having three or more epoxy groups per molecule is more preferred, and an aromatic solid epoxy resin having three or more epoxy groups per molecule is even more preferred.

[0083] Preferred solid epoxy resins include bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin, with naphthalene-type epoxy resin and biphenyl-type epoxy resin being more preferred.

[0084] Specific examples of solid epoxy resins include DIC's "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), "N-690" (cresol novolac-type epoxy resin), "N-695" (cresol novolac-type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene-type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether-type epoxy resin); Nippon Kayaku's "EPPN-502H" (trisphenol-type epoxy resin), "NC7000L" (naphthol novolac-type epoxy resin), "NC3000H", "NC3000", "NC3000L", Examples include "NC3100" (biphenyl-type epoxy resin); "ESN475V" (naphthalene-type epoxy resin) and "ESN485" (naphthol novolac-type epoxy resin) from Nippon Steel Chemical & Material Co., Ltd.; "YX4000H" and "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin) and "YX8800" (anthracene-type epoxy resin) from Mitsubishi Chemical Corporation; "PG-100" and "CG-500" from Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF-type epoxy resin), "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin) and "jER1031S" (tetraphenylethane-type epoxy resin) from Mitsubishi Chemical Corporation; and "WHR-991S" (phenolphthaleimidine-type epoxy resin) from Nippon Kayaku Co., Ltd. These may be used individually or in combination of two or more types.

[0085] (B) When a liquid epoxy resin and a solid epoxy resin are used in combination as component, their mass ratio (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5. By having the mass ratio of the liquid epoxy resin and the solid epoxy resin within this range, the desired effects of the present invention can be remarkably obtained.

[0086] The epoxy equivalent of component (B) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. This range ensures that the cured resin composition has sufficient crosslinking density. The epoxy equivalent is the mass of epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0087] The weight-average molecular weight (Mw) of component (B) is preferably 100 to 5000, more preferably 150 to 3000, and even more preferably 200 to 1500, from the viewpoint of significantly obtaining the desired effects of the present invention. The weight-average molecular weight of the epoxy resin is the weight-average molecular weight on a polystyrene basis, measured by gel permeation chromatography (GPC).

[0088] (B) The content of component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, preferably 45% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, or 12% by mass or less, when the nonvolatile components in the resin composition are considered to be 100% by mass.

[0089] (B) The content of component (B) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, when the total resin component in the resin composition is considered to be 100% by mass, from the viewpoint of obtaining a cured product that exhibits good mechanical strength and insulation reliability.

[0090] <(C) Hardener> The resin composition contains a curing agent as component (C). This curing agent as component (C) does not include those corresponding to components (A) and (B) described above. Component (C) usually has the function of curing the resin composition by reacting with component (B). Component (C) may be used alone, or two or more types may be used in any ratio.

[0091] Component (C) can be a compound that reacts with component (B) to cure the resin composition, and examples include active ester curing agents, phenol curing agents, benzoxazine curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, and cyanate ester curing agents. In particular, from the viewpoint of obtaining the effects of the present invention, component (C) preferably contains any of an active ester curing agent, a phenol curing agent, a cyanate ester curing agent, and a carbodiimide curing agent, and more preferably contains either an active ester curing agent or a phenol curing agent.

[0092] Examples of active ester curing agents include those having one or more active ester groups in one molecule. Among these, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferred as active ester curing agents. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferred.

[0093] Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0094] Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by the condensation of two phenol molecules with one dicyclopentadiene molecule.

[0095] Preferred examples of active ester-based curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolac, and active ester compounds containing a benzoylated phenol novolac. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. "Dicyclopentadiene-type diphenol structure" refers to a divalent structure consisting of phenylene-dicyclopentylene-phenylene.

[0096] Commercially available active ester curing agents include, as active ester compounds containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", and "EXB-8000L-65TM" (manufactured by DIC); and as active ester compounds containing a naphthalene structure, "HPC-8150-60T", "HPC-8150-62T", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T", and "EXB9416- Examples include "70BK" and "EXB-8151-62T" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent that is an acetylated phenol novolac; and "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester curing agents that are benzoylated phenol novolacs.

[0097] From the viewpoint of significantly obtaining the effects of the present invention, the content of the active ester-based curing agent is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, when the non-volatile components in the resin composition are considered to be 100% by mass.

[0098] From the viewpoint of significantly obtaining the effects of the present invention, the content of the active ester-based curing agent is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, preferably 70% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less, when the resin component in the resin composition is considered to be 100% by mass.

[0099] Examples of phenolic curing agents include those having one or more, preferably two or more, hydroxyl groups bonded to aromatic rings (benzene rings, naphthalene rings, etc.) per molecule. Among these, compounds having hydroxyl groups bonded to benzene rings are preferred. Furthermore, from the viewpoint of heat resistance and water resistance, phenolic curing agents having a novolac structure are preferred. Moreover, from the viewpoint of adhesion, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic curing agents are more preferred. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, triazine skeleton-containing phenol novolac curing agents are preferred.

[0100] Specific examples of phenol-based and naphthol-based curing agents include "MEH-7700," "MEH-7810," "MEH-7851," and "MEH-8000H" from Meiwa Kasei Co., Ltd.; "NHN," "CBN," and "GPH" from Nippon Kayaku Co., Ltd.; and "SN-170," "SN-180," "SN-190," "SN-475," "SN-485," "SN-495," "SN-495V," and "SN-375" from Nippon Steel Chemical & Material Co., Ltd. Examples include "SN-395"; DIC Corporation's "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165"; and Gun-ei Chemical Co., Ltd.'s "GDP-6115L", "GDP-6115H", "ELPC75", etc.

[0101] Specific examples of benzoxazine-based curing agents include "ODA-BOZ" from JFE Chemical Corporation, "HFB2006M" from Showa Polymer Co., Ltd., and "Pd" and "Fa" from Shikoku Chemicals Co., Ltd.

[0102] Specific examples of carbodiimide-based curing agents include "V-03," "V-05," and "V-07" manufactured by Nisshinbo Chemical Co., Ltd., and Stavaxol® P manufactured by Rhein Chemie Co., Ltd.

[0103] Examples of acid anhydride-based curing agents include those having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexen-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone. Examples of acid anhydrides include tetracarboxylic dianhydrides, biphenyltetracarboxylic dianhydrides, naphthalenetetracarboxylic dianhydrides, oxydiphthalic acid dianhydrides, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydrides, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid. Commercially available acid anhydride-based curing agents may also be used, such as "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

[0104] Examples of amine-based curing agents include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines. Among these, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxy Examples include bis(4-(4-aminophenoxy)phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Commercial amine-based curing agents may also be used, such as "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" from Nippon Kayaku Co., Ltd., and "Epicure W" from Mitsubishi Chemical Corporation.

[0105] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) thioether, and bis(4-cyanatephenyl) ether; polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, etc.; and prepolymers in which these cyanate resins are partially triazined. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins) manufactured by Lonza Japan Co., Ltd.; "ULL-950S" (polyfunctional cyanate ester resin); "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazined and trimerized); and others.

[0106] When the number of epoxy groups in component (B) is set to 1, the number of active groups in curing agent (C) is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. Here, "number of epoxy groups in component (A)" is the sum of all values ​​obtained by dividing the mass of the nonvolatile components of component (B) present in the resin composition by the epoxy equivalent. Also, "number of active groups in curing agent (C)" is the sum of all values ​​obtained by dividing the mass of the nonvolatile components of curing agent (C) present in the resin composition by the active group equivalent. By having the number of active groups in curing agent (C) when the number of epoxy groups in component (B) is set to 1 fall within the above range, the desired effects of the present invention can be significantly obtained.

[0107] (C) From the viewpoint of obtaining the effects of the present invention in a remarkable manner, the content of the curing agent is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less, when the nonvolatile components in the resin composition are considered to be 100% by mass.

[0108] (C) From the viewpoint of significantly obtaining the effects of the present invention, the content of the curing agent is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, preferably 70% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less, when the resin component in the resin composition is considered to be 100% by mass.

[0109] <(D) Inorganic filler> The resin composition contains (D) an inorganic filler as component (D). By including the (D) inorganic filler in the resin composition, a cured product with low dielectric properties can be obtained. The (D) inorganic filler is usually included in the resin composition in granular form. Component (D) may be used alone or in combination of two or more types.

[0110] (D) Inorganic compounds are used as the material for the inorganic filler. (D) Examples of materials for the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred as the silica.

[0111] (D) Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" from Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" from Admatex Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" from Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" from Tokuyama Corporation; "Cellspheres" and "MGH-005" from Taiheiyo Cement Corporation; and "Esferique" and "BA-1" from JGC Catalysts & Chemicals Co., Ltd.

[0112] (D) The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, even more preferably 0.3 μm or more, preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less.

[0113] (D) The average particle size of the inorganic filler can be measured by the laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis using a laser diffraction-scattering particle size distribution analyzer, and the average particle size can be measured by taking the median diameter as the average particle size. A sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them with ultrasound for 10 minutes. The sample can be measured using a laser diffraction-type particle size distribution analyzer with blue and red light source wavelengths, using a flow cell method to measure the volume-based particle size distribution of the inorganic filler, and the average particle size can be calculated as the median diameter from the obtained particle size distribution. An example of a laser diffraction-type particle size distribution analyzer is the "LA-960" manufactured by Horiba, Ltd.

[0114] (D) The BET specific surface area of ​​the inorganic filler is preferably 0.1 m². 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 It is 100m or more / g, preferably 100m 2 / g or less, more preferably 70m 2 / g or less, more preferably 40m 2 It is less than / g.

[0115] (D) The specific surface area of ​​the inorganic filler can be measured by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0116] (D) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. One type of surface treatment agent may be used alone, or two or more types may be used in any combination.

[0117] Examples of commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0118] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent preferably falls within a specific range. Specifically, it is preferable that 100% by mass of the inorganic filler is surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably surface-treated with 0.2% to 3% by mass of the surface treatment agent, and even more preferably surface-treated with 0.3% to 2% by mass of the surface treatment agent.

[0119] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, it is preferably 小于等于 1.0 mg / m 2 or less, more preferably 小于等于 0.8 mg / m 2 or less, and even more preferably 小于等于 0.5 mg / m 2 or less.

[0120] (D) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after cleaning the inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)) after surface treatment. Specifically, a sufficient amount of MEK as the solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solids, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, a Horiba "EMIA-320V" or similar can be used.

[0121] Furthermore, the degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit mass of the inorganic filler. The amount of carbon per unit mass of the inorganic filler is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and also preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less. The amount of carbon per unit mass of the inorganic filler (D) can be measured using a carbon analyzer, just like the amount of carbon per unit surface area of ​​the inorganic filler (D).

[0122] (D) The content of inorganic fillers is preferably 50% by mass or more, more preferably 55% by mass or more, even more preferably 60% by mass or more, 65% by mass or more, or 70% by mass or more, when the nonvolatile components in the resin composition are considered to be 100% by mass.

[0123] <(E) Radical polymerizable compounds> The resin composition may contain (E) a radical polymerizable compound as an optional component. This (E) radical polymerizable compound excludes those corresponding to components (A) to (D). Component (E) may be used alone or in combination of two or more types.

[0124] (E) Radical polymerizable compounds may contain ethylenically unsaturated bonds. Therefore, (E) radical polymerizable compounds may have radical polymerizable groups containing ethylenically unsaturated bonds. Examples of radical polymerizable groups include unsaturated hydrocarbon groups such as vinyl groups, allyl groups, 1-propenyl groups, 3-cyclohexenyl groups, 3-cyclopentenyl groups, 2-vinylphenyl groups, 3-vinylphenyl groups, and 4-vinylphenyl groups; and α,β-unsaturated carbonyl groups such as acryloyl groups, methacryloyl groups, and maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl groups). (E) Radical polymerizable compounds preferably have two or more radical polymerizable groups.

[0125] Examples of radical polymerizable compounds (E) include (meth)acrylic radical polymerizable compounds, styrene radical polymerizable compounds, allyl radical polymerizable compounds, and maleimide radical polymerizable compounds. Among these, component (E) preferably contains a maleimide radical polymerizable compound from the viewpoint of obtaining the effects of the present invention.

[0126] (Meth)acrylic radical polymerizable compounds are, for example, compounds having one or more, preferably two or more, acryloyl groups and / or methacryloyl groups. Examples of (meth)acrylic radical polymerizable compounds include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, and 1,9-non- Low molecular weight (molecular weight less than 1000) aliphatic (meth)acrylic acid ester compounds such as dioxanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate; dioxaneglycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate; Examples include low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylic acid ester compounds such as (meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, and propoxylated bisphenol A di(meth)acrylate; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylic acid ester compounds such as tris(3-hydroxypropyl) isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, and ethoxylated isocyanurate tri(meth)acrylate; and high molecular weight (molecular weight 1000 or more) acrylic acid ester compounds such as (meth)acrylic-modified polyphenylene ether resins.Examples of commercially available (meth)acrylic radical polymerizable compounds include "A-DOG" (dioxane glycol diacrylate) from Shin Nakamura Chemical Industry Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate) and "DCP" (tricyclodecane dimethanol dimethacrylate) from Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate) and "KAYARAD R-604" (dioxane glycol diacrylate) from Nippon Kayaku Co., Ltd., and "SA9000" and "SA9000-111" (methacrylic modified polyphenylene ether) from SABIC Innovative Plastics Co., Ltd.

[0127] Styrene-based radical polymerizable compounds are, for example, compounds having one or more, preferably two or more vinyl groups directly bonded to an aromatic carbon atom. Examples of styrene-based radical polymerizable compounds include low molecular weight (molecular weight less than 1000) styrene compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl) ether; and high molecular weight (molecular weight 1000 or more) styrene compounds such as vinylbenzyl-modified polyphenylene ether resins and styrene-divinylbenzene copolymers. Examples of commercially available styrene-based radical polymerizable compounds include "ODV-XET(X03)", "ODV-XET(X04)", and "ODV-XET(X05)" (styrene-divinylbenzene copolymer) from Nippon Steel Chemical & Material Co., Ltd., and "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin) from Mitsubishi Gas Chemical Co., Ltd.

[0128] Allyl radical polymerizable compounds are, for example, compounds having one or more, preferably two or more, allyl groups. Examples of allyl radical polymerizable compounds include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylic acid, and diallyl 2,3-naphthalenecarboxylic acid; isocyanuric acid allyl ester compounds such as 1,3,5-trialyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazine-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-trialyl etherbenzene; and allyl silane compounds such as diallyldiphenylsilane. Examples of commercially available allyl radical polymerizable compounds include "TAIC" (1,3,5-triallyl isocyanurate) from Nippon Chemical Industries, Ltd., "DAD" (diallyl diphenate) from Nichishoku Techno Fine Chemicals Co., Ltd., "TRIAM-705" (triallyl trimellitate) from Wako Pure Chemical Industries, Ltd., "DAND" (2,3-diallyl naphthalenecarboxylate) from Nippon Distillation Industry Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazine-3-yl)phenyl]methane) from Shikoku Chemicals, Ltd., "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) from Nippon Kayaku Co., Ltd., and "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) from Shikoku Chemicals, Ltd.

[0129] Maleimide-based radical polymerizable compounds are, for example, compounds having one or more, preferably two or more, maleimide groups. Maleimide-based radical polymerizable compounds may be aliphatic maleimide compounds containing an aliphatic amine skeleton, or aromatic maleimide compounds containing an aromatic amine skeleton. Examples of commercially available maleimide-based radical polymerizable compounds include "SLK-2600" from Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", and "BMI-2500" (maleimide compounds containing a dimer amine structure) from Dezikner Molecules, "BMI-6100" (aromatic maleimide compound) from Dezikner Molecules, "MIR-5000-60T" and "MIR-3000-70MT" (biphenyl aralkyl type maleimide compounds) from Nippon Kayaku Co., Ltd., "BMI-70" and "BMI-80" from K.I. Chemicals Co., Ltd., and "BMI-2300" and "BMI-TMH" from Yamato Chemical Industries, Ltd. Furthermore, as a maleimide-based radical polymerizable compound, a maleimide resin (indane ring skeleton-containing maleimide compound) disclosed in the Japan Institute of Invention and Innovation Publication No. 2020-500211 may be used.

[0130] (E) The ethylenically unsaturated bond equivalent of the radical polymerizable compound is preferably 20 g / eq. to 3,000 g / eq., more preferably 50 g / eq. to 2,500 g / eq., even more preferably 70 g / eq. to 2,000 g / eq., and particularly preferably 90 g / eq. to 1,500 g / eq. The ethylenically unsaturated bond equivalent represents the mass of the radical polymerizable compound per equivalent of ethylenically unsaturated bonds.

[0131] (E) The weight-average molecular weight (Mw) of the radical polymerizable compound is preferably 40,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, but may be, for example, 150 or more. The weight-average molecular weight can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC).

[0132] The content of component (E) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, when the nonvolatile components in the resin composition are considered to be 100% by mass.

[0133] The content of component (E) is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, when the total resin component in the resin composition is considered to be 100% by mass.

[0134] <(F)Thermoplastic resin> The resin composition may contain (F) thermoplastic resin as an optional component. This (F) thermoplastic resin is excluded from components (A) to (E). Component (F) may be used alone or in combination of two or more types.

[0135] (F) Examples of thermoplastic resins include phenoxy resin, polycarbonate resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamide-imide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, polyester resin, etc. Among these, at least one selected from polyimide resin and phenoxy resin is preferred from the viewpoint of significantly obtaining the desired effects of the present invention.

[0136] As the polyimide resin, a resin having an imide structure can be used. Polyimide resins generally include those obtained by the imidation reaction of a diamine compound and an acid anhydride. Specific examples of polyimide resins include the polyimide resin described in Japanese Patent Publication No. 2021-14544.

[0137] Commercially available polyimide resins can be used. Examples of commercially available products include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin-Nippon Rika Co., Ltd.

[0138] As the polycarbonate resin, a resin having a carbonate structure can be used. Examples of such resins include carbonate resins without reactive groups, carbonate resins containing hydroxyl groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing acid anhydride groups, carbonate resins containing isocyanate groups, and carbonate resins containing urethane groups. Here, a reactive group refers to a functional group that can react with other components, such as a hydroxyl group, phenolic hydroxyl group, carboxyl group, acid anhydride group, isocyanate group, urethane group, and epoxy group.

[0139] Commercially available polycarbonate resins can be used. Examples of commercially available products include "FPC0220" from Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diols) from Asahi Kasei Chemicals Corporation, and "C-1090," "C-2090," and "C-3090" (polycarbonate diols) from Kuraray Co., Ltd.

[0140] Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal end of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.

[0141] Specific examples of phenoxy resins include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton) manufactured by Mitsubishi Chemical Corporation; "YX8100" (phenoxy resin containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation; "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton) manufactured by Mitsubishi Chemical Corporation; "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; and "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482" manufactured by Mitsubishi Chemical Corporation.

[0142] Examples of polyvinyl acetal resins include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resins include S-Rec BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0143] Specific examples of polyamide-imide resins include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd. Other specific examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Co., Ltd.

[0144] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0145] Specific examples of polyphenylene ether resins include the oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company.

[0146] Specific examples of polysulfone resins include Solvay Advanced Polymers' polysulfones "P1700" and "P3500".

[0147] (F) The weight-average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 70,000 or less, more preferably 60,000 or less, and particularly preferably 50,000 or less, from the viewpoint of significantly obtaining the desired effects of the present invention.

[0148] (F) The content of thermoplastic resin is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.08% by mass or more, preferably 3% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0149] (F) The content of thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, when the total resin components in the resin composition are considered to be 100% by mass.

[0150] <(G) Curing accelerator> The resin composition may contain (G) a curing accelerator as an optional component. This curing accelerator (G) excludes components (A) to (F). Examples of curing accelerators (G) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferred, with amine-based curing accelerators and imidazole-based curing accelerators being more preferred. The curing accelerator may be used alone or in combination of two or more types.

[0151] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0152] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0153] Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-Cyanoethyl-2-methylimidazole, 1-Cyanoethyl-2-undecylimidazole, 1-Cyanoethyl-2-ethyl-4-methylimidazole, 1-Cyanoethyl-2-phenylimidazole, 1-Cyanoethyl-2-undecylimidazolium trimellitate, 1-Cyanoethyl-2-phenylimidazolium trimellitate, 2,4-Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2, 4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-F Examples include imidazole compounds such as phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

[0154] Commercial imidazole-based curing accelerators may be used, such as "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0155] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene. Examples include ro[4.4.0]deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]deca-5-ene being preferred.

[0156] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0157] (G) The content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, preferably 3% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0158] (G) The content of the curing accelerator is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, when the resin component in the resin composition is considered to be 100% by mass.

[0159] <(H)Organic filler> The resin composition may contain an optional component, (H) an organic filler. This (H) organic filler does not include any of the components (A) to (G) described above. Component (H) may be used alone or in combination of two or more types.

[0160] Component (H) exists in particulate form in the resin composition. Examples of component (H) include rubber particles, polyamide fine particles, silicone particles, and core-shell particles. In the present invention, from the viewpoint of significantly obtaining the desired effects of the present invention, it is preferable to use either rubber particles or core-shell particles, and more preferable to use core-shell particles.

[0161] Examples of rubber components included in rubber particles include olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, and ethylene-propylene-butene terpolymer; and acrylic-based thermoplastic elastomers such as propyl poly(meth)acrylate, butyl poly(meth)acrylate, cyclohexyl poly(meth)acrylate, and octyl poly(meth)acrylate. Preferably, the rubber component is an olefin-based thermoplastic elastomer, and more preferably, a styrene-butadiene copolymer. Furthermore, silicone-based rubbers such as polyorganosiloxane rubber may be mixed into the rubber component. The rubber component contained in the rubber particles has a glass transition temperature of, for example, 0°C or lower, preferably -10°C or lower, more preferably -20°C or lower, and even more preferably -30°C or lower.

[0162] Commercially available rubber particles may be used, such as "AC3401N" and "AC3816N" manufactured by Aica Kogyo Co., Ltd.

[0163] Core-shell particles are particulate organic fillers consisting of core particles containing rubber components as described above, and one or more shell layers covering them. Furthermore, it is preferable that core-shell particles are core-shell graft copolymer particles consisting of core particles containing rubber components as described above, and shell portions formed by graft copolymerization of monomer components copolymerizable with the rubber components contained in the core particles. The term "core-shell type" here does not necessarily refer only to those in which the core particles and shell portions are clearly distinguishable, but also includes those in which the boundary between the core particles and shell portions is unclear, and the core particles do not necessarily have to be completely covered by the shell portion.

[0164] The rubber component is preferably contained in the core-shell type graft copolymer particles at a concentration of 40% by mass or more, more preferably at a concentration of 50% by mass or more, and even more preferably at a concentration of 60% by mass or more. The upper limit of the rubber component content in the core-shell type graft copolymer particles is not particularly limited, but from the viewpoint of sufficiently covering the core particles with the shell portion, it is preferably, for example, 95% by mass or less, or 90% by mass.

[0165] Examples of monomer components that form the shell portion of core-shell type graft copolymer particles include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, and glycidyl (meth)acrylate; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimides; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; and (meth)acrylonitrile, with (meth)acrylic acid esters being preferred and methyl (meth)acrylate being more preferred.

[0166] Examples of commercially available core-shell type graft copolymer particles include "CHT" from Cheil Industries, Ltd.; "B602" from UMGABS, Inc.; "Paraloid EXL2602", "Paraloid EXL2603", "Paraloid EXL2655", "Paraloid EXL2311", "Paraloid EXL2313", "Paraloid EXL2315", "Paraloid KM330", "Paraloid KM336P", and "Paraloid KCZ201" from Dow Chemical Japan, "Metabren C-223A", "Metabren E-901", "Metabren S-2001", "Metabren W-450A", and "Metabren SRK-200" from Mitsubishi Rayon, Inc.; and "Kaneka M-511", "Kaneka M-600", "Kaneka M-400", "Kaneka M-580", and "Kaneka MR-01" from Kaneka Corporation. These may be used individually or in combination of two or more types.

[0167] The average particle size (average primary particle diameter) of the core-shell type graft copolymer particles is not particularly limited, but is preferably 20 nm or more, more preferably 50 nm or more, even more preferably 80 nm or more, particularly preferably 100 nm or more, preferably 5,000 nm or less, more preferably 2,000 nm or less, even more preferably 1,000 nm or less, and particularly preferably 500 nm or less. The average particle size (average primary particle diameter) of the core-shell type graft copolymer particles can be measured using a zeta potential particle size distribution analyzer or the like.

[0168] The content of component (H) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, particularly preferably 0.3% by mass or more, preferably 3% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass.

[0169] The content of component (H) is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, when the total resin components in the resin composition are considered as 100% by mass.

[0170] <(I) Other additives> The resin composition may contain, in addition to the components described above, other additives as optional components. (I) Other additives include, for example, elastomers; polymerization initiators; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion ferrants such as triazole-based adhesion ferrants, tetrazole-based adhesion ferrants, and triazine-based adhesion ferrants; and hindered phenol-based Examples include antioxidants such as antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers; photopolymerization initiators such as tertiary amines; and photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, and thioxanthones. (I) Other additives may be used individually or in combination of two or more types.

[0171] <(J) Solvent> The resin composition may contain, in addition to the non-volatile components described above, any solvent as a volatile component. (J) Any known solvent can be used as appropriate, and the type is not particularly limited, but an organic solvent is preferred. (J) Examples of solvents include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methoxypropionate. Examples include ether ester solvents such as tyl; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (J) The solvent may be used alone or in combination of two or more in any ratio.

[0172] From the viewpoint of significantly obtaining the effects of the present invention, the resin composition preferably contains 0.5% to 3% by mass of solvent (J) based on 100% by mass of all components of the resin composition. Specifically, the solvent (J) preferably contains 3% by mass or less, more preferably 2% by mass or less, even more preferably 1.5% by mass or less, preferably 0.5% by mass or more, more preferably 0.8% by mass or more, and even more preferably 1% by mass or more, based on 100% by mass of all components of the resin composition.

[0173] The method for preparing the resin composition of the present invention is not particularly limited, and examples include mixing and dispersing the constituent components using a rotary mixer or the like, with the addition of a solvent as necessary.

[0174] <Physical properties and applications of resin compositions> The cured product obtained by heat-curing the resin composition at 190°C for 90 minutes exhibits the characteristic of having a low dielectric constant. Therefore, it provides an insulating layer with a low dielectric constant. The dielectric constant is preferably 3.5 or less, more preferably 3.4 or less, and even more preferably 3.3 or less. There is no particular lower limit, but it can be 0.01 or more. The dielectric constant can be measured by the method described in the examples below. The cured product obtained by heat-curing the resin composition at 190°C for 90 minutes exhibits the characteristic of a low dielectric loss tangent. Therefore, it provides an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.003 or less, more preferably 0.0028 or less, and even more preferably 0.0025 or less. There is no particular lower limit, but it can be 0.0001 or more. The dielectric loss tangent can be measured by the method described in the examples below.

[0175] The cured product obtained by heat-curing the resin composition at 190°C for 90 minutes exhibits the characteristic of high maximum point stress. Therefore, it provides an insulating layer with high maximum point stress. The maximum point stress is preferably 100 MPa or higher, more preferably 101 MPa or higher, and even more preferably 102 MPa or higher. There is no particular upper limit, but it can be 1000 MPa or lower, etc. The maximum point stress can be measured by the method described in the examples below.

[0176] The cured product obtained by heat-curing the resin composition at 190°C for 90 minutes exhibits excellent elongation at break. Therefore, it provides an insulating layer with excellent elongation at break. The elongation at break is preferably 1% or more, more preferably 1.2% or more, even more preferably 1.5% or more, or 2% or more. There is no particular upper limit, but it can be 50% or less, 100% or less, etc. The elongation at break can be measured by the method described in the examples below.

[0177] The cured product obtained by heat-curing the resin composition at 190°C for 90 minutes exhibits excellent adhesion (peel strength) to the copper foil. Therefore, it provides an insulating layer with excellent adhesion to the copper foil. The peel strength is preferably 0.3 kgf / cm or more, more preferably 0.35 kgf / cm or more, and even more preferably 4 kgf / cm or more. There is no particular upper limit, but it can be 10 kgf / cm or less, for example. The peel strength can be measured by the method described in the examples below.

[0178] The resin composition of the present invention yields a cured product with excellent dielectric properties, high adhesion to a conductor layer, and excellent mechanical strength. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating applications. Specifically, it can be suitably used as a resin composition for forming an insulating layer (including a redistribution layer) that is formed on an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer).

[0179] Furthermore, in multilayer printed circuit boards described later, it can be suitably used as a resin composition for forming the insulating layer of a multilayer printed circuit board (resin composition for forming the insulating layer of a multilayer printed circuit board) and as a resin composition for forming the interlayer insulating layer of a printed circuit board (resin composition for forming the interlayer insulating layer of a printed circuit board).

[0180] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a redistribution-forming layer (resin composition for forming a redistribution-forming layer) as an insulating layer for forming a redistribution layer, and as a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When the semiconductor chip package is manufactured, a redistribution layer may be further formed on the sealing layer. (1) A step of laminating a temporary fixing film onto the substrate, (2) A step of temporarily fixing the semiconductor chip onto a temporary fixing film, (3) A step of forming a sealing layer on a semiconductor chip, (4) Steps to peel off the substrate and temporary fixing film from the semiconductor chip, (5) A step of forming a rewiring layer as an insulating layer on the surface from which the substrate and temporary fixing film of the semiconductor chip have been peeled off, and (6) Step of forming a redistribution layer as a conductor layer on the redistribution formation layer.

[0181] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention, provided on the support.

[0182] The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 μm or less, from the viewpoint of thinning the printed circuit board and providing a cured product with excellent insulating properties even if the cured product of the resin composition is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

[0183] Examples of support materials include films made of plastic materials, metal foils, and release paper, with films made of plastic materials and metal foils being preferred.

[0184] When using a film made of plastic material as a support, examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketones, and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0185] When using metal foil as a support, examples of metal foil include copper foil and aluminum foil, with copper foil being preferred. As for copper foil, foil made of single-metal copper may be used, or foil made of an alloy of copper with another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0186] The support may have a matte finish, corona treatment, or antistatic treatment applied to the surface that bonds with the resin composition layer.

[0187] Furthermore, as the support, a support with a release layer may be used, which has a release layer on the surface that is bonded to the resin composition layer. Examples of release agents used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. Commercially available products may be used as the support with a release layer, for example, PET films having a release layer mainly composed of an alkyd resin-based release agent, such as "SK-1", "AL-5", and "AL-7" from Lintec Corporation, "Lumirror T60" from Toray Industries, Inc., "Purex" from Teijin Corporation, and "Unipeel" from Unitika Corporation.

[0188] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When using a support with a release layer, it is preferable that the overall thickness of the support with the release layer is within the above range.

[0189] In one embodiment, the resin sheet may further include other layers as needed. Such other layers include, for example, a protective film similar to the support, provided on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, but for example, it is 1 μm to 40 μm. By laminating the protective film, the adhesion of dust and other debris and scratches to the surface of the resin composition layer can be suppressed.

[0190] A resin sheet can be manufactured, for example, by preparing a resin varnish by dissolving a resin composition in a solvent, applying this resin varnish to a support using a die coater or the like, and then drying it to form a resin composition layer. The solvent is as described above.

[0191] Drying may be carried out by known methods such as heating or blowing hot air. The drying conditions are not particularly limited, but the drying should be carried out so that the solvent content in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it also depends on the boiling point of the solvent in the resin varnish, for example, when using a resin varnish containing 30% to 60% by mass of solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0192] The resin sheet can be stored by rolling it up. If the resin sheet has a protective film, it can be used after removing the protective film.

[0193] [Printed wiring board] The printed circuit board of the present invention includes an insulating layer formed from a cured product of the resin composition of the present invention.

[0194] Printed circuit boards can be manufactured, for example, using the resin sheet described above, by a method including the following steps (I) and (II). (I) A process of laminating a resin composition layer of a resin sheet onto an inner layer substrate so that it is bonded to the inner layer substrate. (II) A process of forming an insulating layer by thermal curing the resin composition layer.

[0195] The "internal layer substrate" used in process (I) is a material that serves as the substrate for a printed wiring board, and examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. The substrate may also have a conductive layer on one or both sides, and this conductive layer may be patterned. An internal layer substrate in which a conductive layer (circuit) is formed on one or both sides of the substrate may be called an "internal layer circuit board." Furthermore, an intermediate product on which an insulating layer and / or a conductive layer is to be formed during the manufacturing of a printed wiring board is also included in the "internal layer substrate" as defined in this invention. If the printed wiring board is a circuit board with embedded components, an internal layer substrate with embedded components may be used.

[0196] Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet onto the inner layer substrate from the support side. Examples of the member used to heat and press the resin sheet onto the inner layer substrate (hereinafter also referred to as the "heat-pressing member") include a heated metal plate (such as a SUS end plate) or a metal roll (such as a SUS roll). It is preferable to press the resin sheet via an elastic material such as heat-resistant rubber, rather than directly pressing the heat-pressing member onto the resin sheet, so that the resin sheet can adequately follow the surface irregularities of the inner layer substrate.

[0197] Lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the heat-pressure temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heat-pressure pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the heat-pressure time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

[0198] Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressure laminators manufactured by Meiki Seisakusho Co., Ltd., vacuum applicators manufactured by Nikko Materials Co., Ltd., and batch-type vacuum pressure laminators.

[0199] After lamination, the laminated resin sheets may be smoothed by pressing a heat-sealing member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing process can be the same as the heat-sealing conditions for lamination. The smoothing process can be performed using a commercially available laminator. Lamination and smoothing may be performed continuously using the commercially available vacuum laminator mentioned above.

[0200] The support may be removed between steps (I) and (II), or after step (II).

[0201] In step (II), the resin composition layer is thermally cured to form an insulating layer. The thermal curing conditions for the resin composition layer are not particularly limited, and conditions commonly used when forming an insulating layer for printed circuit boards may be used.

[0202] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, but the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. The curing time can be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0203] Prior to thermal curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermal curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C or higher but less than 120°C (preferably 60°C or higher but less than 115°C, more preferably 70°C or higher but less than 110°C) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes).

[0204] In manufacturing printed circuit boards, the following steps may be further performed: (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming the conductor layer. These steps (III) through (V) may be carried out according to various methods known to those skilled in the art that are used in the manufacture of printed circuit boards. If the support is removed after step (II), the removal of the support may be carried out between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). Furthermore, if necessary, the formation of the insulating layer and the conductor layer in steps (II) through (V) may be repeated to form a multilayer circuit board.

[0205] Step (III) is a step of drilling holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be carried out using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed circuit board.

[0206] Step (IV) is a step of roughening the insulating layer. Typically, smear removal is also performed in this step (IV). The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are normally used when forming the insulating layer of a printed circuit board can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution in this order. The swelling solution used for the roughening treatment is not particularly limited, but examples include alkaline solutions and surfactant solutions, and an alkaline solution is preferred, with sodium hydroxide solution and potassium hydroxide solution being more preferred as the alkaline solution. Examples of commercially available swelling solutions include "Swelling Dip Securigant P", "Swelling Dip Securigant SBU", and "Swelling Dip Securigant P" manufactured by Atotec Japan Co., Ltd. The swelling treatment with a swelling solution is not particularly limited, but can be carried out, for example, by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes. The oxidizing agent used for the roughening treatment is not particularly limited, but examples include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigant P" manufactured by Atotec Japan. Furthermore, an acidic aqueous solution is preferred as the neutralizing solution used for roughening treatment; an example of a commercially available product is "Reduction Solution Securigant P" manufactured by Atotec Japan. The treatment with the neutralizing solution can be carried out by immersing the treated surface, which has undergone roughening treatment with the oxidizing agent, in a neutralizing solution at 30°C to 80°C for 1 to 30 minutes.From the standpoint of workability and other factors, a preferred method is to immerse the object that has been roughened with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0207] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. The lower limit is not particularly limited, but is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The arithmetic mean roughness (Ra) of the insulating layer surface can be measured using a non-contact surface roughness meter.

[0208] Step (V) is a step of forming a conductive layer, in which a conductive layer is formed on an insulating layer. The conductive material used for the conductive layer is not particularly limited. In a preferred embodiment, the conductive layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductive layer may be a single-metal layer or an alloy layer, and examples of alloy layers include layers formed from alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). In particular, from the viewpoint of versatility in conductor layer formation, cost, and ease of patterning, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy are preferred, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy are more preferred, and single metal layers of copper are even more preferred.

[0209] The conductive layer may be a single-layer structure, or it may be a multi-layer structure in which two or more single-metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductive layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0210] The thickness of the conductor layer depends on the desired printed circuit board design, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0211] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using conventionally known techniques such as the semi-additive method or the fully additive method. From the viewpoint of ease of manufacture, it is preferable to form it by the semi-additive method. An example of forming the conductor layer by the semi-additive method is shown below.

[0212] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer corresponding to the desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. Subsequently, the unnecessary plating seed layer can be removed by etching or other means to form a conductor layer having the desired wiring pattern.

[0213] [Semiconductor device] The semiconductor device of the present invention includes the printed circuit board of the present invention. The semiconductor device of the present invention can be manufactured using the printed circuit board of the present invention.

[0214] Examples of semiconductor devices include various types of semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft).

[0215] The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) on conductive locations on a printed circuit board. A "conductive location" is a "location on the printed circuit board that transmits electrical signals," and this location may be on the surface or embedded. Furthermore, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of semiconductor material.

[0216] The method of mounting semiconductor chips when manufacturing semiconductor devices is not particularly limited as long as the semiconductor chip functions effectively, but specific examples include wire bonding mounting methods, flip-chip mounting methods, bumpless build-up layer (BBUL) mounting methods, anisotropic conductive film (ACF) mounting methods, and non-conductive film (NCF) mounting methods. Here, "bumpless build-up layer (BBUL) mounting method" refers to "a mounting method in which the semiconductor chip is directly embedded in the recesses of the printed circuit board and the semiconductor chip is connected to the wiring on the printed circuit board." [Examples]

[0217] The present invention will be described in detail below with reference to examples. The present invention is not limited to these examples. In the following, unless otherwise specified, "parts" and "%" refer to "parts by mass" and "% by mass," respectively.

[0218] <Synthesis Example 1: Synthesis of PPE-1> A 1.5-liter jacketed reactor, equipped with a sparger for introducing oxygen-containing gas at the bottom, stirring turbine blades and baffles, and a reflux condenser in the vent gas line at the top of the reactor, was filled with a pre-prepared mixture of 0.1026 g of cuprous oxide and 0.7712 g of 47% hydrogen bromide, along with 0.2471 g of N,N'-di-t-butylethylenediamine, 3.6407 g of dimethyl-n-butylamine, 1.1962 g of di-n-butylamine, 894.04 g of toluene, 73.72 g of 2,6-dimethylphenol, and 26.28 g of 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane (ADEKA: AO-30). Air was then introduced into the reactor through the sparger at a rate of 1.05 L / min while vigorously stirring, and the polymerization temperature was maintained at 40°C by passing a heat transfer medium through the jacket. 160 minutes after introducing air, the air supply was stopped, and 1.1021 g of tetrasodium ethylenediaminetetraacetate tetrahydrate (reagent manufactured by Dojin Chemical Laboratories) was added to the polymerization mixture as an aqueous solution in 100 g of solution, and the mixture was heated to 70°C. After maintaining the temperature at 70°C for 2 hours to perform catalyst extraction and removal of the by-product diphenoquinone, the mixture was transferred to a Sharpless centrifuge and separated into a polyphenylene ether composition solution (organic phase) and an aqueous phase to which the catalyst metal had been transferred. The obtained polyphenylene ether composition solution was transferred to a jacketed concentrator, and the solution was concentrated by distilling off toluene until the solid content in the polyphenylene ether composition solution was 55% by mass. Next, toluene was further distilled off using an oil bath set to 230°C and a rotary evaporator, and the solid content was dried to obtain the polyphenylene ether composition.

[0219] <Synthesis Example 2: Synthesis of PPE-2> A stirring bar was placed in a three-necked flask, and a Liebig condenser with a three-way stopcock attached to the main tube was mounted. A rubber stopper with a thermometer inserted was attached to one of the side tubes. 20 g of the unmodified polyphenylene ether composition obtained in Synthesis Example 1 was added through the other side tube, and the rubber stopper was attached. After purging the inside of the flask with nitrogen, the mixture was stirred with a magnetic stirrer and dissolved in 140 g of toluene using a syringe, followed by the addition of 6.32 g of triethylamine. Then, 3.27 g of methacryloyl chloride was taken in a syringe and added dropwise to the system through the rubber stopper. After the addition was complete, stirring was continued at room temperature for 3 hours, and then the flask was heated in an oil bath and the reaction was continued under reflux. Heating was stopped 2 hours after the start of reflux, and after returning to room temperature, 1.00 g of methanol was added to stop the reaction. The reaction solution was then concentrated to a solid content of 20% by weight, and then washed with an equal weight of deionized water. Subsequently, the water tank was removed, and the organic layer was added dropwise to methanol (5 times the weight of the organic layer) with stirring. The precipitate was then filtered, and the filtrate was vacuum-dried at 110°C for 1 hour to obtain a modified polyphenylene ether composition.

[0220] <Synthesis Example 3: Synthesis of PPE-3> A 1.5-liter jacketed reactor, equipped with a sparger for introducing oxygen-containing gas at the bottom, stirring turbine blades and baffles, and a reflux condenser in the vent gas line at the top of the reactor, was filled with a pre-prepared mixture of 0.1026 g of cuprous oxide and 0.7712 g of 47% hydrogen bromide, along with 0.2471 g of N,N'-di-t-butylethylenediamine, 3.6407 g of dimethyl-n-butylamine, 1.1962 g of di-n-butylamine, 894.04 g of toluene, 73.72 g of 2,6-dimethylphenol, and 39.69 g of pentaerythritol=tetrakis[3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate] (ADEKA: AO-60). Next, while vigorously stirring, air was introduced into the reactor from a sparger at a rate of 1.05 L / min, and at the same time, the polymerization temperature was adjusted by passing a heat transfer medium through the jacket to maintain a temperature of 40°C. 160 minutes after the introduction of air, the air supply was stopped, and 1.1021 g of ethylenediaminetetraacetate tetrasodium salt tetrahydrate (reagent manufactured by Dojin Chemical Laboratories) was added to the polymerization mixture as an aqueous solution in a volume of 100 g, and the mixture was heated to 70°C. After maintaining the temperature at 70°C for 2 hours to perform catalyst extraction and removal of the by-product diphenoquinone, the mixture was transferred to a Sharpless centrifuge and separated into a polyphenylene ether composition solution (organic phase) and an aqueous phase to which the catalyst metal had been transferred. The obtained polyphenylene ether composition solution was transferred to a jacketed concentrator, and the solution was concentrated by distilling off toluene until the solid content in the polyphenylene ether composition solution was 55% by mass. Next, toluene was further removed using an oil bath set to 230°C and a rotary evaporator, and the solid components were dried to obtain a polyphenylene ether composition.

[0221] <Measurement of number-average molecular weight (Mn)> A Showa Denko Gel Permeation Chromatography System 21 was used as the measuring instrument. Calibration curves were created using standard polystyrene and ethylbenzene, and the number-average molecular weight (Mn) of the obtained PPE-1, PPE-2, and PPE-3 was measured using these calibration curves. The standard polystyrenes used had molecular weights of 3,650,000, 2,170,000, 1,090,000, 681,000, 204,000, 52,000, 30,200, 13,800, 3,360, 1,300, and 550. Two Showa Denko K-805L columns connected in series were used. Chloroform was used as the solvent, with a solvent flow rate of 1.0 mL / min and a column temperature of 40°C. A 1 g / L chloroform solution of PPE-1 synthesized in Synthesis Example 1 was prepared and used as the measurement sample. The UV wavelength of the detection unit was set to 254 nm for standard polystyrene and 283 nm for polyphenylene ether.

[0222] <Measurement of glass transition temperature (Tg)> The glass transition temperatures of PPE-1, PPE-2, and PPE-3 were measured using a differential scanning calorimeter (DSC, PerkinElmer-Pyrisl). The samples were heated from room temperature to 200°C in a nitrogen atmosphere at a rate of 20°C / min, then cooled to 50°C at 20°C / min. The glass transition temperature was then measured again at a rate of 20°C / min.

[0223] <Measurement of the number of terminal hydroxyl groups contained in resin> 5.0 mg each of PPE-1 and PPE-3 were weighed out. The weighed PPE-1 was then dissolved in 25 mL of methylene chloride. To 2.0 mL of the prepared solution, 150 μL of ethanol solution of 2% by mass tetraethylammonium hydroxide (TEAH) was added, and the absorbance (Abs) at 318 nm was measured using a UV spectrophotometer (Hitachi, Ltd.: U-3210 model) (using a 1 cm cell length absorbance measurement cell). Based on the measurement results, the pseudomolecular weight obtained from the absorbance was calculated using the following formula (1). Formula (1): The pseudomolecular weight (g / mol) obtained from absorbance = [((ε×5) / (25×Abs)] In formula (1), ε represents the absorption coefficient and is 4700 L / mol·cm. Also, by multiplying the reciprocal of the above pseudo molecular weight by 106, the number of OH terminals per gram (μmol / g) of PPE-1 or PPE-3 was calculated.

[0224] <Measurement of the number of terminal methacrylic groups contained in the resin> A specified amount of PPE-2 synthesized in Synthesis Example 2 and 1,3,5-trimethoxybenzene standard (manufactured by FUJIFILM Wako Pure Chemical Corporation, molecular weight 168.19) as an internal standard sample were taken, dissolved in heavy chloroform containing trimethylsilane, 1 and 1H-NMR measurement (JEOL 500 MHz) was performed.

[0225] Next, the integral value of the peak of the protons derived from the methoxy group of 1,3,5-trimethoxybenzene (3.7 - 3.8 ppm: 9H), and the integral value of the peak that appears on the high magnetic field side among the protons at the C=C bond terminal of the methacrylic group (5.5 - 5.9 ppm: 1H) were determined. From these integral values and the weights of the polyphenylene ether composition and 1,3,5-trimethoxybenzene used in the measurement, the number of methacrylic groups per gram (unit: μmol / g) of the modified polyphenylene ether composition was calculated.

[0226] Regarding S202A and OPE-2St used in the comparative examples, the number average molecular weight and the number of terminal functional groups were measured in the same manner as for PPE-1.

[0227]

Table 1

[0228] <Synthesis Example 4: Synthesis of maleimide A> A MEK solution of maleimide compound A (non-volatile component 62% by mass, t’’ = 1.47 (mainly 1, 2 or 3), Mw / Mn = 1.81) synthesized by the method described in Synthesis Example 1 of JP-A 2020-500211 was prepared. This maleimide compound A has a structure represented by the following formula.

Chemical formula

[0229] <Synthesis Example 5: Synthesis of Polyimide B> A 500 mL separable flask equipped with a water content measuring receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane were added to this flask, and the mixture was stirred at 45 °C for 2 hours under a nitrogen stream to carry out the reaction. Next, the temperature of this reaction solution was raised, and while maintaining it at about 160 °C, the condensed water was removed by azeotropic distillation together with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the water content measuring receiver and that the outflow of water was no longer observed. After confirmation, the temperature of the reaction solution was further raised, and it was stirred at 200 °C for 1 hour. Then, it was cooled to obtain a polyimide solution (non-volatile content: 20% by mass) containing a polyimide resin having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin had a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). Also, the weight average molecular weight of the above polyimide resin was 12,000. [Chemical formula]

[0230] <Production of Resin Varnish> Each component was weighed in the number of parts by mass shown in the table, and further 10 parts of MEK and 10 parts of cyclohexanone were mixed and uniformly dispersed using a high-speed rotary mixer to obtain a resin varnish. The details of each component shown in the table are as follows.

[0231] [Table 2]

[0232] (Component (A)) ·PPE-1: Poly(phenylene ether) resin synthesized in Synthesis Example 1 ·PPE-2: Polyphenylene ether resin synthesized in Synthesis Example 2 ·PPE-3: Polyphenylene ether resin synthesized in Synthesis Example 3 (Component (B)) ·HP-4032-SS: Naphthalene-type epoxy resin (functional group equivalent: 144 g / eq., manufactured by DIC Corporation) ·NC-3000-L: Biphenyl-type epoxy resin (functional group equivalent: 269 g / eq., manufactured by Nippon Kayaku Co., Ltd.) ·ZX-1059: 1:1 mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin (functional group equivalent: 169 g / eq., manufactured by Nippon Steel Chemical & Material Co., Ltd.) ·ESN-475V: Naphthalene-type epoxy resin (functional group equivalent: 332 g / eq., manufactured by Nippon Steel Chemical & Material Co., Ltd.) (Component (C)) ·HPC-8150-62T: Active ester-based curing agent (active ester resin having a naphthalene structure, functional group equivalent: 223 g / eq., manufactured by DIC Corporation) ·HPC-8000L-65MT: Active ester resin containing a dicyclopentadiene-type diphenol structure, functional group equivalent: 229 g / eq., manufactured by DIC Corporation ·PC1300-02-65MA: Active ester resin having a naphthalene structure, functional group equivalent: 199 g / eq., manufactured by Air Water Inc. ·LA-3018-50P: 1-methoxy-2-propanol solution with a functional group equivalent of 151 g / eq. and a non-volatile content of 50% by mass, manufactured by DIC Corporation ·V03: Toluene solution with a functional group equivalent of 216 g / eq. and a non-volatile content of 50% by mass, manufactured by Nisshinbo Chemical Inc. ·BA230S75: Prepolymer of bisphenol A dicyanate, functional group equivalent: 232 g / eq., manufactured by Lonza Japan Ltd. (Component (D)) ·SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd. "KBM573"), average particle size 0.5 μm, specific surface area 5.8 m 2 / g, manufactured by Admatechs Co., Ltd. • UFP-30: Spherical silica surface-treated with an amine-based alkoxysilane compound (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.), with an average particle size of 0.3 μm and a specific surface area of ​​30.7 m². 2 / g, manufactured by Denka Co., Ltd. (E) Component • Maleimide A: Synthesized in Synthesis Example 4, a maleimide-based radical polymerizable compound. • ODV-XET-X04: Styrene-based radical polymerizable compound, manufactured by Nippon Steel Chemical & Material Co., Ltd. (F) component • YX7553BH30: Phenoxy resin, a 1:1 solution of MEK and cyclohexanone with 30% by mass of non-volatile content, manufactured by Mitsubishi Chemical Corporation. • Polyimide B: Synthesized in Synthesis Example 5 (G) Component • 1B2PZ: Imidazole-based reaction accelerator, manufactured by Shikoku Chemicals Co., Ltd. • DMAP: Amine-based curing accelerator, manufactured by Tokyo Chemical Industry Co., Ltd. • Co(III): Metal-based hardening accelerator, manufactured by Tokyo Chemical Industry Co., Ltd. (H) Component • EXL2655: Core-shell graft copolymer rubber particles, manufactured by Dow Chemical. catalyst (I) component • S202A: Modified polyphenylene ether, number average molecular weight 16,000, manufactured by Asahi Kasei Corporation, number of terminal functional groups: 2 OPE-2St: Vinyl benzyl-modified polyphenylene ether, number average molecular weight 1200, manufactured by Mitsubishi Gas Chemical Co., Ltd., number of terminal functional groups: 2

[0233] <Measurement of dielectric constant, dielectric loss tangent, and mechanical strength> (1) Preparation of resin sheet A with a resin composition layer thickness of 40 μm A polyethylene terephthalate film (Lintec Corporation's "AL5", 38 μm thick) with a release layer was prepared as a support. The resin varnish obtained in the examples and comparative examples was uniformly applied to the release layer of this support so that the thickness of the resin composition layer after drying was 40 μm. The resin composition was then dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain a resin sheet A including the support and the resin composition layer.

[0234] (2) Preparation of the cured product of the resin composition layer The resin sheet A obtained in the examples and comparative examples was cured in an oven at 190 °C for 90 minutes. By peeling off the support from the resin sheet A taken out of the oven, a cured product of the resin composition layer was obtained.

[0235] (3) Measurement of dielectric constant and dielectric loss tangent (dielectric properties) The cured product was cut into pieces with a length of 80 mm and a width of 2 mm, and using "HP8362B" manufactured by Agilent Technologies, the values of dielectric constant and dielectric loss tangent (Dk value and Df value) were measured at a measurement frequency of 5.8 GHz, measurement temperatures of 23 °C and 90 °C by the cavity resonance perturbation method. The measurement was carried out on two test pieces, and the average value was calculated.

[0236] (4) Measurement of maximum point stress and elongation at break (mechanical strength) The cured product was subjected to a tensile strength measurement using a tensile testing machine "RTC-1250A" manufactured by Orientec, and the maximum point stress and elongation at break at 23 °C were measured. The measurement was carried out in accordance with JIS K7127. The measurement was carried out 5 times, and the average value of the top 3 points was calculated.

[0237] <Evaluation of Adhesion>[[]] (1) Substrate treatment of copper foil The shiny surface of an electrolytic copper foil ("3EC-III" manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 35 μm) was etched by 1 μm with a micro-etching agent ("CZ8101" manufactured by Meck) for roughening the copper surface, and then a rust prevention treatment (CL8300) was applied. The copper foil whose surface was etched with the above micro-etching agent is sometimes referred to as "CZ copper foil" hereinafter. Further, this copper foil was heat-treated in an oven at 130 °C for 30 minutes to obtain copper foil I having a roughened treatment surface.

[0238] (2) Preparation of inner layer substrate A glass cloth substrate epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") was prepared, with copper foil on the surface and an inner layer circuit formed on it. Both sides of this glass cloth substrate epoxy resin double-sided copper-clad laminate were etched to a thickness of 1 μm with a micro-etching agent (MEC "CZ8101") to roughen the surface of the copper foil. As a result, an inner layer substrate having a CZ copper foil with a treated surface was obtained.

[0239] (3) Lamination of resin composition layers The resin sheets prepared in the examples and comparative examples were laminated to both sides of the inner layer substrate. This lamination was performed using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700") so that the resin composition layer was in contact with the inner layer substrate. The lamination was carried out by reducing the pressure to 13 hPa or less by depressurizing for 30 seconds, and then pressing at 120°C and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheet was heat-pressed at 100°C and a pressure of 0.5 MPa for 60 seconds. After that, the support was peeled off to expose the resin composition layer.

[0240] (4) Lamination of copper foil and curing of resin composition layer: The treated surface of the copper foil I was laminated onto the exposed resin composition layer under the same conditions as described in "(3) Lamination of the resin composition layer". The resin composition layer was then cured at 200°C for 90 minutes to form an insulating layer containing the cured resin composition. Through the above operations, an evaluation substrate C was obtained in which CZ copper foil was laminated on both sides of the insulating layer. This evaluation substrate C had a layer structure of copper foil I / insulating layer / inner layer substrate / insulating layer / copper foil I.

[0241] <Measurement of adhesion (peel strength) between the copper foil and the surrounding material> The evaluation substrate C was cut into small pieces measuring 150 mm x 30 mm. A cut was made in the copper foil I of each piece using a cutter, enclosing a section 10 mm wide and 100 mm long. One end of this section was peeled off and grasped with the grips of a tensile testing machine (Autocom universal testing machine "AC-50C-SL" manufactured by TSE Corporation). At room temperature (25°C), the copper foil peel strength was measured by pulling it vertically at a speed of 50 mm / min and removing 35 mm of the foil. The measurement was performed in accordance with the Japanese Industrial Standard JIS C6481. In Comparative Example 3, blistering occurred between the copper foil and the insulating layer, making it impossible to measure the peel strength.

[0242] [Table 3]

[0243] In Examples 1 to 6, it was confirmed that even when components (E) to (H) were not included, the results were similar to those of the above examples, albeit to varying degrees.

Claims

1. (A) Polyphenylene ether resins with more than 2 terminal functional groups, (B) Epoxy resin, (C) Hardener, and (D) A resin composition containing an inorganic filler, Component (A) has a structure represented by the following formula (A-1), (A) The content of component is 30000 / 3404% by mass or less, when the nonvolatile components in the resin composition are considered to be 100% by mass. The content of component (D) is 100,000 / 1679% by mass or more, when the non-volatile components in the resin composition are considered to be 100% by mass. (C) A resin composition containing an active ester-based curing agent. 【Chemistry 1】 In formula (A-1), X represents an a-valent linking group, Z independently represents a hydrogen atom or a group represented by formula (A-3), R 11 independently represents a hydrogen atom or a group represented by formula (A-2), R 21 and R 23 independently represent a hydrogen atom, a substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or a halogen atom, and R 22 and R 24 independently represent a hydrogen atom, a substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a group represented by formula (A-2), or a halogen atom. However, this excludes cases where R 22 and R 24 represent hydrogen atoms, and cases where one of R 22 and R 24 is a group represented by formula (A-2) and the other represents a hydrogen atom, a methyl group, or an ethyl group. a and b each independently represent integers from 2 to 6, k each independently represent integers from 1 to 4, and n each independently represent integers from 0 to 200. 【Chemistry 2】 In formula (A-2), R 31 and R 34 each independently represent an alkylene group having 1 to 8 carbon atoms, R 32 and R 33 each independently represent an alkyl group having 1 to 8 carbon atoms, and R 35 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group. * represents a bond. d and e each independently represent 0 or 1. 【Transformation 3】 In formula (A-3), R 41 independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms, and R 42, R 43, and R 44 independently represent a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylamino group, or a hydroxyalkyl group having 1 to 30 carbon atoms. s represents an integer from 0 to 5. * represents a bond.

2. (A) A polyphenylene ether resin having more than 2 terminal functional groups, (B) Epoxy resin, (C) Hardener, and (D) A resin composition containing an inorganic filler, Component (A) has a structure represented by the following formula (A-1), (A) The content of component is 10% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass. The content of component (D) is 65% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass. (B) The content of component is 15% by mass or less, when the non-volatile components in the resin composition are taken as 100% by mass. (C) A resin composition containing an active ester-based curing agent. 【Chemistry 4】 In formula (A-1), X represents an a-valent linking group, Z independently represents a hydrogen atom or a group represented by formula (A-3), R 11 independently represents a hydrogen atom or a group represented by formula (A-2), R 21 and R 23 independently represent a hydrogen atom, a substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or a halogen atom, and R 22 and R 24 independently represent a hydrogen atom, a substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a group represented by formula (A-2), or a halogen atom. However, this excludes cases where R 22 and R 24 represent hydrogen atoms, and cases where one of R 22 and R 24 is a group represented by formula (A-2) and the other represents a hydrogen atom, a methyl group, or an ethyl group. a and b each independently represent integers from 2 to 6, k each independently represent integers from 1 to 4, and n each independently represent integers from 0 to 200. 【Transformation 5】 In formula (A-2), R 31 and R 34 each independently represent an alkylene group having 1 to 8 carbon atoms, R 32 and R 33 each independently represent an alkyl group having 1 to 8 carbon atoms, and R 35 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group. * represents a bond. d and e each independently represent 0 or 1. 【Transformation 6】 In formula (A-3), R 41 independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms, and R 42, R 43, and R 44 independently represent a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylamino group, or a hydroxyalkyl group having 1 to 30 carbon atoms. s represents an integer from 0 to 5. * represents a bond.

3. (A) A polyphenylene ether resin having more than 2 terminal functional groups, (B) Epoxy resin, (C) Hardener, and (D) A resin composition containing an inorganic filler, Component (A) has a structure represented by the following formula (A-1), (A) The content of component is 10000 / 2424% by mass or less, when the nonvolatile components in the resin composition are taken as 100% by mass. (C) A resin composition containing an active ester-based curing agent. 【Transformation 7】 In formula (A-1), X represents an a-valent linking group, Z independently represents a hydrogen atom or a group represented by formula (A-3), R 11 independently represents a hydrogen atom or a group represented by formula (A-2), R 21 and R 23 independently represent a hydrogen atom, a substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or a halogen atom, and R 22 and R 24 independently represent a hydrogen atom, a substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a group represented by formula (A-2), or a halogen atom. However, this excludes cases where R 22 and R 24 represent hydrogen atoms, and cases where one of R 22 and R 24 is a group represented by formula (A-2) and the other represents a hydrogen atom, a methyl group, or an ethyl group. a and b each independently represent integers from 2 to 6, k each independently represent integers from 1 to 4, and n each independently represent integers from 0 to 200. 【Transformation 8】 In formula (A-2), R 31 and R 34 each independently represent an alkylene group having 1 to 8 carbon atoms, R 32 and R 33 each independently represent an alkyl group having 1 to 8 carbon atoms, and R 35 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group. * represents a bond. d and e each independently represent 0 or 1. 【Chemistry 9】 In formula (A-3), R 41 independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms, and R 42, R 43, and R 44 independently represent a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylamino group, or a hydroxyalkyl group having 1 to 30 carbon atoms. s represents an integer from 0 to 5. * represents a bond.

4. (A) A polyphenylene ether resin having more than 2 terminal functional groups, (B) Epoxy resin, (C) Hardener, and (D) A resin composition containing an inorganic filler. (A) The number-average molecular weight of component is 1600 or less. The content of component (D) is 55% by mass or more, when the nonvolatile components in the resin composition are taken as 100% by mass. Component (A) has a structure represented by the following formula (A-1), (C) A resin composition containing an active ester-based curing agent. 【Chemistry 10】 In formula (A-1), X represents an a-valent linking group, Z independently represents a hydrogen atom or a group represented by formula (A-3), R 11 independently represents a hydrogen atom or a group represented by formula (A-2), R 21 and R 23 independently represent a hydrogen atom, a substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, or a halogen atom, and R 22 and R 24 independently represent a hydrogen atom, a substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, a group represented by formula (A-2), or a halogen atom. However, this excludes cases where R 22 and R 24 represent hydrogen atoms, and cases where one of R 22 and R 24 is a group represented by formula (A-2) and the other represents a hydrogen atom, a methyl group, or an ethyl group. a and b each independently represent integers from 2 to 6, k each independently represent integers from 1 to 4, and n each independently represent integers from 0 to 200. 【Chemistry 11】 In formula (A-2), R 31 and R 34 each independently represent an alkylene group having 1 to 8 carbon atoms, R 32 and R 33 each independently represent an alkyl group having 1 to 8 carbon atoms, and R 35 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group. * represents a bond. d and e each independently represent 0 or 1. 【Chemistry 12】 In formula (A-3), R 41 independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms, and R 42, R 43, and R 44 independently represent a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylamino group, or a hydroxyalkyl group having 1 to 30 carbon atoms. s represents an integer from 0 to 5. * represents a bond.

5. The resin composition according to any one of claims 1 to 4, wherein component (C) contains a phenolic curing agent.

6. Furthermore, the resin composition according to any one of claims 1 to 4, further comprising (E) a radical polymerizable compound.

7. The resin composition according to claim 6, wherein component (E) contains a maleimide-based radical polymerizable compound.

8. A resin sheet comprising a support and a resin composition layer provided on the support, the layer comprising the resin composition according to any one of claims 1 to 4.

9. A printed circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 4.

10. A semiconductor device comprising a printed circuit board as described in claim 9.

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