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] The present invention relates to a resin composition. The present invention further relates to a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition. [Background technology]

[0002] 2. Description of the Related Art A known manufacturing technique for printed wiring boards is a build-up method in which insulating layers and conductor layers are alternately stacked.

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

[0004] [Patent Document 1] Patent Publication No. 2022-60800 [Patent Document 2] JP 2013-181132 A Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, with the increasing functionality of printed wiring boards, there is a demand for further improvements in the dielectric tangent and dielectric constant of the insulating layer, as well as further improvements in adhesion to plating. In addition, in order to increase the mechanical strength of printed wiring boards, there is a demand for further improvements in the maximum stress and breaking elongation of the insulating layer. Hereinafter, the dielectric tangent and dielectric constant may be collectively referred to as the dielectric properties, and the maximum stress and breaking elongation may be collectively referred to as the mechanical strength.

[0006] The present invention has been devised in view of the above problems, and aims to provide a resin composition which is capable of giving a cured product having low dielectric properties, high adhesion (peel strength) with a conductor layer, and excellent mechanical strength; a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device which have an insulating layer formed using the resin composition. [Means for solving the problem]

[0007] As a result of intensive research into the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by incorporating in combination (A) a polyphenylene ether resin having more than two terminal functional groups, (B) an epoxy resin, (C) a curing agent, and (D) an inorganic filler, and have thus completed the present invention.

[0008] That is, the present invention includes the following. [1] (A) a polyphenylene ether resin having more than two terminal functional groups; (B) epoxy resin, (C) a curing agent, and (D) A resin composition containing an inorganic filler. [2] The resin composition according to [1], wherein the component (A) has a structure represented by the following formula (A-1): [ka] In formula (A-1), X represents a linking group having a valence of a, each Z independently represents a hydrogen atom or a group represented by formula (A-3), R 11 each independently represents a hydrogen atom or a group represented by formula (A-2), R 21 , and R 23 each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or a halogen atom; R 22 , and R 24 each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, a group represented by formula (A-2), or a halogen atom. 22 , and R 24When represents a hydrogen atom, and R 22 and R 24 wherein one of the groups 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 of 2 to 6, k each independently represent an integer of 1 to 4, and n each independently represent an integer of 0 to 200. [ka] In formula (A-2), R 31 , and R 34 each independently represents an alkylene group having 1 to 8 carbon atoms; R 32 , and R 33 each independently represents an alkyl group having 1 to 8 carbon atoms; 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 41 each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms; R 42 , R 43 , and R 44 each independently represents a hydrogen atom, a hydroxy 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 of 0 to 5. * represents a bond. [3] The resin composition according to [1] or [2], wherein the component (C) contains an active ester-based curing agent. [4] The resin composition according to any one of [1] to [3], wherein the component (C) contains a phenol-based curing agent. [5] The resin composition according to any one of [1] to [4], further comprising (E) a radically polymerizable compound. [6] The resin composition according to [5], wherein the component (E) contains a maleimide-based radically polymerizable compound. [7] A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of [1] to [6]. [8] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [6]. [9] A semiconductor device comprising the printed wiring board according to [8]. Effect of the Invention

[0009] According to the present invention, it is possible to provide a resin composition which can give a cured product having low dielectric properties, high adhesion (peel strength) with a conductor layer, and excellent mechanical strength, as well as a resin sheet, a printed wiring board, and a semiconductor device which use the resin composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0011] [Resin composition] The resin composition of the present invention contains (A) a polyphenylene ether resin having more than two terminal functional groups, (B) an epoxy resin, (C) a curing agent, and (D) an inorganic filler. In the present invention, by containing a combination of the (A), (B), (C), and (D) components, it is possible to obtain a cured product that has a low dielectric tangent, high adhesion to a conductor layer, and excellent mechanical strength.

[0012] The resin composition of the present invention may further contain optional components in combination with the components (A) to (D). Examples of the optional components include a radical polymerizable compound (E), a thermoplastic resin (F), a curing accelerator (G), an organic filler (H), other additives (I), and a solvent (J). Each component contained in the resin composition of the present invention will be described in detail below.

[0013] <(A) Polyphenylene ether resin with more than two terminal functional groups> The resin composition contains, as component (A), a polyphenylene ether resin having more than 2 terminal functional groups. By including component (A) in the resin composition, it is possible to obtain a cured product having excellent dielectric properties, high adhesion to the conductor layer, and excellent mechanical strength. The component (A) may be used alone or in combination of two or more types.

[0014] The component (A) may be a resin having a polyphenylene ether skeleton with more than two terminal functional groups. The polyphenylene ether skeleton refers to a skeleton having a repeating unit represented by the following formula (a), or a repeating unit in which the hydrogen atom in the phenylene group of formula (a) is replaced with a substituent or the like. In the formula, * represents a bond. [ka]

[0015] The number of terminal functional groups in component (A) is more 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 having a number of terminal functional groups in this range, it is possible to obtain a cured product having excellent dielectric properties, high adhesion to the conductor layer, and excellent mechanical strength. The number of terminal functional groups is a numerical value representing the average number of functional groups present at the end of one molecule of component (A). The method for measuring the terminal functional group varies depending on the type of functional group. For example, when the terminal functional group is a hydroxyl group, it can be obtained 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. When the terminal functional group is other than a hydroxyl group, component (A) and a standard sample such as 1,3,5-trimethoxybenzene are dissolved in a heavy solvent, and the absorbance can be measured. 1 Measure H-NMR. 1The number of terminal functional groups can be determined by H-NMR from the integral value of the peak derived from the terminal functional group, the integral value of the peak derived from the functional group of the standard sample, the mass of the component (A), and the mass of the standard sample. For details, the number of terminal functional groups can be determined by the method described in the examples below.

[0016] From the viewpoint of obtaining the effects of the present invention significantly, the number of terminal functional groups per 1 g of component (A) is preferably 100 μmol / g or more, more preferably 500 μmol / g or more, and even more preferably 1000 μmol / g or more, and is preferably 5000 μmol / g or less, more preferably 3000 μmol / g or less, and even more preferably 2000 μmol / g or less. The number of terminal functional groups per 1 g of component (A) can be measured by the method described in the Examples below.

[0017] Examples of the functional group at the end of the component (A) include a hydroxy group, an acryloyl group, a methacryloyl group, a styryl group, etc. Of these, from the viewpoint of obtaining the effects of the present invention significantly, the functional group is preferably either a hydroxy group or a methacryloyl group, and a hydroxy group is more preferable.

[0018] From the viewpoint of obtaining the effects of the present invention significantly, the number average molecular weight of the component (A) is 100 or more, more preferably 500 or more, and even more preferably 1000 or more, and is preferably 5000 or less, more preferably 3000 or less, and even more preferably 2000 or less. 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 described later.

[0019] From the viewpoint of significantly obtaining the effects of the present invention, the glass transition temperature (Tg) of the 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 is preferably 300° C. or lower, more preferably 250° C. or lower, even more preferably 200° C. or lower, or 190° C. or lower. The glass transition temperature (Tg) can be measured by the method described in the examples below.

[0020] The component (A) preferably has a structure represented by the following formula (A-1). [ka] In formula (A-1), X represents a linking group having a valence of a, each Z independently represents a hydrogen atom or a group represented by formula (A-3), R 11 each independently represents a hydrogen atom or a group represented by formula (A-2), R 21 , and R 23 each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or a halogen atom; R 22 , and R 24 each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, a group represented by formula (A-2), or a halogen atom. 22 , and R 24 represents a hydrogen atom, and R 22 and R 24 wherein one of the groups 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 of 2 to 6, k each independently represent an integer of 1 to 4, and n each independently represent an integer of 0 to 200. [ka] In formula (A-2), R 31 , and R 34 each independently represents an alkylene group having 1 to 8 carbon atoms; R 32 , and R 33 each independently represents an alkyl group having 1 to 8 carbon atoms; 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 independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms; R 42 , R 43 , and R 44 each independently represents a hydrogen atom, a hydroxy 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 of 0 to 5. * represents a bond.

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

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

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

[0024] Examples of the a-valent hydrocarbon group include an a-valent aliphatic hydrocarbon group, an a-valent aromatic hydrocarbon group, and a group consisting of a combination thereof, and an a-valent aliphatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and a saturated aliphatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be a chain-like hydrocarbon group, a cyclic hydrocarbon group (i.e., an alicyclic hydrocarbon group), or a combination thereof. Furthermore, the chain-like hydrocarbon group may be either a straight-chain or a branched one, and a branched one is preferred. The a-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 represented by 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] The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). Unless otherwise specified, the same substituents as the above-mentioned substituents may be used as the secondary substituents.

[0029] Examples of the a-valent group formed by a combination of an ester bond and a hydrocarbon group include an a-valent group formed by a combination of an ester bond and an alkylene group, an a-valent group formed by a combination of an ester bond and an arylene group, an a-valent group formed by a combination of an ester bond, an alkylene group, and an a-valent hydrocarbon group, and an a-valent group formed by a combination of an ester bond, an arylene group, and an a-valent hydrocarbon group, and an a-valent group formed by a combination of an ester bond, an alkylene group, and an a-valent hydrocarbon group are preferred.

[0030] The alkylene group is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a 1,2-propylene group, a tetramethylene group, a 2-methyl-1,3-trimethylene group, a 1,1-dimethylethylene group, a pentamethylene group, a 1-ethyl-1,3-propylene group, a 1-methyl-1,4-butylene group, a 2-methyl-1,4-butylene group, a 3-methyl-1,4-butylene group, a 2,2-dimethyl-1,3-propylene group, a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a 2,2-dimethyl-1,3-propylene group, a dimethyl-1,3-propylene, 3,3-dimethyl-1,3-propylene, hexamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-ethyl-1,4-butylene, 2-ethyl-1,4-butylene, 3-ethyl-1,4-butylene, 1-methyl-1,5-pentylene, 2-methyl-1,5-pentylene, 3-methyl-1,5-pentylene, 4-methylpentylene, 1,1-dimethyl-1,4-butylene, 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-cyclopentene group ethylene 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 group dimethyl-1,6-hexylene group, 5-ethyl-1,6-hexylene group, 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)ethylene group, propyl)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-cyclohexylene group cyclohexylene 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-cyclohexyl Examples of the alkyl group include an xylethylene group, a 1-cyclohexyl-2-ethylene group, a nonylmethylene group, a 1-methyl-1,8-octylene group, a decylmethylene group, a 1-methyl-1,8-nonylene group, an undecylmethylene group, a dodecylmethylene group, a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a methylene-1,4-phenylene-methylene group, and an ethylene-1,4-phenylene-ethylene group. Of these, a methylene group and an ethylene group are preferred, and an ethylene group is more preferred.

[0031] The arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and further preferably an arylene group having 6 to 12 carbon atoms. Specific examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

[0032] Specific examples of the a-valent group formed by combining an ester bond and a hydrocarbon group include the group shown in the following formula (a3): In the formula, * represents a bond. [ka]

[0033] The alkylene group and the arylene group may have a substituent. The substituent is the same as the substituent that may be possessed by the a-valent linking group represented by X in the formula (A-1).

[0034] In formula (A-1), X preferably represents an a-valent hydrocarbon group or an a-valent group consisting of a combination of an ester bond, an alkylene group, and an a-valent hydrocarbon group, more preferably an a-valent aliphatic hydrocarbon group or an a-valent group consisting of a combination of an ester bond, an alkylene group, and an a-valent hydrocarbon group, and further preferably represents a group represented by formula (a1) or a group represented by formula (a3).

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

[0036] In formula (A-3), R 41 each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms. Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group, and a divalent aliphatic hydrocarbon group is preferred.

[0037] The divalent aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, with a saturated aliphatic hydrocarbon group being preferred. The divalent aliphatic hydrocarbon group may be a chain-like hydrocarbon group, a cyclic hydrocarbon group (i.e., an alicyclic hydrocarbon group), or a combination thereof. Furthermore, the chain-like hydrocarbon group may be either a straight-chain or branched chain, with a branched chain 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 the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, an alkynylene group, and the like, with an alkylene group 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 still more preferably a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Specific examples of the divalent aromatic hydrocarbon group include an arylene group.

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

[0040] Examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, a nonenylene group, and a decenylene group.

[0041] Examples of the alkynylene group include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, a decynylene group, etc. Examples of the arylene group include a phenylene group, a naphthylene group, etc.

[0042] Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

[0043] The alkylene group, alkenylene group, alkynylene group, and arylene group may have a substituent. The substituent is the same as the substituent that may be possessed by the a-valent linking group represented by X in formula (A-1).

[0044] In formula (A-3), R 42 , R 43 , and R 44 each independently represents a hydrogen atom, a hydroxy 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] Examples of the monovalent hydrocarbon group having 1 to 30 carbon atoms include a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, and a group consisting of a combination thereof, and the like, and the monovalent aliphatic hydrocarbon group is preferred. The monovalent aliphatic hydrocarbon group may be either a monovalent saturated aliphatic hydrocarbon group or a monovalent unsaturated aliphatic hydrocarbon group, and the monovalent saturated aliphatic hydrocarbon group is preferred. The monovalent aliphatic hydrocarbon group may be a chain-like hydrocarbon group, a cyclic hydrocarbon group (i.e., an alicyclic hydrocarbon group), or a combination thereof. Furthermore, the chain-like hydrocarbon group may be either a straight-chain or branched one, and the branched one is preferred. The monovalent 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 the monovalent aliphatic hydrocarbon group include an alkyl group and the like.

[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 still more preferably a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Specific examples of the monovalent aromatic hydrocarbon group include aryl groups.

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

[0048] Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

[0049] Examples of groups formed from a combination of these include a benzyl group and a 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 the alkoxy group having 1 to 30 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a 2-butoxy group, a t-butoxy group, a 1-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a 2,2-dimethylpropoxy group, a 2-ethylpropoxy group, a 3,3-dimethylpropoxy group, a 1,1-dimethylpropoxy group, a cyclopentoxy group, a 1-hexoxy group, a 2-hexoxy group, a 3-hexoxy group, a 4-methylpentoxy group, a 3-methylpentoxy group, a 2 ... Examples of such aryl groups include arylpentoxy 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 the aryloxy group having 6 to 30 carbon atoms include a phenoxy group, a 4-methylphenoxy group, a 3-methylphenoxy group, a 2-methylphenoxy group, a 2,6-dimethylphenoxy group, a 2,4-dimethylphenoxy group, a 2,3-dimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a 4-isopropylphenoxy group, a 2-isopropylphenoxy group, a 3-isopropylphenoxy group, and a 4-isobutylphenoxy group. , 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, and is preferably a dialkylamino group. 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 further preferably an alkylamino group having 1 to 10 carbon atoms. Examples of the alkylamino group include a dimethylamino group, an ethylmethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-t-butylamino group, and a dicyclohexylamino group.

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

[0054] The monovalent hydrocarbon group having 1 to 30 carbon atoms, the alkoxy group having 1 to 30 carbon atoms, the aryloxy group having 6 to 30 carbon atoms, the alkylamino group, and the hydroxyalkyl group having 1 to 30 carbon atoms may have a substituent. The substituent is the same as the substituent that may be possessed by the a-valent linking group represented by X in formula (A-1).

[0055] Among them, in the formula (A-3), R 42 , R 43 , and R 44 each independently preferably represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and R 42 , and R 43 represents a hydrogen atom, and R 44 more preferably represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and R 42 , and R 43 represents a hydrogen atom, and R 44 More preferably, represents a hydrogen atom or a methyl group.

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

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

[0058] In formula (A-2), R 31 , and R 34 each 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, and more preferably 1 to 3. Specific alkylene groups having 1 to 8 carbon atoms are the same as the alkylene groups having 1 to 8 carbon atoms among the alkylene groups in the a-valent group formed by a combination of an ester bond and an alkylene group which can be represented by X in formula (A-1).

[0059] In formula (A-2), R 32 , and R33 each 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, and more preferably 1 to 3. Specific examples of the alkyl group having 1 to 8 carbon atoms include R 42 Among the alkyl groups in the hydrocarbon group having 1 to 30 carbon atoms represented by R, R is the same as the alkyl group having 1 to 8 carbon atoms. 32 , and R 33 preferably represents a methyl group.

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

[0061] The alkyl group having 1 to 8 carbon atoms may have a substituent. The substituent is the same as the substituent that may be possessed by the linking group having a valence of a 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 formula (A-2), d and e represent 0, R 32 , R 33 , and R 35 Preferably, formula (A-2) represents an alkyl group having 1 to 8 carbon atoms, and more preferably formula (A-2) represents a t-butyl group.

[0064] In formula (A-1), k represents an integer of 1 to 4, and preferably an integer of 1 to 3.

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

[0066] Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, and a group consisting of a combination thereof, and the like, and the monovalent aliphatic hydrocarbon group is preferred. The monovalent aliphatic hydrocarbon group may be either a monovalent saturated aliphatic hydrocarbon group or a monovalent unsaturated aliphatic hydrocarbon group, and the monovalent saturated aliphatic hydrocarbon group is preferred. The monovalent aliphatic hydrocarbon group may be a chain-like hydrocarbon group, a cyclic hydrocarbon group (i.e., an alicyclic hydrocarbon group), or a combination thereof. Furthermore, the chain-like hydrocarbon group may be either a straight-chain or branched one, and the branched one is preferred. The monovalent aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and even more preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Specific examples of the monovalent aliphatic hydrocarbon group include an alkyl group and the like.

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

[0068] Specific examples of the alkyl group having 1 to 12 carbon atoms include R 42 Among the alkyl groups in the hydrocarbon group having 1 to 30 carbon atoms represented by R, R is the same as the alkyl group having 1 to 12 carbon atoms. 21 , and R 23 preferably each independently represents 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 represents a methyl group or an ethyl group, and even more preferably represents a methyl group.

[0069] The alkyl group having 1 to 12 carbon atoms may have a substituent. The substituent is the same as the substituent that may be possessed by the linking group having a valence of a represented by X in formula (A-1).

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

[0071] The component (A) can be synthesized by a known method. As a specific synthesis method, for example, it can be synthesized by the method described in WO 2022 / 190497.

[0072] From the viewpoint of obtaining a cured product having low dielectric properties, high adhesion and excellent mechanical strength, the content of the (A) component is preferably 0.1 mass % or more, more preferably 0.5 mass % or more, and even more preferably 1 mass % or more, and is preferably 15 mass % or less, more preferably 13 mass % or less, and even more preferably 10 mass % or less, based on 100 mass % of the non-volatile components in the resin composition.

[0073] From the viewpoint of obtaining a cured product having low dielectric properties, high adhesion and excellent mechanical strength, the content of the (A) component, relative to 100 mass% of the resin component in the resin composition, is preferably 1 mass% or more, more preferably 2 mass% or more, and even more preferably 3 mass% or more, and is preferably 45 mass% or less, more preferably 40 mass% or less, and even more preferably 35 mass% or less, or 20 mass% or less.

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

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

[0076] (B) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester type Examples of the epoxy resin include epoxy resins, glycidyl cyclohexane 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, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, phenolphthalimidine type epoxy resins, etc. The epoxy resins may be used alone or in combination of two or more.

[0077] The resin composition preferably contains, as component (B), an epoxy resin having two or more epoxy groups in one molecule. 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 in one molecule to 100% by mass of the 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 a temperature of 20° C. (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20° C. (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin as component (B), may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. Of these, from the viewpoint of achieving the effects of the present invention significantly, it is preferable to contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0079] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0080] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure, glycidyl cyclohexane type epoxy resin, phenolphthalimidine type epoxy resin, and alkyl diglycidyl ether type epoxy resin are preferred, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and alkyl diglycidyl ether type epoxy resin are more preferred, and naphthalene type epoxy resin, bisphenol A type epoxy resin, and bisphenol F type epoxy resin are even more preferred.

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

[0082] As the solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferable, a solid epoxy resin having three or more epoxy groups in one molecule is more preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is even more preferable.

[0083] As the solid epoxy resin, 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 are preferred, and naphthalene type epoxy resin and biphenyl type epoxy resin are more preferred.

[0084] Specific examples of solid epoxy resins include "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), and "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L" manufactured by Nippon Kayaku Co., Ltd. Examples of epoxy resins include "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin) and "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), and "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by 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) manufactured by Mitsubishi Chemical Co., Ltd.; and "WHR-991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more.

[0085] When a liquid epoxy resin and a solid epoxy resin are used in combination as component (B), the ratio by mass (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. When the ratio by mass of the liquid epoxy resin and the solid epoxy resin is within this range, the desired effects of the present invention can be significantly obtained.

[0086] The epoxy equivalent of the (B) component 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. Within this range, a cured product having sufficient crosslink density of the cured product of the resin composition can be obtained. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy group. This epoxy equivalent can be measured according to JIS K7236.

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

[0088] From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the (B) component is preferably 1 mass % or more, more preferably 3 mass % or more, and even more preferably 5 mass % or more, and is preferably 45 mass % or less, more preferably 20 mass % or less, and even more preferably 15 mass % or less, or 12 mass % or less, based on 100 mass % of non-volatile components in the resin composition.

[0089] From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the (B) component, relative to 100 mass% of the resin component in the resin composition, is preferably 5 mass% or more, more preferably 10 mass% or more, even more preferably 15 mass% or more, and is preferably 40 mass% or less, more preferably 35 mass% or less, even more preferably 30 mass% or less.

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

[0091] As the (C) component, a compound capable of reacting with the (B) component to cure the resin composition can be used, and examples thereof include active ester curing agents, phenolic curing agents, benzoxazine curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, cyanate ester curing agents, etc. Among these, from the viewpoint of obtaining the effects of the present invention significantly, the (C) component preferably contains any one of an active ester curing agent, a phenolic curing agent, a cyanate ester curing agent, and a carbodiimide curing agent, and more preferably contains any one of an active ester curing agent and a phenolic curing agent.

[0092] Examples of active ester curing agents include curing agents having one or more active ester groups in one molecule. Among them, active ester curing agents are preferably 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. The active ester curing agent is preferably one 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. In particular, 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 the carboxylic acid compound 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, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, phenol novolac, etc. Here, the term "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

[0095] Preferred specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac. Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structure consisting of phenylene-dicyclopentylene-phenylene.

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

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

[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, and even more preferably 30% by mass or more, and is 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 taken as 100% by mass.

[0099] The phenol-based curing agent may be a curing agent having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring (such as a benzene ring or a naphthalene ring) in one molecule. Among them, a compound having a hydroxyl group bonded to a benzene ring is preferred. From the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure is preferred. From the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent is more preferred. In particular, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion, a triazine skeleton-containing phenol novolac curing agent is preferred.

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

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

[0102] Specific examples of carbodiimide-based curing agents include "V-03", "V-05", and "V-07" manufactured by Nisshinbo Chemical Inc.; and Stavaxol (registered trademark) P manufactured by Rhein Chemie.

[0103] Examples of the acid anhydride curing agent include a curing agent having one or more acid anhydride groups in one molecule.Specific examples of the acid anhydride curing agent 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-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone. Examples of the acid anhydride include tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 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 polymeric acid anhydrides such as styrene-maleic acid resins in which styrene and maleic acid are copolymerized. Commercially available acid anhydride curing agents may be used, such as "MH-700" manufactured by New Japan Chemical Co., Ltd.

[0104] The amine-based curing agent may be a curing agent having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc., and among them, 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'-diaminodiphenylether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propanediamine, and the like. bis(4-aminophenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 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. The amine-based curing agent may be a commercially available product, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by 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-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester curing agents include "PT30" and "PT60" manufactured by Lonza Japan Co., Ltd. (both are phenol novolac type multifunctional cyanate ester resins); "ULL-950S" (multifunctional cyanate ester resin); "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been converted to triazine to form a trimer); and the like.

[0106] When the number of epoxy groups in the (B) component is taken as 1, the number of active groups in the (C) curing agent is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and preferably 10 or less, more preferably 5 or less, even more preferably 3 or less. Here, the "number of epoxy groups in the (A) component" refers to the total value obtained by dividing the mass of the non-volatile components of the (B) component present in the resin composition by the epoxy equivalent. In addition, the "number of active groups in the (C) curing agent" refers to the total value obtained by dividing the mass of the non-volatile components of the (C) curing agent present in the resin composition by the active group equivalent. When the number of epoxy groups in the (B) component is taken as 1, the number of active groups in the (C) curing agent is within the above range, so that the desired effects of the present invention can be significantly obtained.

[0107] From the viewpoint of significantly obtaining the effects of the present invention, the content of the (C) curing agent is preferably 1 mass % or more, more preferably 5 mass % or more, and even more preferably 8 mass % or more, and is preferably 30 mass % or less, more preferably 20 mass % or less, and even more preferably 18 mass % or less, based on 100 mass % of non-volatile components in the resin composition.

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

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

[0110] (D) An inorganic compound is used as the material of the inorganic filler. (D) Examples of the material of 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 suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, spherical silica is preferable as the silica.

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

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

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

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

[0115] (D) The specific surface area of ​​the inorganic filler can be measured according to the BET method by adsorbing nitrogen gas onto the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and 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 the surface treatment agent 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. The surface treatment agent may be used alone or in any combination of two or more.

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

[0118] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably with 0.2% to 3% by mass of the surface treatment agent, and even more preferably 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 set to 0.02 mg / m 2 More than 0.1 mg / m is preferable. 2 More preferably, 0.2 mg / m or more 2 On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, it is more preferable that the content is 1.0 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0120] (D) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a 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 solid content, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, the "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used.

[0121] The degree of surface treatment with 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, and even more preferably 0.1% by mass or more, and is 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 (D) inorganic filler can be measured using a carbon analyzer in the same manner as the amount of carbon per unit surface area of ​​the (D) inorganic filler.

[0122] The content of the (D) inorganic filler, relative to 100 mass% of the non-volatile components in the resin composition, is preferably 50 mass% or more, more preferably 55 mass% or more, even more preferably 60 mass% or more, 65 mass% or more, or 70 mass% or more, and is preferably 90 mass% or less, more preferably 85 mass% or less, and particularly preferably 80 mass% or less.

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

[0124] The (E) radical polymerizable compound may contain an ethylenically unsaturated bond. Thus, the (E) radical polymerizable compound may have a radical polymerizable group containing an ethylenically unsaturated bond. Examples of the radical polymerizable group include unsaturated hydrocarbon groups such as vinyl group, allyl group, 1-propenyl group, 3-cyclohexenyl group, 3-cyclopentenyl group, 2-vinylphenyl group, 3-vinylphenyl group, and 4-vinylphenyl group; and α,β-unsaturated carbonyl groups such as acryloyl group, methacryloyl group, and maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl group). The (E) radical polymerizable compound preferably has two or more radical polymerizable groups.

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

[0126] The (meth)acrylic radical polymerizable compound is, for example, a compound having one or more, preferably two or more, acryloyl groups and / or methacryloyl groups. Examples of the (meth)acrylic radical polymerizable compound 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, 1,9-nonanediol di(meth)acrylate, 1,2-diphenylmethane di(meth)acrylate, 1,3-diphenylmethane di(meth)acrylate, 1,4-diphenylmethane di(meth)acrylate, 1,5-diphenylmethane di(meth)acrylate, 1,6-diphenylmethane di(meth)acrylate, 1,8-diphenylmethane di(meth)acrylate, 1,9-diphenylmethane ...5-diphenylmethane di(meth)acrylate, 1,5-diphenylmethane di(meth)acrylate, 1,6-diphenylmethane di(meth)acrylate, 1,8-diphenylmethane di(meth)acrylate, 1,9-diphenylmethane di(meth)acrylate, 1,5-diphenylmethane di(meth)acrylate, 1,5-diphenylmethane di(meth)acrylate, 1,5-diphenylmethane di(meth)acrylate, 1,5-diphenylmethane aliphatic (meth)acrylic acid ester compounds with low molecular weight (molecular weight less than 1000), such as dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; Examples of the ether-containing (meth)acrylic acid ester compound include low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylic acid ester compounds such as 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 isocyanuric acid tri(meth)acrylate; and high molecular weight (molecular weight 1000 or more) acrylic acid ester compounds such as (meth)acrylic modified polyphenylene ether resin.Examples of commercially available (meth)acrylic radically polymerizable compounds include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate) and "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate) and "KAYARAD R-604" (dioxane glycol diacrylate) manufactured by Nippon Kayaku Co., Ltd., and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether) manufactured by SABIC Innovative Plastics.

[0127] The styrene radical polymerizable compound is, for example, a compound having one or more, preferably two or more, vinyl groups directly bonded to an aromatic carbon atom. Examples of the styrene radical polymerizable compound 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; high molecular weight (molecular weight 1000 or more) styrene compounds such as vinylbenzyl-modified polyphenylene ether resin and styrene-divinylbenzene copolymer. Examples of commercially available styrene-based radically polymerizable compounds include "ODV-XET(X03)", "ODV-XET(X04)", and "ODV-XET(X05)" (styrene-divinylbenzene copolymers) manufactured by Nippon Steel Chemical & Material Co., Ltd., and "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Co., Inc.

[0128] The allyl radical polymerizable compound is, for example, a compound 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-naphthalenedicarboxylate, and diallyl 2,3-naphthalenecarboxylate; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl 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-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; and allyl silane compounds such as diallyl diphenyl silane. Commercially available allyl radical polymerizable compounds include, for example, "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Chemical Industry Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Wako Pure Chemical Industries, Ltd., trade name "DAND" (2,3-naphthalene carboxylate diallyl) manufactured by Nippon Distillation Industry Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Kasei Corporation, "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., and "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Corporation.

[0129] The maleimide radical polymerizable compound is, for example, a compound having one or more, preferably two or more, maleimide groups. The maleimide radical polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton, or an aromatic maleimide compound containing an aromatic amine skeleton. Commercially available maleimide radical polymerizable compounds include, for example, "SLK-2600" manufactured by Shin-Etsu Chemical Co., Ltd., "BMI-1500", "BMI-1700", "BMI-3000J", "BMI-689", and "BMI-2500" (dimer diamine structure-containing maleimide compounds) manufactured by DigiCner Molecules, Inc., "BMI-6100" (aromatic maleimide compound) manufactured by DigiCner Molecules, "MIR-5000-60T" and "MIR-3000-70MT" (biphenylaralkyl-type maleimide compounds) manufactured by Nippon Kayaku Co., Ltd., "BMI-70" and "BMI-80" manufactured by K.I. Chemical Industry Co., Ltd., and "BMI-2300" and "BMI-TMH" manufactured by Daiwa Kasei Kogyo Co., Ltd. In addition, as the maleimide-based radically polymerizable compound, a maleimide resin (maleimide compound containing an indane ring skeleton) disclosed in the Japan Institute of Invention and Innovation's Technical Journal Publication No. 2020-500211 may be used.

[0130] The ethylenically unsaturated bond equivalent of the (E) radical polymerizable compound is preferably 20 g / eq. to 3,000 g / eq., more preferably 50 g / eq. to 2,500 g / eq., further 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 the ethylenically unsaturated bond.

[0131] The weight average molecular weight (Mw) of the radical polymerizable compound (E) is preferably 40,000 or less, more preferably 10,000 or less, further 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), based on 100 mass% of nonvolatile components in the resin composition, is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, even more preferably 0.5 mass% or more, and is preferably 10 mass% or less, more preferably 5 mass% or less, even more preferably 3 mass% or less.

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

[0134] <(F)Thermoplastic resin> The resin composition may contain a thermoplastic resin (F) as an optional component. The thermoplastic resin (F) as the component (F) does not include those corresponding to the components (A) to (E). The component (F) may be used alone or in combination of two or more kinds.

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

[0136] As the polyimide resin, a resin having an imide structure can be used. Polyimide resins generally include those obtained by an imidization reaction between a diamine compound and an acid anhydride. Specific examples of polyimide resins include the polyimide resins described in JP 2021-14544 A.

[0137] The polyimide resin may be a commercially available product, such as "Rikacoat SN20" and "Rikacoat PN20" manufactured by New Japan Chemical Co., Ltd.

[0138] As the polycarbonate resin, a resin having a carbonate structure can be used. Examples of such resins include carbonate resins having no reactive group, hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Here, the reactive group refers to a functional group that can react with other components, such as a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, a urethane group, and an epoxy group.

[0139] Commercially available carbonate resins can be used, including "FPC0220" manufactured by Mitsubishi Gas Chemical Company, "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals Corporation, and "C-1090", "C-2090", and "C-3090" (polycarbonate diol) manufactured by Kuraray Co., Ltd.

[0140] Examples of the phenoxy resin 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 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" manufactured by Mitsubishi Chemical Corporation (both of which are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482" manufactured by Mitsubishi Chemical Corporation.

[0142] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include S-LEC 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. Specific examples of polyamide-imide resins also include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Co., Ltd.

[0144] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0145] A specific example of the polyphenylene ether resin is the oligophenylene ether-styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company.

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

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

[0148] The content of the (F) thermoplastic resin, based on 100 mass% of the non-volatile components in the resin composition, is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.08 mass% or more, and is preferably 3 mass% or less, more preferably 1.5 mass% or less, even more preferably 1 mass% or less.

[0149] The content of the (F) thermoplastic resin, based on 100 mass% of the resin component in the resin composition, is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, even more preferably 0.3 mass% or more, and is preferably 5 mass% or less, more preferably 4 mass% or less, even more preferably 3 mass% or less.

[0150] <(G) Curing accelerator> The resin composition may contain a curing accelerator (G) as an optional component. The curing accelerator (G) as the component (G) does not include those corresponding to the components (A) to (F). Examples of the curing accelerator (G) include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. The amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferred, and either the amine-based curing accelerators or the imidazole-based curing accelerators are more preferred. The curing accelerator may be used alone or in combination of two or more types.

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

[0152] Examples of the amine curing accelerator 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 the imidazole curing accelerator 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 isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-furan Examples of the imidazole compounds include imidazole compounds such as 2-ethyl-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 and epoxy resins. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0154] As the imidazole-based curing accelerator, a commercially available product may be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0155] Examples of the guanidine curing accelerator 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]dec-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene. Examples of such biguanide include o-[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0156] Examples of metal-based curing 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 octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

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

[0159] <(H)Organic filler> The resin composition may contain an organic filler (H) as an optional component. The organic filler (H) as the component (H) does not include those corresponding to the above-mentioned components (A) to (G). The component (H) may be used alone or in combination of two or more.

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

[0161] Examples of the rubber component contained in the rubber particles include 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, ethylene-propylene-butene terpolymer, and other olefin-based thermoplastic elastomers; poly(propyl meth)acrylate, poly(butyl meth)acrylate, poly(cyclohexyl meth)acrylate, poly(octyl meth)acrylate, and other acrylic thermoplastic elastomers, and preferably olefin-based thermoplastic elastomers, and more preferably styrene-butadiene copolymers. Furthermore, the rubber component may be mixed with silicone-based rubbers such as polyorganosiloxane rubber. 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] As the rubber particles, commercially available products may be used, for example, "AC3401N" and "AC3816N" manufactured by Aica Kogyo Co., Ltd.

[0163] The core-shell type particles are particulate organic fillers consisting of a core particle containing a rubber component as described above and one or more shell layers covering the core particle. Furthermore, the core-shell type particles are preferably core-shell type graft copolymer particles consisting of a core particle containing a rubber component as described above and a shell portion obtained by graft copolymerization of a monomer component copolymerizable with the rubber component contained in the core particle. The core-shell type as used herein does not necessarily refer only to particles in which the core particle and the shell portion are clearly distinguishable, but also includes particles in which the boundary between the core particle and the shell portion is unclear, and the core particle does not necessarily have to be completely covered with the shell portion.

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

[0165] Examples of monomer components forming the shell portion of the 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; maleimide; 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. Of these, (meth)acrylic acid esters are preferred, and methyl (meth)acrylate is more preferred.

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

[0167] The average particle size (average primary particle size) of the core-shell 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, particularly preferably 500 nm or less. The average particle size (average primary particle size) of the core-shell graft copolymer particles can be measured using a zeta potential particle size distribution measuring device or the like.

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

[0169] The content of the (H) component, relative to 100 mass% of the resin component in the resin composition, is preferably 0.5 mass% or more, more preferably 1 mass% or more, and even more preferably 1.5 mass% or more, and is preferably 5 mass% or less, more preferably 4 mass% or less, and even more preferably 3 mass% or less.

[0170] <(I) Other additives> The resin composition may further contain other additives as optional components in addition to the above-mentioned components. (I) Other additives include, for example, elastomers; polymerization initiators; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, 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 bentone 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 imparters such as triazole-based adhesion imparters, tetrazole-based adhesion imparters, and triazine-based adhesion imparters; hindered phenol-based antioxidants such as antioxidants; fluorescent brightening 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 anhydride-based stabilizers; photopolymerization initiation assistants such as tertiary amines; and photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, and thioxanthones. (I) Other additives may be used alone or in combination of two or more kinds.

[0171] <(J) Solvent> The resin composition may further contain an arbitrary solvent as a volatile component in addition to the non-volatile components described above. As the (J) solvent, a known solvent may be appropriately used, and the type is not particularly limited, and an organic solvent is preferable. As the (J) solvent, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole, etc.; alcohol-based solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, etc.; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate, etc. Examples of the solvent include ether ester solvents such as ethyl acetate, 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 (butylcarbitol), 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. The (J) solvent may be used alone or in combination of two or more in any ratio.

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

[0173] The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the blending components are mixed and dispersed using a rotary mixer or the like, with the addition of a solvent or the like as necessary.

[0174] <Physical properties and applications of resin compositions> The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes exhibits the characteristic of a low dielectric constant. Thus, an insulating layer with a low dielectric constant is obtained. 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 may be 0.01 or more. The dielectric constant can be measured by the method described in the examples below. The resin composition is thermally cured at 190°C for 90 minutes to produce a cured product with a low dielectric tangent. This results in an insulating layer with a low dielectric tangent. The dielectric 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 may be 0.0001 or more. The dielectric tangent can be measured by the method described in the examples below.

[0175] The resin composition is thermally cured at 190°C for 90 minutes to produce a cured product with a high maximum point stress. This results in an insulating layer with a high maximum point stress. The maximum point stress is preferably 100 MPa or more, more preferably 101 MPa or more, and even more preferably 102 MPa or more. There is no particular upper limit, but it may be 1000 MPa or less. The maximum point stress can be measured by the method described in the examples below.

[0176] The resin composition is thermally cured at 190°C for 90 minutes to produce a cured product with excellent breaking elongation. This results in an insulating layer with excellent breaking elongation. The breaking elongation is preferably 1% or more, more preferably 1.2% or more, and even more preferably 1.5% or more, or 2% or more. There is no particular upper limit, but it may be 50% or less, 100% or less, etc. The breaking elongation can be measured by the method described in the examples below.

[0177] The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes exhibits excellent adhesion (peel strength) to the copper foil. This results in 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 may be 10 kgf / cm or less. The peel strength can be measured by the method described in the examples below.

[0178] The resin composition of the present invention can obtain a cured product having 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 insulation purposes. Specifically, it can be suitably used as a resin composition for forming an insulating layer (resin composition for forming an insulating layer) for forming a conductor layer (including a rewiring layer) formed on an insulating layer.

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

[0180] In addition, 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 rewiring formation layer (resin composition for forming a rewiring formation layer) as an insulating layer for forming a rewiring layer, and as a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the sealing layer. (1) A step of laminating a temporary fixing film onto a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A process of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0181] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed from 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 making the printed wiring board thinner and being able to provide a cured product with excellent insulation 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 the support include films made of plastic materials, metal foils, and release papers, with films made of plastic materials and metal foils being preferred.

[0184] When a film made of a plastic material is used as the support, examples of the plastic material 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, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0185] When a metal foil is used as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of a single metal, copper, or an alloy of copper and another metal (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0186] The surface of the support to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0187] In addition, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the support with a release layer may be, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The support with a release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Unipeel" manufactured by Unitika Limited, which are PET films having a release layer mainly composed of an alkyd resin-based release agent.

[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 a support with a release layer is used, it is preferable that the total thickness of the support with a release layer is in the above range.

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

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

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

[0192] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

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

[0194] The printed wiring board can be produced, for example, by using the above-mentioned resin sheet by a method including the following steps (I) and (II). (I) A step of laminating a resin sheet on an inner layer substrate so that a resin composition layer of the resin sheet is bonded to the inner layer substrate. (II) A step of thermally curing the resin composition layer to form an insulating layer

[0195] The "inner layer substrate" used in step (I) is a member that becomes the substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The substrate may have a conductor layer on one or both sides, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be called an "inner layer circuit substrate". In addition, an intermediate product on which an insulating layer and / or a conductor layer is to be further formed during the manufacture of a printed wiring board is also included in the "inner layer substrate" of the present invention. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0196] The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as the "thermocompression bonding member") include a heated metal plate (such as a SUS plate) or a metal roll (SUS roll). It is preferable to press the thermocompression member not directly onto the resin sheet, but via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the surface irregularities of the inner layer substrate.

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

[0198] The lamination can be performed by a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch type vacuum pressure laminator.

[0199] After lamination, the laminated resin sheet may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. The lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

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

[0201] In step (II), the resin composition layer is thermally cured to form an insulating layer. The conditions for thermally curing the resin composition layer are not particularly limited, and conditions that are usually employed when forming an insulating layer for a printed wiring board may be used.

[0202] For example, the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, etc., 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 is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0203] Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50° C. or more and less than 120° C. (preferably 60° C. or more and 115° C. or less, more preferably 70° C. or more and 110° C. or less) 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 a printed wiring board, the steps of (III) drilling holes in the insulating layer, (IV) roughening the insulating layer, and (V) forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art for use in manufacturing printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board, as necessary.

[0205] Step (III) is a step of drilling holes in the insulating layer, which allows holes such as via holes and through holes to be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a 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 depending on the design of the printed wiring board.

[0206] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), smears are also removed. The procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid used in the roughening treatment is not particularly limited, but includes an alkaline solution, a surfactant solution, and the like, and is preferably an alkaline solution, and as the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P", "Swelling Dip Securigans SBU", and "Swelling Dip Securigant P" manufactured by Atotech Japan. The swelling treatment using a swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid 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 liquid at 40°C to 80°C for 5 to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. The neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and a commercially available product is, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan. Treatment with a neutralizing solution can be performed by immersing the surface that has been roughened with an oxidizing agent in the neutralizing solution at 30°C to 80°C for 1 to 30 minutes.From the viewpoint of workability etc., a method in which the object that has been subjected to roughening treatment with an oxidizing agent is immersed in a neutralizing solution at 40° C. to 70° C. for 5 minutes to 20 minutes is preferred.

[0207] In one embodiment, the arithmetic mean roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 300 nm or less, more preferably 250 nm or less, and even more preferably 200 nm or less. There is no particular limit to the lower limit, but it 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 conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor 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 conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer 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). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0209] The conductor layer may be a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has 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 a nickel-chromium alloy.

[0210] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, and 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 by a conventionally known technique such as a semi-additive method or a full-additive method, and from the viewpoint of ease of production, it is preferable to form the conductor layer by the semi-additive method. An example of forming the conductor layer by the semi-additive method will be described below.

[0212] First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a part of the plating seed layer corresponding to a desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

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

[0214] Examples of the semiconductor device include various semiconductor devices used in electric appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

[0215] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a portion of a printed wiring board that transmits an electric signal, and the portion may be either on the surface or embedded. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of semiconductor material.

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

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

[0218] <Synthesis Example 1: Synthesis of PPE-1> A 1.5-liter jacketed reactor equipped with a sparger for introducing an oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux condenser on the vent gas line at the top of the reactor was charged with a mixture of 0.1026 g of cuprous oxide and 0.7712 g of 47% hydrogen bromide, 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). Then, air was introduced into the reactor from the sparger at a rate of 1.05 L / min while vigorously stirring, and the polymerization temperature was adjusted by passing a heat medium through the jacket to maintain it at 40°C. 160 minutes after the start of air introduction, the aeration was stopped, and 1.1021 g of ethylenediaminetetraacetic acid tetrasodium salt tetrahydrate (a reagent manufactured by Dojindo Laboratories) was added to the polymerization mixture as a 100 g aqueous solution, and the mixture was heated to 70 ° C. After keeping the temperature at 70 ° C for 2 hours to perform catalyst extraction and by-product diphenoquinone removal treatment, 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 was transferred. The obtained polyphenylene ether composition solution was transferred to a jacketed concentration tank, and toluene was distilled off until the solid content in the polyphenylene ether composition solution reached 55 mass % to concentrate it. Next, toluene was further distilled off using an oil bath and a rotary evaporator set at 230 ° C., and the solid content was dried to obtain a polyphenylene ether composition.

[0219] <Synthesis Example 2: Synthesis of PPE-2> A stirrer was placed in a three-neck flask, a Dimroth condenser with a three-way cock was installed on the main tube, and a rubber stopper with a thermometer was attached to one side tube. 20 g of the unmodified polyphenylene ether composition obtained in Synthesis Example 1 was added from the other side tube, and a rubber stopper was attached. After the inside of the flask was replaced with nitrogen, the mixture was dissolved in 140 g of toluene using a syringe while stirring the inside with a magnetic stirrer, and then 6.32 g of triethylamine was added. Then, 3.27 g of methacryloyl chloride was collected in a syringe and dropped into the system through the rubber stopper. After the dropwise addition, stirring was continued at room temperature for 3 hours, and then the flask was heated in an oil bath to continue the reaction under reflux. Heating was stopped 2 hours after the start of reflux, and after the temperature returned to room temperature, 1.00 g of methanol was added to stop the reaction. Next, the reaction liquid was concentrated until the solid content concentration was 20% by weight, and then washed with ion-exchanged water of the same weight as the concentrated liquid. Thereafter, the water bath 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 residue 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 an oxygen-containing gas at the bottom of the reactor, stirring turbine blades and baffles, and a reflux condenser on the vent gas line at the top of the reactor was charged with a previously prepared mixture of 0.1026 g of cuprous oxide and 0.7712 g of 47% hydrogen bromide, 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). Then, while vigorously stirring, air was introduced into the reactor from the sparger at a rate of 1.05 L / min, and the polymerization temperature was adjusted by passing a heat medium through the jacket so as to maintain 40°C. 160 minutes after the start of air introduction, the air aeration was stopped, and 1.1021 g of ethylenediaminetetraacetic acid tetrasodium salt tetrahydrate (a reagent manufactured by Dojindo Laboratories) was added to the polymerization mixture as a 100 g aqueous solution, and the mixture was heated to 70°C. After keeping the mixture at 70°C for 2 hours to perform catalyst extraction and by-product diphenoquinone removal treatment, 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 concentration tank, and concentrated by distilling off toluene until the solid content in the polyphenylene ether composition solution reached 55% by mass. Next, the toluene was further distilled off using an oil bath and a rotary evaporator set at 230° C., and the solid content was dried to obtain a polyphenylene ether composition.

[0221] <Measurement of number average molecular weight (Mn)> As a measuring device, a gel permeation chromatography System 21 manufactured by Showa Denko K.K. was used, and a calibration curve was prepared using standard polystyrene and ethylbenzene. Using this calibration curve, the number average molecular weight (Mn) of the obtained PPE-1, PPE-2, and PPE-3 was measured. As standard polystyrene, those with 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 were used. As a column, two Showa Denko K-805L columns connected in series were used. As a solvent, chloroform was used, and the solvent flow rate was 1.0 mL / min, and the column temperature was 40° C., and a 1 g / L chloroform solution of PPE-1 synthesized in Synthesis Example 1 was prepared and used as a measurement sample. The UV wavelength of the detection unit was 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). In a nitrogen atmosphere, the samples were heated from room temperature to 200°C at a heating rate of 20°C per minute, then cooled to 50°C at a heating rate of 20°C per minute, and the glass transition temperatures were then measured at a heating rate of 20°C per minute.

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

[0224] <Measurement of the number of terminal methacrylic groups contained in the resin> The PPE-2 synthesized in Synthesis Example 2 and a standard 1,3,5-trimethoxybenzene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight 168.19) were taken in a specified amount as an internal standard sample, and dissolved in deuterated chloroform containing trimethylsilane. 1 H-NMR measurements were performed using a JEOL 500 MHz microscope.

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

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

[0227] [Table 1]

[0228] <Synthesis Example 4: Synthesis of Maleimide A> An MEK solution of maleimide compound A (62% by mass of non-volatile components, t'' = 1.47 (mainly 1, 2 or 3), Mw / Mn = 1.81) synthesized by the method described in Synthesis Example 1 of the Japan Institute of Invention and Innovation's Technical Journal Publication No. 2020-500211 was prepared. This maleimide compound A has a structure represented by the following formula. [ka]

[0229] <Synthesis Example 5: Synthesis of Polyimide B> A 500 mL separable flask equipped with a water content 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 a reaction. Next, the reaction solution was heated and, while maintaining the temperature at about 160°C, condensed water was azeotropically removed together with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water had accumulated in the water content receiver and that no water was flowing out. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. The mixture was then 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). The weight average molecular weight of the polyimide resin was 12,000. [ka]

[0230] <Production of resin varnish> Each component was weighed out in the amount shown in the table, and then mixed with 10 parts of MEK and 10 parts of cyclohexanone, and uniformly dispersed using a high-speed rotating 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: Polyphenylene 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 (B) Component HP-4032-SS: Naphthalene type epoxy resin (functional group equivalent weight 144g / 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 epoxy resin and bisphenol F epoxy resin (functional group equivalent: 169g / eq., manufactured by Nippon Steel Chemical & Material Co., Ltd.) ESN-475V: Naphthalene type epoxy resin (functional group equivalent weight 332g / eq., manufactured by Nippon Steel Chemical & Material Co., Ltd.) (C) Component HPC-8150-62T: Active ester curing agent (active ester resin with naphthalene structure, functional group equivalent weight 223g / eq., manufactured by DIC) HPC-8000L-65MT: Active ester resin containing dicyclopentadiene-type diphenol structure, functional group equivalent weight 229g / eq., manufactured by DIC Corporation PC1300-02-65MA: Activated ester resin with naphthalene structure, functional group equivalent weight 199g / eq., manufactured by Air Water Corporation LA-3018-50P: 1-methoxy-2-propanol solution with functional group equivalent of 151 g / eq. and non-volatile content of 50% by mass, manufactured by DIC Corporation V03: Functional group equivalent weight 216g / eq., non-volatile content 50% by mass in toluene solution, manufactured by Nisshinbo Chemical Co., Ltd. BA230S75: Prepolymer of bisphenol A dicyanate, functional group equivalent weight 232g / eq., manufactured by Lonza Japan (D) Component SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd.'s "KBM573"), with an average particle size of 0.5 μm and a specific surface area of ​​5.8 m 2 / g, manufactured by Admatechs Co., Ltd. UFP-30: Spherical silica surface-treated with an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd.'s "KBM573"), with an average particle size of 0.3 μm and a specific surface area of ​​30.7 m 2 / g, manufactured by Denka (E) Component Maleimide A: The compound 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. Ingredient (F) YX7553BH30: Phenoxy resin, 1:1 solution of MEK and cyclohexanone with 30% non-volatile content by mass, manufactured by Mitsubishi Chemical Corporation Polyimide B: Synthesized in Synthesis Example 5 (G) Component 1B2PZ: Imidazole-based reaction accelerator, manufactured by Shikoku Chemical Industry Co., Ltd. DMAP: Amine-based curing accelerator, manufactured by Tokyo Chemical Industry Co., Ltd. Co(III): Metallic hardening accelerator, manufactured by Tokyo Chemical Industry Co., Ltd. (H) Component EXL2655: Core-shell type graft copolymer rubber particles, manufactured by The Dow Chemical Company catalyst Component (I) S202A: Modified polyphenylene ether, number average molecular weight 16000, manufactured by Asahi Kasei Corporation, terminal functional group number 2 OPE-2St: Vinylbenzyl modified polyphenylene ether, number average molecular weight 1200, manufactured by Mitsubishi Gas Chemical Co., Ltd., terminal functional group number 2

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

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

[0235] (3) Measurement of dielectric constant and dielectric tangent (dielectric properties) The cured product was cut into a piece 80 mm long and 2 mm wide, and the dielectric constant and dielectric tangent (Dk and Df values) were measured by the cavity resonance perturbation method using an Agilent Technologies HP8362B at a measurement frequency of 5.8 GHz and measurement temperatures of 23°C and 90°C. Measurements were performed on two test pieces, and the average was calculated.

[0236] (4) Measurement of maximum stress and breaking elongation (mechanical strength) The tensile strength of the cured product was measured using an Orientec tensile tester "RTC-1250A" to measure the maximum stress and breaking elongation at 23°C. The measurement was performed in accordance with JIS K7127. The measurement was performed five times, and the average of the top three points was calculated.

[0237] <Evaluation of Adhesion> (1) Copper foil preparation The shiny side of an electrolytic copper foil (Mitsui Mining & Metals Co., Ltd. "3EC-III", thickness 35 μm) was etched by 1 μm with a micro-etching agent (Mech Co., Ltd. "CZ8101") to roughen the copper surface, and then anti-rust treatment (CL8300) was performed. The copper foil whose surface was etched with the micro-etching agent in this way may be referred to as "CZ copper foil" hereinafter. Furthermore, this copper foil was heat-treated in an oven at 130°C for 30 minutes to obtain copper foil I having a roughened treated surface.

[0238] (2) Preparation of inner layer board A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") was prepared, which had copper foil on its surface and an inner layer circuit formed thereon. Both sides of this glass cloth-based epoxy resin double-sided copper-clad laminate were etched to a thickness of 1 μm with a microetching agent (Mec "CZ8101") to roughen the copper foil surface. This resulted in an inner layer substrate having a CZ copper foil with a treated surface on its surface.

[0239] (3) Lamination of the resin composition layer The resin sheets prepared in the examples and comparative examples were laminated on both sides of the inner layer substrate. This lamination was performed using a batch-type vacuum pressure laminator (two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) so that the resin composition layer was in contact with the inner layer substrate. The lamination was performed by reducing the pressure for 30 seconds to adjust the air pressure to 13 hPa or less, 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. Thereafter, 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 on the exposed resin composition layer under the same conditions as in "(3) Lamination of the resin composition layer" above. The resin composition layer was then cured at 200°C for 90 minutes to form an insulating layer containing a cured product of the 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 copper foil> The evaluation board C was cut into small pieces of 150 mm x 30 mm. A cutter was used to make a cut in the small piece of copper foil I, surrounding a portion of 10 mm in width and 100 mm in length. One end of this portion was peeled off and held with a gripper of a tensile tester (Autocom universal tester "AC-50C-SL" manufactured by TSE Corporation). The load [kgf / cm] when 35 mm was peeled off by pulling vertically at a speed of 50 mm / min at room temperature (25°C) was measured as the copper foil peel strength. The measurement was performed in accordance with the Japanese Industrial Standard JIS C6481. In addition, in Comparative Example 3, a bulge occurred between the copper foil and the insulating layer, and the peel strength could not be measured.

[0242] [Table 3]

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

Claims

1. (A) a polyphenylene ether resin having more than two terminal functional groups; (B) an epoxy resin, (C) a curing agent, and (D) A resin composition containing an inorganic filler.

2. The resin composition according to claim 1, wherein the component (A) has a structure represented by the following formula (A-1): 【Chemistry 1】 In formula (A-1), X represents a linking group having a valence of a, each Z independently represents a hydrogen atom or a group represented by formula (A-3), R １１ each independently represents a hydrogen atom or a group represented by formula (A-2), R ２１ , and R ２３ each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or a halogen atom; R ２２ , and R ２４ each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, a group represented by formula (A-2), or a halogen atom. ２２ , and R ２４ represents a hydrogen atom, and R ２２ and R ２４ The case where one of the groups is a group represented by formula (A-2) and the other is a hydrogen atom, a methyl group, or an ethyl group is excluded. a and b each independently represent an integer of 2 to 6; k each independently represent an integer of 1 to 4; and n each independently represent an integer of 0 to 200. 【Chemistry 2】 In formula (A-2), R ３１ , and R ３４ each independently represents an alkylene group having 1 to 8 carbon atoms; R ３２ , and R ３３ each independently represents an alkyl group having 1 to 8 carbon atoms; 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 3】 In formula (A-3), R ４１ each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms; R ４２ , R ４３ , and R ４４ each independently represents a hydrogen atom, a hydroxy 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 of 0 to 5. * represents a bond.

3. The resin composition according to claim 1 , wherein the component (C) contains an active ester-based curing agent.

4. The resin composition according to claim 1 , wherein the component (C) contains a phenol-based curing agent.

5. The resin composition according to claim 1 , further comprising (E) a radically polymerizable compound.

6. The resin composition according to claim 5 , wherein the component (E) contains a maleimide-based radically polymerizable compound.

7. A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition layer comprising the resin composition according to any one of claims 1 to 6.

8. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 6.

9. A semiconductor device comprising the printed wiring board according to claim 8.

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