Resin composition

Abstract

The present invention addresses the problem of providing a resin composition and the like which can provide a cured product having low dielectric properties, high adhesion to a conductor layer, and excellent mechanical strength. [Solution] A resin composition containing (A) a polyphenylene ether resin having more than 2 terminal functional groups, (B) an epoxy resin, (C) a curing agent, and (D) an inorganic filler.

Description

Technical Field

[0001] The present invention relates to a resin composition and further to a resin sheet, a printed wiring board and a semiconductor device obtained by using the resin composition. Background Art

[0002] As a manufacturing technology for a printed wiring board, a manufacturing method based on a build-up method in which insulating layers and conductive layers are alternately stacked is known.

[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 literature

[0004] Patent Literature Patent Document 1: Japanese Patent Application Publication No. 2022-60800 Patent Document 2: Japanese Patent Application Publication No. 2013-181132 Summary of the invention

[0005] Problems to be solved by the invention In recent years, with the high functionality of printed wiring boards, further improvements in dielectric loss tangent and dielectric constant of the insulating layer and further improvements in adhesion with plating are required. In addition, in order to improve the mechanical strength of the printed wiring board, further improvements in maximum point stress and elongation at break of the insulating layer are also required. Hereinafter, dielectric loss tangent and dielectric constant are sometimes collectively referred to as dielectric properties, and maximum point stress and elongation at break are sometimes collectively referred to as mechanical strength.

[0006] The subject of the present invention is proposed in view of the above-mentioned problems. Among the above-mentioned problems, the problems of adhesion between the conductor layer and mechanical strength become significant when the inorganic filler is highly filled. The subject of the present invention is to provide: a resin composition that can obtain a cured product with low dielectric properties, high adhesion (peel strength) between the conductor layer and excellent mechanical strength; a resin sheet containing the resin composition; a printed wiring board and a semiconductor device having an insulating layer formed using the resin composition.

[0007] Means for solving problems The present inventors have conducted intensive studies on the above-mentioned problems and have found that the above-mentioned problems can be solved by combining (A) a polyphenylene ether resin having a terminal functional group number greater than 2, (B) an epoxy resin, (C) a curing agent and (D) an inorganic filler, thereby completing the present invention.

[0008] That is, the present invention includes the following contents. [1] A resin composition comprising: (A) polyphenylene ether resin having a terminal functional group number greater than 2, (B) Epoxy resin, (C) a curing agent, and (D) Inorganic filling materials. [2] The resin composition according to [1], wherein the component (A) has a structure represented by the following formula (A-1): [Chemical formula 1] In formula (A-1), X represents an a-valent linking group, Z each 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 the formula (A-2), or a halogen atom, but R 22 and R 24 In the case of hydrogen atoms, R 22 and R 24 Except when one of them is a group represented by formula (A-2) and the other represents a hydrogen atom, a methyl group or an ethyl group, a and b each independently represent an integer of 2 to 6, k each independently represents an integer of 1 to 4, n each independently represents an integer from 0 to 200; [Chemical formula 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, * indicates a bond, d and e independently represent 0 or 1; [Chemical formula 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 hydroxyl group, a monovalent hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylamino group or a hydroxyalkyl group having 1 to 30 carbon atoms, s represents an integer of 0 to 5, * indicates a bonding bond. [3] The resin composition according to [1] or [2], wherein the component (C) contains an active ester curing agent. [4] The resin composition according to any one of [1] to [3], wherein the component (C) contains a phenolic curing agent. [5] The resin composition according to any one of [1] to [4], further comprising (E) a radical polymerizable compound. [6] The resin composition according to [5], wherein the component (E) contains a maleimide-based radical polymerizable compound. [7] A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of [1] to [6], which is provided on the support. [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 described in [8]. Effects of the Invention

[0009] According to the present invention, there can be provided a resin composition which can produce a cured product having low dielectric properties, high adhesion to a conductor layer (peel strength), and excellent mechanical strength, a resin sheet using the resin composition, a printed wiring board, and a semiconductor device. DETAILED DESCRIPTION

[0010] Hereinafter, the present invention will be described in detail based on its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be implemented with arbitrary changes within the scope of the claims and their equivalents.

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

[0012] In the resin composition of the present invention, it is possible to further include any component (optionally included component) in combination with components (A) to (D). As the arbitrary component, for example, (E) a free radical polymerizable compound, (F) a thermoplastic resin, (G) a curing accelerator, (H) an organic filler, (I) other additives, and (J) a solvent, etc. can be cited. Hereinafter, each component contained in the resin composition of the present invention is described in detail.

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

[0014] As component (A), a resin having a terminal functional group number greater than 2 and having a polyphenylene ether skeleton can be used. 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 atoms in the phenylene group of formula (a) are substituted by a substituent or the like. In the formula, * represents a bonding bond. [Chemical formula 4]

[0015] The number of terminal functional groups of component (A) is greater than 2, preferably greater than 2.1, and more preferably greater than 2.2. The upper limit is preferably less than 10, more preferably less than 5, and further preferably less than 3. By using a polyphenylene ether resin having a terminal functional group number within such a range, a cured product having excellent dielectric properties, high adhesion to the conductor layer, and excellent mechanical strength can be obtained. The number of terminal functional groups is a numerical value representing the average value of the functional groups present at the end of each molecule of component (A). The method for determining the terminal functional group varies depending on the type of functional group. For example, when the terminal functional group is a hydroxyl group, a mixed solution can be prepared by adding tetraethylammonium hydroxide that associates with the hydroxyl group in component (A), and the absorbance of the prepared mixed solution is measured to determine the absorbance. In addition, 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 deuterated solvent and measured. 1 H-NMR. 1H-NMR can determine the number of terminal functional groups based on the integrated value of the peak derived from the terminal functional group, the integrated 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. The details can be determined by the method described in the examples below.

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

[0017] The functional group at the end of the component (A) includes a hydroxyl group, an acryloyl group, a methacryloyl group, a styryl group, etc. Among them, from the viewpoint of significantly obtaining the effects of the present invention, the functional group is preferably any of a hydroxyl group and a methacryloyl group, and more preferably a hydroxyl group.

[0018] The number average molecular weight of the component (A) is 100 or more, more preferably 500 or more, and further preferably 1000 or more, from the viewpoint of significantly obtaining the effects of the present invention, and is preferably 5000 or less, more preferably 3000 or less, and further 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] The glass transition temperature (Tg) of the component (A) is preferably 120° C. or higher, more preferably 130° C. or higher, further 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, further preferably 200° C. or lower, or 190° C. or lower, from the viewpoint of significantly obtaining the effects of the present invention. The glass transition temperature (Tg) can be measured by the method described in the Examples described below.

[0020] The component (A) preferably has a structure represented by the following formula (A-1). [Chemical formula 5] In formula (A-1), X represents an a-valent linking group, Z each independently represents a hydrogen atom or a group represented by formula (A-3), and R 11 Each independently represents a hydrogen atom or a group represented by formula (A-2), 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, and 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 In the case of hydrogen atoms, R 22 and R 24 Except for the case where one of them is a group represented by formula (A-2) and the other represents a hydrogen atom, a methyl group or an ethyl group. a and b each independently represent an integer of 2 to 6, k each independently represents an integer of 1 to 4, and n each independently represents an integer of 0 to 200. [Chemical formula 6] In formula (A-2), R 31 and R 34 Each independently represents an alkylene group having 1 to 8 carbon atoms, and 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. [Chemical formula 7] In formula (A-3), R 41 Each independently represents a divalent hydrocarbon group having 1 to 30 carbon atoms, and R 42 , R 43 and R 44 Each independently represents a hydrogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylamino group, or a hydroxyalkyl group having 1 to 30 carbon atoms. 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 represent an integer of 2 to 4. It is preferred that a and b represent the same integer.

[0022] In formula (A-1), n ​​represents an integer of 0 to 200, and preferably represents 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 formed by 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 a-valent aliphatic hydrocarbon groups, a-valent aromatic hydrocarbon groups, groups formed by combinations thereof, etc., with a-valent aliphatic hydrocarbon groups being preferred. The aliphatic hydrocarbon group can be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, with a saturated aliphatic hydrocarbon group being preferred. The aliphatic hydrocarbon group can be a chain hydrocarbon group, a cyclic hydrocarbon group (i.e., an alicyclic hydrocarbon group), or a combination thereof. Furthermore, the chain hydrocarbon group can be either straight-chain or branched-chain, with a branched-chain being 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 a-valent aromatic hydrocarbon group 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 a-valent hydrocarbon group include the groups represented by the following formulas (a1) to (a2). In the formulas, * represents a bonding site. [Chemical formula 8]

[0027] The a-valent hydrocarbon group may optionally have a substituent. There is no particular limitation on the substituent, and examples thereof include a halogen atom, -OH, -O-C 1-6 alkyl, -N(C 1-10 alkyl)2, C 1-10 alkyl, C 6-10 aryl, -NH2, -CN, -C(O)O-C 1-10 alkyl, -COOH, -C(O)H, -NO2, etc. Here, the term "C p-q " (where p and q are positive integers and p < q) means that the number of carbon atoms in the organic group immediately following this term is p to q. For example, the expression "C 1-10 alkyl" means an alkyl group having 1 to 10 carbon atoms. These substituents may also combine with each other to form a ring, and the ring structure also includes a spiro ring or a fused ring.

[0028] The above-mentioned substituents may further optionally have a substituent (hereinafter sometimes referred to as a "secondary substituent"). As the secondary substituent, the same groups as the above-mentioned substituents can be used as long as there is no particular description.

[0029] Examples of the a-valent group formed by the combination of an ester bond and a hydrocarbon group include: an a-valent group formed by the combination of an ester bond and an alkylene group, an a-valent group formed by the combination of an ester bond and an arylene group, an a-valent group formed by the combination of an ester bond, an alkylene group, and an a-valent hydrocarbon group, an a-valent group formed by the combination of an ester bond, an arylene group, and an a-valent hydrocarbon group, etc., with an a-valent group formed by the combination of an ester bond, an alkylene group, and an a-valent hydrocarbon group being 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 still 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 1,1-dimethyl-1,3-propylene group, a 3,3-dimethyl-1,3-propylene group, a hexamethylene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, a 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, 3,3-dimethyl-1,4-butylene, 1,2-dimethyl-1,4-butylene, 1,3-dimethyl-1,4-butylene, 2,3-dimethyl-1,4-butylene, heptamethylene, 1-methyl-1,6-hexylene, 2-methyl-1,6-hexylene, 3-methyl-1,6-hexylene, 4-methyl-1,6-hexylene , 5-methyl-1,6-hexylene, 1-ethyl-1,5-pentylene, 2-ethyl-1,5-pentylene, 3-ethyl-1,5-pentylene, 1,1-dimethyl-1,5-pentylene, 2,2-dimethyl-1,5-pentylene, 3,3-dimethyl-1,5-pentylene, 4,4-dimethyl-1,5-pentylene, 1,2-dimethyl-1,5-pentylene, 1,3-dimethyl-1,5-pentylene, 1,4-dimethyl-1,5-pentylene, 2,3-dimethyl-1,5-pentylene, 2,4-dimethyl-1,5-pentylene, 3,4-dimethyl-1,5-pentylene, 2-methyl-3,3-dimethyl-1,4-butylene, 1- Methyl-3,3-dimethyl-1,4-butylene, 1,2,3-trimethyl-1,4-butylene, 1,3-dimethyl-1,4-pentylene, 2-isopropyl-1,4-butylene, 2-methyl-1,4-cyclohexylene, 3-methyl-1,4-cyclohexylene, 4-methyl-1,4-cyclohexylene, 1-cyclohexylmethylene, 2-ethyl-1,3-cyclopentylene, 3-ethyl-1,3-cyclopentylene, 2,3-dimethyl-1,3-cyclopentylene, 2,4-dimethyl-1,3-cyclopentylene, 2-methyl-1,3-cyclopentylmethylene, 2-cyclopentylethylidene, 1-cyclopentylethylidene, octamethylene, 1-methyl-1,7-heptylene, 1-ethyl-1,6-hexylene, 1-propyl-1,5-pentylene, 2-methyl-1,7-heptylene, 3-methyl-1,7-heptylene, 4-methyl-1,7-heptylene, 5-methyl-1,7-heptylene, 6-methyl-1,7-heptylene, 2-ethyl-1,6-hexylene, 3-ethyl-1,6-hexylene, 4-ethyl-1,6-hexylene, 5-ethyl-1,6-hexylene, 1,1-dimethyl-1,6-hexylene, 2,2-dimethyl-1,6-hexylene, 3,3-dimethyl-1,6-hexylene, 4,4-dimethyl-1,6-hexylene, 5,5-dimethyl-1,6-hexylene, 1,2-dimethyl-1,6-hexylene, 1,3-dimethyl-1,6 -hexylene, 1,4-dimethyl-1,6-hexylene, 1,5-dimethyl-1,6-hexylene, 2,3-dimethyl-1,6-hexylene, 2,4-dimethyl-1,6-hexylene, 2,5-dimethyl-1,6-hexylene, 1,1-ethylmethyl-1,5-pentylene, 2,2-ethylmethyl-1,5-pentylene, 3,3-ethylmethyl-1,5-pentylene, 4,4-ethylmethyl-1,5-pentylene, 1-ethyl-2-methyl-1,5-pentylene, 1-ethyl-3-methyl-1,5-pentylene, 1-ethyl-4-methyl-1,5-pentylene, 2-ethyl-1-methyl-1,5-pentylene, 3-ethyl-1-methyl-1,5-pentylene, 4 -ethyl-1-methyl-1,5-pentylidene, 2-ethyl-3-methyl-1,5-pentylidene, 2-ethyl-4-methyl-1,5-pentylidene, 3-ethyl-2-methyl-1,5-pentylidene, 4-ethyl-3-methyl-1,5-pentylidene, 3-ethyl-4-methyl-1,5-pentylidene, 4-ethyl-3-methyl-1,5-pentylidene, 1-(2-methylpropyl)-1,4-butylene, 1-(2-methylpropyl)-2-methyl-1,4-butylene, 1,1-(2-methylpropyl)ethylidene, 1,1-(2-methylpropyl)ethyl-1,3-propylene, 1,1-diethyl-1,3-propylene, 2,2-diethyl-1,3-propylene, 1,1- Ethylmethyl-2,2-dimethyl-1,3-propylene, 2,2-ethylmethyl-1,1-dimethyl-1,3-propylene, 2-ethyl-1,1-dimethyl-1,4-butylene, 2,3-dimethyl-1,4-cyclohexylene, 2,3-dimethyl-1,4-cyclohexylene, 2,5-dimethyl-1,4-cyclohexylene, 2,6-dimethyl-1,4-cyclohexylene, 3,5-dimethyl-1,4-cyclohexylene, 2-methyl-1,4-cyclohexyl-1-methylene, 3-methyl-1,4-cyclohexyl-1-methylene, 4-methyl-1,4-cyclohexyl-1-methylene, 2-ethyl-1,4-cyclohexylene, 3-ethyl-1,4-cyclohexylene, 4-ethyl-1,4-cyclohexylene, 2-cyclohexylethylene, 1-cyclohexylethylene, 1-cyclohexyl-2-ethylene, nonylmethylene, 1-methyl-1,8-octylene, decylmethylene, 1-methyl-1,8-nonylene, undecylmethylene, dodecylmethylene, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, methylene-1,4-phenylene-methylene, ethylene-1,4-phenylene-ethylene, etc., preferably methylene and ethylene, more preferably ethylene.

[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 still more preferably an arylene group having 6 to 12 carbon atoms. Specific examples of the arylene group include phenylene, naphthylene, anthrylene, and the like.

[0032] Specific examples of the a-valent group formed by a combination of an ester bond and a hydrocarbon group include a group represented by the following formula (a3): wherein * represents a bonding bond. [Chemical formula 9]

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

[0034] In formula (A-1), X preferably represents an α-valent hydrocarbon group, or an α-valent group formed by a combination of an ester bond, an alkylene group and an α-valent hydrocarbon group, more preferably represents an α-valent aliphatic hydrocarbon group, or an α-valent group formed by a combination of an ester bond, an alkylene group and an α-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), Z each 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 a carbon number of 1 to 30. 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 any of a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group, and is preferably a saturated aliphatic hydrocarbon group. The divalent aliphatic hydrocarbon group may be a chain hydrocarbon group, a cyclic hydrocarbon group (i.e., an alicyclic hydrocarbon group), or a combination thereof. Furthermore, the chain hydrocarbon group may be any of a straight chain and a branched chain, and is preferably a branched chain. 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 further 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, and is preferably an alkylene group.

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

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

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

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

[0042] Examples of the arylene group include a phenylene group, a naphthylene group, and an anthracene 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 the a-valent linking group represented by X in formula (A-1) may have.

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

[0045] The monovalent hydrocarbon group having 1 to 30 carbon atoms includes a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a group formed by a combination thereof, and the like, preferably a monovalent aliphatic hydrocarbon group. The monovalent aliphatic hydrocarbon group may be any of a monovalent saturated aliphatic hydrocarbon group and a monovalent unsaturated aliphatic hydrocarbon group, and preferably a monovalent saturated aliphatic hydrocarbon group. The monovalent aliphatic hydrocarbon group may be a chain hydrocarbon group, a cyclic hydrocarbon group (i.e., an alicyclic hydrocarbon group), or a combination thereof. Furthermore, the chain hydrocarbon group may be any of a straight chain and a branched chain, and preferably a branched chain. 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 further 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 more preferably a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Specific examples of the monovalent aromatic hydrocarbon group include aryl groups and the like.

[0047] Examples of the alkyl group include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, pentyl, cyclopentyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, n-hexyl, cyclohexyl, 1-ethylbutyl, 2-ethylbutyl, 3-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentylidene, 4-methylpentylidene, 1,1-dimethylbutylene, 2,2-dimethylbutylene, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 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-dimethyl Cyclopentyl, 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, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, 1,1-ethyl 2,2-ethylmethylpentyl, 3,3-ethylmethylpentyl, 4,4-ethylmethylpentyl, 1-ethyl-2-methylpentyl, 1-ethyl-3-methylpentyl, 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, 1,1-(2-methylpropyl)ethyl, 1,1-(2-methylpropyl)ethylpropyl, 1,1-diethylpropyl, 2,2-diethylpropyl, 1,1-ethylmethyl-2,2-dimethylpropyl, 2,2-ethylmethyl-1,1-dimethylpropyl, 2-ethyl-1,1-dimethylbutyl, 2,3-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 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, propargyl, etc. ,

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

[0049] Examples of the group formed by a combination of these groups 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 methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, 2-butoxy, tert-butoxy, 1-pentyloxy, 2-pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, 2-ethylpropoxy, 3,3-dimethylpropoxy, 1,1-dimethylpropoxy, cyclopentyloxy, 1-hexyloxy, 2-hexyloxy, 3-hexyloxy, 4-methylpentyloxy, 3-methylpentyloxy, 2-methylpentyloxy, 1, 1-dimethyl-1-butoxy, 2,2-dimethyl-1-butoxy, 3,3-dimethyl-1-butoxy, 4,4-dimethyl-1-butoxy, 1,2-dimethyl-1-butoxy, 1,3-dimethyl-1-butoxy, 2-ethyl-1-butoxy, 3-ethyl-1-butoxy, 3,3-ethylmethyl-1-propoxy, cyclohexyloxy, 1-octyloxy, 2-octyloxy, 3-octyloxy, 4-octyloxy, 2-ethyl-1-hexyloxy, phenylmethoxy and the like.

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

[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 dimethylamino, ethylmethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-tert-butylamino, and dicyclohexylamino.

[0053] The carbon number of the hydroxyalkyl group having 1 to 30 carbon atoms is preferably 1 to 20, 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 the a-valent linking group represented by X in formula (A-1) may have.

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

[0056] In the 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 of the alkylene group having 1 to 8 carbon atoms is preferably 1 to 6, and more preferably 1 to 3. Specific examples of the alkylene group having 1 to 8 carbon atoms are the same as the alkylene group having 1 to 8 carbon atoms 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 R 33 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 are 42 The alkyl groups in the hydrocarbon groups having 1 to 30 carbon atoms represented by are the same as the alkyl groups having 1 to 8 carbon atoms. 32 and R 33 Preferably it represents methyl.

[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 and R in formula (A-2) 32 The alkyl groups having 1 to 8 carbon atoms represented by R are the same. 35 , preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, 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 the a-valent linking group represented by X in formula (A-1) may have.

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

[0063] In formula (A-2), d and e represent 0, R 32 , R 33 and R 35 It preferably represents an alkyl group having 1 to 8 carbon atoms, and more preferably represents a tert-butyl group in formula (A-2).

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

[0065] In formula (A-1), 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. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0066] The monovalent hydrocarbon group having 1 to 12 carbon atoms includes a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a group formed by a combination thereof, and is preferably a monovalent aliphatic hydrocarbon group. The monovalent aliphatic hydrocarbon group may be any of a monovalent saturated aliphatic hydrocarbon group and a monovalent unsaturated aliphatic hydrocarbon group, and is preferably a monovalent saturated aliphatic hydrocarbon group. The monovalent aliphatic hydrocarbon group may be a chain hydrocarbon group, a cyclic hydrocarbon group (i.e., an alicyclic hydrocarbon group), or a combination thereof. Furthermore, the chain hydrocarbon group may be any of a straight chain and a branched chain, and is preferably a branched chain. 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 further 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, and more preferably a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. Specific examples of the monovalent aromatic hydrocarbon group include aryl groups, and examples of the aryl group include phenyl and naphthyl groups.

[0068] Specific examples of the alkyl group having 1 to 12 carbon atoms include: 42 The alkyl groups in the hydrocarbon groups having 1 to 30 carbon atoms represented by are the same as the alkyl groups 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 further 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 the a-valent linking group represented by X in formula (A-1) may have.

[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 Both represent hydrogen atoms, and R 22 and R24 Except for the case where one of them is a group represented by formula (A-2) and the other represents a hydrogen atom, a methyl group or an ethyl group. 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] (A) Component can be synthesized by a known method. As a specific synthesis method, for example, it can be synthesized by the method described in International Publication No. 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 component (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and preferably 15% by mass or less, more preferably 13% by mass or less, further preferably 10% by mass or less, when the non-volatile component in the resin composition is set to 100% by mass.

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

[0074] In the present invention, unless otherwise expressly stated, the content of each component in the resin composition is the value when the non-volatile component in the resin composition is set to 100% by mass, and the non-volatile component refers to all non-volatile components in the resin composition except the solvent. In addition, the resin component in the resin composition represents the component other than the (D) inorganic filler in the non-volatile component in the resin composition.

[0075] <(B) Epoxy resin> The resin composition contains (B) epoxy resin as (B) component. The (B) epoxy resin as the (B) component does not contain any substance belonging to the above-mentioned (A) component. By containing (B) epoxy resin in the resin composition, a cured product showing good mechanical strength and insulation reliability can be obtained. (B) Epoxy resins can be used alone or in combination of two or more.

[0076] Examples of the epoxy resin (B) include bixylene 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 epoxy resins, glycidylcyclohexane type epoxy resins. 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, epoxy resins containing spiro rings, cyclohexane type epoxy resins, cyclohexanedimethanol 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] In the resin composition, as component (B), an epoxy resin having two or more epoxy groups in one molecule is preferably included. From the viewpoint of significantly obtaining the desired effect of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the epoxy resin (B).

[0078] The epoxy resin includes an epoxy resin that is liquid at a temperature of 20°C (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20°C (hereinafter sometimes referred to as "solid epoxy resin"). The resin composition may contain only a liquid epoxy resin or only a solid epoxy resin as component (B), and preferably contains a liquid epoxy resin and a solid epoxy resin in combination. Among them, from the viewpoint of significantly obtaining the effect of the present invention, it is preferred to contain a liquid epoxy resin and a solid epoxy resin in combination.

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

[0080] As the liquid epoxy resin, preferred are 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, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resin having a butadiene structure, glycidyl cyclohexane type epoxy resin, phenol benzopyrrolone type epoxy resin, alkyl diglycidyl ether type epoxy resin, more preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, alkyl diglycidyl ether type epoxy resin, and further preferably naphthalene type epoxy resin, bisphenol A type epoxy resin, and bisphenol F type epoxy resin.

[0081] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "EPIKOTE828EL" (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; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical Materials Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; and "CELLOXIDE 2021P" (alicyclic epoxy resin with an ester skeleton); "PB-3600" manufactured by Daicel Corporation (epoxy resin with a butadiene structure); "ZX1658" and "ZX1658GS" manufactured by Nippon Steel Chemical Materials Co., Ltd. (liquid 1,4-glycidylcyclohexane type epoxy resin), "YED216D" (alkyl diglycidyl ether type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. They can be used alone or in combination of two or more.

[0082] The solid epoxy resin is preferably a solid epoxy resin having two or more epoxy groups in one molecule, more preferably a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

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

[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) manufactured by DIC Corporation; “EPPN-502H” (trisphenol type epoxy resin), “NC7000L” (naphthol novolac type epoxy resin), “NC3000H”, “NC3000L” (naphthylene ether type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. 000", "NC3000L", "NC3100" (biphenyl epoxy resin); "ESN475V" (naphthalene epoxy resin), "ESN485" (naphthol novolac epoxy resin) made by Nippon Steel Chemical Materials Co., Ltd.; "YX4000H", "YL6121" (biphenyl epoxy resin), "YX4000HK" (biphenyl epoxy resin), "YX8800" (anthracene epoxy resin) made by Mitsubishi Chemical Corporation. "PG-100", "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), "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR-991S" (phenol benzopyrrolidone 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), their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5. By making the mass ratio of the liquid epoxy resin to the solid epoxy resin within such a range, the desired effect of the present invention can be significantly obtained.

[0086] The epoxy equivalent of component (B) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., further preferably 80 g / eq. to 2000 g / eq., and further more preferably 110 g / eq. to 1000 g / eq. Within this range, a cured product of the resin composition having a sufficient crosslinking density can be obtained. The epoxy equivalent is the mass of an epoxy resin containing 1 equivalent of epoxy groups. The epoxy equivalent can be measured according to JIS K 7236.

[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 even more 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 showing good mechanical strength and insulation reliability, the content of the component (B) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 45% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less or 12% by mass or less, when the non-volatile component in the resin composition is set to 100% by mass.

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

[0090] <(C) Curing agent> The resin composition contains a (C) curing agent as the (C) component. The (C) curing agent as the (C) component does not contain any substance belonging to the above-mentioned (A) to (B) components. The (C) component generally has the function of reacting with the (B) component to cure the resin composition. The (C) component can be used alone or in combination of two or more in any ratio.

[0091] As the component (C), a compound that can react with the component (B) 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 curing agents, etc. Among them, as the component (C), from the viewpoint of significantly obtaining the effect of the present invention, it is preferred that any one of active ester curing agents, phenolic curing agents, cyanate curing agents, and carbodiimide curing agents be included, and it is more preferred that any one of active ester curing agents and phenolic curing agents be included.

[0092] As active ester curing agent, curing agent with more than one active ester group in one molecule can be enumerated. Wherein, as active ester curing agent, preferably esters of phenolic esters, thiophenolic esters, N-hydroxylamine esters, heterocyclic hydroxy compounds, etc. have more than two compounds with high reactive ester groups in one molecule. The active ester curing agent is preferably obtained by the condensation reaction of carboxylic acid compounds and / or thiocarboxylic acid compounds with hydroxy compounds and / or thiol compounds. Particularly from the viewpoint of heat resistance improvement, the active ester curing agent preferably obtained by carboxylic acid compounds and hydroxy compounds, more preferably the active ester curing agent obtained by carboxylic acid compounds and phenol compounds and / or naphthol compounds.

[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 the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the so-called "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0095] Preferred specific examples of active ester curing agents include active ester compounds containing dicyclopentadiene diphenol structures, active ester compounds containing naphthalene structures, active ester compounds containing acetylated products of novolac resins, and active ester compounds containing benzoylated products of novolac resins. Among them, active ester compounds containing naphthalene structures and active ester compounds containing dicyclopentadiene diphenol structures are more preferred. "Dicyclopentadiene diphenol structure" means a divalent structure formed by phenylene-dicyclopentylene-phenylene.

[0096] As commercially available products of active ester curing agents, as active ester compounds containing a dicyclopentadiene-type diphenol structure, there are "EXB-9451", "EXB-9460", "EXB-9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65TM" (manufactured by DIC Corporation); as active ester compounds containing a naphthalene structure, there are "HPC-8150-60T", "HPC-8150-62T", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65 T", "EXB-9416-70BK", "EXB-8150-62T" (manufactured by DIC Corporation); as an active ester compound containing an acetylated product of a linear phenolic resin, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be cited; as an active ester compound containing a benzoylated product of a linear phenolic resin, "YLH1026" (manufactured by Mitsubishi Chemical Corporation) can be cited; as an active ester curing agent that is an acetylated product of a linear phenolic resin, "DC808" (manufactured by Mitsubishi Chemical Corporation) can be cited; as an active ester curing agent that is a benzoylated product of a linear phenolic resin, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) can be cited.

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

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

[0099] As phenolic curing agents, curing agents having one or more, preferably two or more, hydroxyl groups bonded to aromatic rings (benzene rings, naphthalene rings, etc.) in one molecule can be cited. Among them, compounds having hydroxyl groups bonded to benzene rings are preferred. In addition, from the viewpoints of heat resistance and water resistance, phenolic curing agents having a phenolic structure are preferred. Furthermore, from the viewpoint of close adhesion, nitrogen-containing phenolic curing agents are preferred, and phenolic curing agents containing a triazine skeleton are more preferred. In particular, from the viewpoint of highly satisfying heat resistance, water resistance and close adhesion, linear phenolic resin curing agents containing a triazine skeleton are preferred.

[0100] Specific examples of phenolic curing agents and naphthol curing agents include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" manufactured by Meiwa Chemicals; "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 Chemicals Co., Ltd. , "SN-395"; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" manufactured by DIC; "GDP-6115L", "GDP-6115H", "ELPC 75" and so on manufactured by Qunrong Chemical Co., Ltd.

[0101] Specific examples of the benzoxazine-based curing agent include “ODA-BOZ” manufactured by JFE Chemical Co., Ltd., “HFB2006M” manufactured by Showa High Molecular Co., Ltd., and “Pd” and “Fa” manufactured by Shikoku Chemical Industry Co., Ltd.

[0102] Specific examples of the carbodiimide-based curing agent include "V-03", "V-05", and "V-07" manufactured by Nisshinbo Chemical Co., Ltd. and Stabaxol (registered trademark) P manufactured by LANXESS.

[0103] Examples of the acid anhydride curing agent include curing agents 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, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, dicarboxylic anhydride, and the like. Benzophenonetetracarboxylic 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(trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, etc. Acid anhydride curing agents can be commercially available products, for example, "MH-700" manufactured by Shin Nippon Rika Co., Ltd., etc.

[0104] As the amine curing agent, there can be mentioned a curing agent having one or more amino groups in one molecule, for example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. Among them, from the viewpoint of exerting the desired effect of the present invention, aromatic amines are preferred. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine curing agent include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, metaphenylenediamine, metaphenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino- 4-hydroxyphenyl)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. As the amine curing agent, commercially available products can be used, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "EPICUREW" manufactured by Mitsubishi Chemical Corporation can be mentioned.

[0105] Examples of the cyanate curing agent include difunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac resins and cresol novolac resins; and prepolymers obtained by triazinizing a portion of these cyanate resins. Specific examples of cyanate curing agents include "PT30" and "PT60" manufactured by Arxada (both are linear phenolic resin-type multifunctional cyanate resins), "ULL-950S" (multifunctional cyanate resin), "BA230", "BA230S75" (prepolymers obtained by triazine-forming a trimer of part or all of bisphenol A dicyanate), etc.

[0106] When the number of epoxy groups of component (B) is set to 1, the active radical number of the (C) curing agent is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, preferably 10 or less, more preferably 5 or less, and further preferably 3 or less. Here, the so-called "number of epoxy groups of component (B)" refers to the value obtained by adding up all the values ​​obtained by dividing the mass of the non-volatile components of component (B) present in the resin composition by the epoxy equivalent. In addition, the so-called "active radical number of the (C) curing agent" refers to the value obtained by adding up all the values ​​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. By setting the active radical number of the (C) curing agent when the number of epoxy groups of component (B) is set to 1 within the above range, the desired effect 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, when the non-volatile component in the resin composition is set to 100 mass %, is preferably 1 mass % or more, more preferably 5 mass % or more, further preferably 8 mass % or more, and is preferably 30 mass % or less, more preferably 20 mass % or less, and further preferably 18 mass % or less.

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

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

[0110] Inorganic compounds can be used as the material of (D) inorganic filler. As the material of (D) inorganic filler, for example, silicon dioxide, aluminum oxide, 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, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate, etc. can be cited. Among them, silicon dioxide is particularly preferred. As silicon dioxide, for example, amorphous silicon dioxide, fused silica, crystalline silicon dioxide, synthetic silicon dioxide, hollow silica, etc. can be cited. In addition, as silicon dioxide, spherical silicon dioxide is preferably used.

[0111] (D) Commercially available products of the inorganic filler include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemicals Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Yaduma 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 Co., Ltd.; "Cellspheres" and "MGH-005" manufactured by Pacific Cement Co., Ltd.; and "Exfil" and "BA-1" manufactured by JGC Catalysts & Chemicals Co., Ltd.

[0112] The average particle size of the inorganic filler (D) is preferably 0.01 μm or more, more preferably 0.1 μm or more, further preferably 0.3 μm or more, and is preferably 10 μm or less, more preferably 5 μm or less, further 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 Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median particle size can be measured as the average particle size. The sample can be measured using 100 mg of inorganic filler and 10 g of methyl ethyl ketone weighed into a vial and dispersed with ultrasound for 10 minutes. For the sample, a laser diffraction particle size distribution measuring device is used, and the wavelength of the light source is set to blue and red, and the particle size distribution of the volume basis of the inorganic filler is measured by a flow cell method, and the average particle size is calculated as the median particle size by the obtained particle size distribution. As a laser diffraction particle size distribution measuring device, for example, "LA-960" manufactured by Horiba Manufacturing Co., Ltd. can be cited.

[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 obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method.

[0116] From the viewpoint of improving moisture resistance and dispersibility, (D) inorganic filler is preferably treated with a surface treatment agent. As the surface treatment agent, for example, fluorine-containing silane coupling agent, aminosilane coupling agent, epoxysilane coupling agent, mercaptosilane coupling agent, silane coupling agent, alkoxysilane, organosilazane compound, titanate coupling agent, etc. can be cited. The surface treatment agent can be used alone or in any combination of two or more.

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

[0118] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment using 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% by mass to 5% by mass of the surface treatment agent, more preferably with 0.2% by mass to 3% by mass of the surface treatment agent, and further preferably with 0.3% by mass to 2% by mass of the surface treatment agent.

[0119] The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m 2 More preferably 0.1 mg / m 2 More preferably, 0.2 mg / m 2 On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition from increasing, it is preferably 1.0 mg / m 2 Below, more preferably 0.8 mg / m 2 Below, more preferably 0.5 mg / m 2 the following.

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

[0121] In addition, the degree of surface treatment performed by the surface treatment agent can be evaluated by the carbon amount per unit mass of the inorganic filler. The carbon amount per unit mass of the inorganic filler is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and in addition, preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and further preferably 0.5% by mass or less. (D) The carbon amount per unit mass of the inorganic filler can be measured using a carbon analyzer in the same manner as the carbon amount per unit surface area of ​​the inorganic filler (D).

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

[0123] <(E) Radically polymerizable compound> The resin composition may contain (E) a radical polymerizable compound as an arbitrary component (optionally contained component). The (E) radical polymerizable compound as the (E) component does not include substances belonging to the (A) to (D) components. The (E) component may be used alone or in combination of two or more.

[0124] (E) The radical polymerizable compound may contain an ethylenically unsaturated bond. Therefore, 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, allyl, 1-propenyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, and 4-vinylphenyl; α,β-unsaturated carbonyl groups such as acryl, methacryloyl, and maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl). The (E) radical polymerizable compound preferably has two or more radical polymerizable groups.

[0125] (E) radical polymerizable compounds include, for example, (meth)acrylic radical polymerizable compounds, styrene radical polymerizable compounds, allyl radical polymerizable compounds, maleimide radical polymerizable compounds, etc. Among them, as (E) component, it is preferred to include a maleimide radical polymerizable compound from the viewpoint of significantly obtaining the effects of the present invention.

[0126] The (meth)acrylic radical polymerizable compound may be, 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 aliphatic (meth)acrylate compounds having a low molecular weight (molecular weight less than 1000) such as 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, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; and dioxanediol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate. Ether-containing (meth)acrylate compounds having a low molecular weight (molecular weight less than 1000) such as di(meth)acrylate, 3,6,9-trioxaundecane-1,11-diol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, etc.; isocyanurate-containing (meth)acrylate compounds having a low molecular weight (molecular weight less than 1000) such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, etc.; and acrylate compounds having a high molecular weight (molecular weight of 1000 or more) such as (meth)acrylic modified polyphenylene ether resin. Examples of commercially available (meth)acrylic radical polymerizable compounds include “A-DOG” (dioxanediol diacrylate) manufactured by Shin-Nakamura Chemical Industry 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” (dioxanediol diacrylate) manufactured by Nippon Kayaku Co., Ltd., and “SA9000” and “SA9000-111” (methacrylic modified polyphenylene ether) manufactured by SABIC.

[0127] The styrene-based free radical polymerizable compound may be, 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-based free radical polymerizable compound include low molecular weight (molecular weight less than 1000) styrene-based compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether; and high molecular weight (molecular weight greater than 1000) styrene-based compounds such as vinylbenzyl-modified polyphenylene ether resins and styrene-divinylbenzene copolymers. Examples of commercially available styrene-based radical polymerizable compounds include “ODV-XET (X03)”, “ODV-XET (X04)”, and “ODV-XET (X05)” (styrene-divinylbenzene copolymers) manufactured by Nippon Steel Chemical Materials Co., Ltd. and “OPE-2St 1200” and “OPE-2St 2200” (vinyl benzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0128] The allyl radical polymerizable compound may be, for example, a compound having one or more, preferably two or more, allyl groups. Examples of the allyl radical polymerizable compound include aromatic carboxylic acid allyl ester compounds such as diallyldiphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalene dicarboxylate, and diallyl 2,3-naphthalene dicarboxylate; 1,3,5-triallyl isocyanurate, 1,3-diallyl-5-glycidyl isocyanurate; Aromatic allyl compounds containing epoxy groups such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; aromatic allyl compounds containing benzoxazine such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; aromatic allyl compounds containing ethers such as 1,3,5-triallyl ether benzene; allyl silane compounds such as diallyldiphenylsilane. Commercially available products of allyl radical polymerizable compounds include, for example, "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Chemical Industry Co., Ltd., Nisshoku TechnoFine Chemical Co., Ltd., and Nisshoku TechnoFine Chemical Co., Ltd. "DAD" (diallyl dibenzoate) manufactured by Fujifilm Wako Pure Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Fujifilm Wako Pure Chemical Co., Ltd., "DAND" (diallyl 2,3-naphthalenedicarboxylate) manufactured by Nichikyu Techno Fine Chemicals Co., Ltd., "ALP-d" (bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane) manufactured by Shikoku Chemical Co., Ltd., "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 Chemical Co., Ltd.

[0129] The maleimide radical polymerizable compound may be, 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 having an aliphatic amine skeleton, or an aromatic maleimide compound having an aromatic amine skeleton. Commercially available products of maleimide-based 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" (maleimide compounds containing a dimer diamine structure) manufactured by Designer Molecules Inc., "BMI-6100" (aromatic maleimide compound) manufactured by Designer Molecules Inc., "MIR-5000-60T" and "MIR-3000-70MT" (biphenyl aralkyl type maleimide compounds) manufactured by Nippon Kayaku Co., Ltd., "BMI-70" and "BMI-80" manufactured by KI Chemicals Co., Ltd., and "BMI-2300" and "BMI-TMH" manufactured by Yamato Chemicals Co., Ltd. In addition, as the maleimide-based radical polymerizable compound, a maleimide resin (maleimide compound containing an indane ring skeleton) disclosed in Japan Invention Association Publication No. 2020-500211 can also be used.

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

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

[0132] The content of the component (E) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, when the non-volatile component in the resin composition is 100% by mass.

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

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

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

[0136] As the polyimide resin, a resin having an imide structure can be used. The polyimide resin generally includes a resin obtained by an imidization reaction of a diamine compound and an acid anhydride. As a specific polyimide resin, for example, the polyimide resin described in Japanese Patent Publication No. 2021-14544 can be cited.

[0137] A commercially available product may be used as the polyimide resin. Examples of the commercially available product include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Chemical Industries, Ltd.

[0138] As the polycarbonate resin, a resin having a carbonate structure can be used. As such a resin, there can be mentioned carbonate resins without reactive groups, carbonate resins containing hydroxyl groups, carbonate resins containing phenolic hydroxyl groups, carbonate resins containing carboxyl groups, carbonate resins containing anhydride groups, carbonate resins containing isocyanate groups, carbonate resins containing carbamate groups, etc. Reactive groups here refer to functional groups that can react with other components such as hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, anhydride groups, isocyanate groups, carbamate groups, and epoxy groups.

[0139] Commercially available carbonate resins may be used, such as "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei 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, bisphenol acetophenone skeleton, phenolic 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 are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (a phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel Chemical Materials Co., Ltd.; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical Corporation; etc.

[0142] Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin 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 the polyamideimide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane skeleton) manufactured by Resonac.

[0144] Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like.

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

[0146] Specific examples of the polysulfone resin include polysulfone "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, particularly preferably 20,000 or more, and is preferably 70,000 or less, more preferably 60,000 or less, particularly preferably 50,000 or less.

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

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

[0150] <(G) Curing accelerator> The resin composition may contain (G) a curing accelerator as an arbitrary component. The (G) curing accelerator as the (G) component does not include substances belonging to the (A) to (F) components. Examples of the (G) curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Preferably, it is an amine-based curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator, and more preferably, it is any one of an amine-based curing accelerator and an imidazole-based curing accelerator. One curing accelerator may be used alone, or two or more may be used in combination.

[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, and butyltriphenylphosphonium thiocyanate, and preferably triphenylphosphine and tetrabutylphosphonium decanoate.

[0152] Examples of the amine-based 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, and 4-dimethylaminopyridine and 1,8-diazabicyclo[5.4.0]-undecene are 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-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Imidazole compounds such as 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-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

[0154] As the imidazole-based curing accelerator, a commercially available item may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0155] Examples of the guanidine-based 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, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine. Preferred examples include dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0156] As metal curing accelerators, for example, metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin, organic metal complexes or organic metal salts can be cited. As specific examples of organic metal complexes, organic cobalt complexes such as cobalt acetylacetonate (II), cobalt acetylacetonate (III), organic copper complexes such as copper acetylacetonate (II), organic zinc complexes such as zinc acetylacetonate (II), organic iron complexes such as iron acetylacetonate (III), organic nickel complexes such as nickel acetylacetonate (II), and organic manganese complexes such as manganese acetylacetonate (II). As organic metal salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited.

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

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

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

[0160] (H) component is present in the resin composition in the form of particles. As (H) component, for example, rubber particles, polyamide microparticles, silicone particles, core-shell particles, etc. can be cited. In the present invention, from the viewpoint of significantly obtaining the desired effect of the present invention, it is preferred to use any one of rubber particles and core-shell particles, and it is more preferred to use core-shell particles.

[0161] As the rubber component contained in the rubber particles, for example, olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-butadiene terpolymer, ethylene-propylene-butylene terpolymer, and thermoplastic elastomers such as acrylic thermoplastic elastomers such as poly(meth)propyl acrylate, poly(meth)butyl acrylate, poly(meth)cyclohexyl acrylate, and poly(meth)octyl acrylate can be mentioned. In addition, silicone rubbers such as polyorganosiloxane rubber can be mixed in the rubber component. The glass transition temperature of the rubber component contained in the rubber particles is, for example, below 0°C, preferably below -10°C, more preferably below -20°C, and further preferably below -30°C.

[0162] As the rubber particles, commercially available products may be used, and examples thereof include "AC3401N" and "AC3816N" manufactured by Aica Industries, Ltd.

[0163] The so-called core-shell particles are particulate organic fillers formed by core particles containing rubber components such as those listed above and more than one shell portion covering the core particles. Furthermore, the core-shell particles are preferably core-shell graft copolymer particles formed by core particles containing rubber components such as those listed above and a shell portion formed by graft copolymerization of monomer components copolymerizable with the rubber components contained in the core particles. The so-called core-shell type herein does not necessarily refer only to the type that can clearly distinguish the core particles from the shell portion, but also includes the type in which the boundary between the core particles and the shell portion is not clear, and the core particles may not be completely covered by the shell portion.

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

[0165] Examples of the monomer component forming the shell portion of the core-shell graft copolymer particles include (meth)acrylates 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; (meth)acrylonitrile, etc. Among them, (meth)acrylates are preferred, and methyl (meth)acrylate is more preferred.

[0166] Commercially available products of core-shell type graft copolymer particles include, for example, "CHT" manufactured by Samsung SDI; "B602" manufactured by Techno-UMG; "PARALOID EXL2602", "PARALOID XL2603", "PARALOID EXL2655", "PARALOID EXL2311", "PARALOID EXL2313", "PARALOID XL2315", "PARALOID KM330", "PARALOID KM336P", "PARALOID KCZ201" manufactured by Dow Chemical Japan Co., Ltd.; "Metablen C-223A", "Metablen E-901", "Metablen S-2001", "Metablen W-450A", "Metablen SRK-200" manufactured by Mitsubishi Rayon Co., Ltd.; "Kane Ace M-511", "Kane Ace M-600", "Kane AceM-400", "Kane Ace M-580", "Kane Ace MR-01", etc. 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, further preferably 80 nm or more, particularly preferably 100 nm or more, preferably 5,000 nm or less, more preferably 2,000 nm or less, further preferably 1,000 nm or less, and 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 the component (H) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, particularly preferably 0.3% by mass or more, preferably 3% by mass or less, more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, when the non-volatile component in the resin composition is 100% by mass.

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

[0170] <(I) Other additives> In addition to the above-mentioned components, the resin composition may further contain other additives as arbitrary components. As (I) other additives, 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 bentonite and montmorillonite; defoamers such as silicone-based defoamers, acrylic defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion enhancers such as urea silane; adhesion imparting agents such as triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol-based antioxidants; stilbene Fluorescent whitening agents such as derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (such as phosphate compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (such as antimony trioxide); dispersants such as phosphate-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 aids such as tertiary amines; photosensitizers such as pyrazolines, anthracenes, coumarins, xanthones, and thioxanthones. (I) Other additives may be used alone or in combination of two or more in any ratio.

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

[0172] From the viewpoint of significantly obtaining the effect of the present invention, the resin composition preferably contains 0.5% by mass or more and 3% by mass or less of the (J) solvent relative to 100% by mass of all the components of the resin composition. Specifically, for the (J) solvent, relative to 100% by mass of all the components of the resin composition, preferably contains 3% by mass or less, more preferably contains 2% by mass or less, further preferably contains 1.5% by mass or less, preferably contains 0.5% by mass or more, more preferably contains 0.8% by mass or more, and further preferably contains 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 a solvent or the like is added to the compounding components as necessary, and the components are mixed and dispersed using a rotary mixer or the like.

[0174] <Physical Properties and Applications of Resin Composition> The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes shows the characteristic of low dielectric constant. Therefore, an insulating layer with a low dielectric constant is provided. The dielectric constant is preferably less than 3.5, more preferably less than 3.4, and further preferably less than 3.3. The lower limit is not particularly limited, but may be 0.01 or more. The dielectric constant can be measured by the method described in the embodiments described later. The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes shows the characteristic of low dielectric loss tangent. Therefore, an insulating layer with a low dielectric loss tangent is provided. The dielectric loss tangent is preferably less than 0.003, more preferably less than 0.0028, and further preferably less than 0.0025. The lower limit is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be measured by the method described in the embodiments described later.

[0175] The cured product obtained by heat curing the resin composition at 190° C. for 90 minutes shows the characteristic of high maximum point stress. Therefore, an insulating layer with high maximum point stress is provided. The maximum point stress is preferably 100 MPa or more, more preferably 101 MPa or more, and further preferably 102 MPa or more. The upper limit is not particularly limited, but may be 1000 MPa or less, etc. The maximum point stress can be measured by the method described in the embodiments described later.

[0176] The cured product obtained by heat curing the resin composition at 190° C. for 90 minutes shows excellent properties of elongation at break. Therefore, an insulating layer with excellent elongation at break is provided. The elongation at break is preferably 1% or more, more preferably 1.2% or more, further preferably 1.5% or more, 2% or more. The upper limit is not particularly limited, but may be 50% or less, 100% or less, etc. The elongation at break can be measured by the method described in the examples described later.

[0177] The cured product obtained by heat curing the resin composition at 190° C. for 90 minutes shows excellent adhesion (peel strength) to the copper foil. Therefore, an insulating layer with excellent adhesion to the copper foil is provided. The peel strength is preferably 0.3 kgf / cm or more, more preferably 0.35 kgf / cm or more, and further preferably 4 kgf / cm or more. The upper limit is not particularly limited, but may be 10 kgf / cm or less. The peel strength may be measured by the method described in the embodiments described later.

[0178] The resin composition of the present invention can obtain a cured product having excellent dielectric properties, high adhesion to the conductor layer, and excellent mechanical strength. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulating purposes. Specifically, the resin composition of the present invention can be suitably used as: a resin composition for forming an insulating layer (a resin composition for forming an insulating layer for forming a conductor layer), wherein the insulating layer is an insulating layer for forming a conductor layer (including a rewiring layer), and the conductor layer is formed on the insulating layer.

[0179] In addition, in the multilayer printed wiring board described later, it 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 also be suitably used as a resin composition for a rewiring forming layer as an insulating layer for forming a rewiring layer (resin composition for forming a rewiring forming layer), and a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When manufacturing a semiconductor chip package, a rewiring layer can be further formed on the sealing layer. (1) a step of laminating a temporary fixing film on a substrate, (2) a step of temporarily fixing the semiconductor chip on a temporary fixing film, (3) a step of forming a sealing layer on a semiconductor chip, (4) a step of 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 substrate and the temporary fixing film have been peeled off, and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

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

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

[0183] Examples of the support include films made of plastic materials, metal foils, and release papers, and films and metal foils made of plastic materials are preferred.

[0184] When a film formed of a plastic material is used as a support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate (hereinafter sometimes referred to as "PEN"), polycarbonate (hereinafter sometimes referred to as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

[0186] The surface of the support to be in contact with the resin composition layer may be subjected to matte treatment, corona treatment, or antistatic treatment.

[0187] In addition, as a support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent for the release layer of the support with a release layer, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins and silicone resins can be cited. The support with a release layer can use commercially available products, for example: PET film having a release layer with an alkyd resin-based release agent as the main component, "SK-1", "AL-5", "AL-7" made by Lintec, "LUMIRROR T60" made by Toray, "Purex" made by Teijin, "Unipeel" made by UNITIKA, etc.

[0188] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the entire thickness of the support with a release layer is preferably in the above range.

[0189] In one embodiment, the resin sheet may further include other layers as needed. As the other layers, for example, a protective film selected according to the support provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface on the opposite side of the support) can be cited. The thickness of the protective film is not particularly limited, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the attachment of garbage or the formation of damage on the surface of the resin composition layer.

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

[0191] Drying can be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, and the drying is carried out in a manner such that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. The drying conditions also vary depending on the boiling point of the solvent in the resin varnish. For example, when a resin varnish containing 30% to 60% by mass of a solvent is used, a 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 by being wound into a roll. When the resin sheet has a protective film, the resin sheet 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 of 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 and by a method including the following steps (I) and (II): (I) a step of laminating the resin composition layer of the resin sheet on the inner layer substrate so as to bond to the inner layer substrate; and (II) a step of thermally curing the resin composition layer to form an insulating layer.

[0195] The "inner substrate" used in step (I) refers to a component that becomes a 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, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner substrate having a conductor layer (circuit) formed on one or both sides of a substrate is sometimes referred to as an "inner circuit substrate". In addition, an intermediate product to be further formed with an insulating layer and / or a conductor layer when manufacturing a printed wiring board is also included in the "inner substrate" referred to in the present invention. In the case where the printed wiring board is a circuit board with built-in components, an inner substrate with built-in components can be used.

[0196] The lamination of the inner substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner substrate from the support body side. As a member for heat-pressing the resin sheet to the inner substrate (hereinafter also referred to as a "heat-pressing member"), for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller) can be cited. It should be noted that it is preferred that the heat-pressing member is not directly pressed on the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface unevenness of the inner substrate.

[0197] The lamination of the inner substrate and the resin sheet can be implemented by vacuum lamination. In the vacuum lamination, the heating and pressing temperature is preferably 60°C to 160°C, more preferably 80°C to 140°C, the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the heating and pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably implemented under reduced pressure conditions of 26.7hPa or less.

[0198] Lamination can be performed by a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Mfg. Co., Ltd., a vacuum applicator manufactured by Nikko-Materials Co., Ltd., and a batch vacuum pressure laminator.

[0199] After lamination, the laminated resin sheet can be smoothed by, for example, pressing the heating and pressing member from the support body side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing treatment can be the same as the heating and pressing conditions for the above-mentioned lamination. The smoothing treatment can be performed by a commercially available laminator. It should be noted that the lamination and smoothing treatment can be performed continuously using the above-mentioned commercially available vacuum laminator.

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

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

[0202] For example, the heat curing conditions of the resin composition layer vary depending on the type of the resin composition, and 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] The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, 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 further preferably 15 minutes to 100 minutes) before the resin composition layer is thermally cured.

[0204] When manufacturing a printed wiring board, the step of (III) opening holes in the insulating layer, the step of (IV) roughening the insulating layer, and the step of (V) forming a conductor layer can be further implemented. These steps (III) to step (V) can be implemented according to various methods known to those skilled in the art used in the manufacture of printed wiring boards. It should be noted that when the support body is removed after step (II), the removal of the support body can be implemented between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V). In addition, as needed, the formation of the insulating layer and the conductor layer of steps (II) to step (V) can be repeatedly implemented to form a multilayer wiring board.

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

[0206] Step (IV) is a step of roughening the insulating layer. Usually, in this step (IV), contamination is also removed. The steps and conditions of the roughening treatment are not particularly limited, and the known steps and conditions commonly used when forming the insulating layer of the printed wiring board can be adopted. For example, the insulating layer can be roughened by swelling treatment using a swelling solution, roughening treatment using an oxidant, and neutralization treatment using a neutralizing solution in sequence. As the swelling solution used in the roughening treatment, there is no particular limitation, and an alkaline solution, a surfactant solution, etc. can be cited, preferably an alkaline solution, and as the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. As commercially available swelling solutions, for example, "Swelling Dip Securiganth P", "Swelling Dip Securiganth SBU", "Swelling Dip Securigant P" and the like made by Atotech Japan can be cited. The swelling treatment using the swelling solution is not particularly limited, and can be performed, for example, by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred that the insulating layer be immersed in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes. As the oxidant used in the roughening treatment, there is no particular limitation, and an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be cited. The roughening treatment using an oxidant such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidant solution heated to 60°C to 100°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As commercially available oxidants, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing solution Securiganth P" manufactured by Atotech Japan can be cited. In addition, the neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and commercially available products include, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30°C to 80°C for 1 minute to 30 minutes. From the viewpoint of operability, etc., a method in which the object subjected to the roughening treatment with the oxidizing agent is immersed in the 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 roughening treatment is preferably 300nm or less, more preferably 250nm or less, and further preferably 200nm or less. The lower limit is not particularly limited, preferably 30nm or more, more preferably 40nm or more, and further preferably 50nm 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 a 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 comprises one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor layer can be a single metal layer or an alloy layer. As the alloy layer, for example, a layer formed by an alloy of two or more metals selected from the above metals (for example, a nickel-chromium alloy, a copper-nickel alloy and a copper-titanium alloy) can be cited. Among them, from the viewpoints of versatility, cost, ease of pattern formation, etc., of the formation of the conductor layer, preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, and further preferably a single metal layer of copper.

[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 formed of different types of metals or alloys are stacked. When the conductor layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

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

[0211] In one embodiment, the conductor layer can be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. From the perspective of manufacturing simplicity, it is preferably formed by a semi-additive method. An example of forming a conductor layer by a semi-additive method is shown below.

[0212] First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to the desired wiring pattern. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, so that a conductor layer having a desired wiring pattern can be formed.

[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 produced using the printed wiring board of the present invention.

[0214] Examples of the semiconductor device include various semiconductor devices used in electrical products (eg, computers, mobile phones, digital cameras, and televisions) and vehicles (eg, motorcycles, cars, trains, ships, and airplanes).

[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. "Conductive portion" refers to "a portion of a printed wiring board that transmits an electrical signal", which may be a surface or an embedded portion. In addition, the semiconductor chip is not particularly limited as long as it is a circuit element made of semiconductor.

[0216] The method for mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, there are wire bonding mounting methods, flip chip mounting methods, mounting methods based on a built-in non-concave-convex layer (BBUL), mounting methods based on anisotropic conductive film (ACF), and mounting methods based on non-conductive film (NCF). Here, "mounting method based on a built-in non-concave-convex layer (BBUL)" means: "a mounting method in which a semiconductor chip is directly embedded in a recessed portion of a printed wiring board to connect the semiconductor chip to the wiring on the printed wiring board." Example

[0217] The present invention will be specifically described below by way of examples. The present invention is not limited to these examples. It should be noted that, below, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass" respectively unless otherwise indicated.

[0218] <Synthesis Example 1: Synthesis of PPE-1> A 1.5-liter jacketed reactor equipped with an ejector for introducing oxygen-containing gas, stirring turbine blades and baffles at the bottom of the reactor and a reflux condenser at the exhaust line at the top of the reactor was charged with a pre-adjusted mixture of 0.1026 g of cuprous oxide and 0.7712 g of 47% hydrogen bromide, 0.2471 g of N,N'-di-tert-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-tert-butylphenyl)butane (manufactured by ADEKA: AO-30). Next, air was introduced into the reactor from the ejector at a rate of 1.05 L / min while stirring vigorously, and the polymerization temperature was adjusted to 40°C by a heat medium in the jacket. After 160 minutes from the start of air introduction, the air ventilation was stopped, and 1.1021 g of ethylenediaminetetraacetic acid tetrasodium salt tetrahydrate (a reagent manufactured by Dojin Chemical Research Institute) was added to the polymerization mixture in the form of 100 g of aqueous solution, and heated to 70°C. After being kept at 70°C for 2 hours, the catalyst was extracted and the by-product diphenoquinone was removed, and the mixed solution was transferred to a centrifuge manufactured by Shapules Co., Ltd. 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 concentration tank with a jacket, and toluene was distilled off and concentrated to a solid content of 55% by mass in the polyphenylene ether composition solution. Then, toluene was further distilled off using an oil bath set at 230°C and a rotary evaporator, and the solid content was dried to obtain a polyphenylene ether composition.

[0219] <Synthesis Example 2: Synthesis of PPE-2> A stirring bar was placed in a three-necked flask, a serpentine condenser (Dimrothcondenser) equipped with a three-way stopcock was set on the main pipe, and a rubber stopper with a thermometer was installed on 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 installed. After the inside of the flask was replaced with nitrogen, 140 g of toluene was dissolved with 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 into a syringe and added dropwise to the system from the rubber stopper. After the addition was completed, stirring was continued at room temperature for 3 hours, and the flask was heated in an oil bath to continue the reaction under reflux. The heating was stopped at the stage after 2 hours from the start of reflux, and 1.00 g of methanol was added to stop the reaction after returning to room temperature. Next, the reaction solution was concentrated to a solid content concentration of 20% by weight, and then washed with ion exchange water of the same weight as the concentrated solution. Then, the water tank was removed, and methanol (5 times the weight of the organic layer) was added dropwise to the organic layer while stirring. Then, the precipitate was filtered, and the filtrate was vacuum dried at 110° C. for 1 hour to obtain a modified polyphenylene ether composition.

[0220] <Synthesis Example 3: Synthesis of PPE-3> A 1.5-liter jacketed reactor equipped with an ejector for introducing oxygen-containing gas, stirring turbine blades and baffles at the bottom of the reactor and a reflux condenser at the exhaust line at the top of the reactor was charged with a pre-adjusted mixture of 0.1026 g of cuprous oxide and 0.7712 g of 47% hydrogen bromide, 0.2471 g of N,N'-di-tert-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) (manufactured by ADEKA: AO-60). Next, air was introduced into the reactor from the ejector at a rate of 1.05 L / min while stirring vigorously, and the polymerization temperature was adjusted to 40°C by a heat medium in the jacket. After 160 minutes from the start of air introduction, the air ventilation was stopped, and 1.1021 g of ethylenediaminetetraacetic acid tetrasodium salt tetrahydrate (a reagent manufactured by Dojin Chemical Research Institute) was added to the polymerization mixture in the form of 100 g of aqueous solution, and heated to 70°C. After being kept at 70°C for 2 hours, the catalyst was extracted and the by-product diphenoquinone was removed, and the mixed solution was transferred to a centrifuge manufactured by Shapules Co., Ltd. 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 concentration tank with a jacket, and toluene was distilled off and concentrated to a solid content of 55% by mass in the polyphenylene ether composition solution. Then, toluene was further distilled off using an oil bath set at 230°C and a rotary evaporator, and the solid content was dried to obtain a polyphenylene ether composition.

[0221] <Determination of number average molecular weight (Mn)> As a measuring device, a gel permeation chromatography System 21 manufactured by Showa Denko was used, and a standard curve was prepared using standard polystyrene and ethylbenzene. The number average molecular weight (Mn) of the obtained PPE-1, PPE-2 and PPE-3 was measured using the standard curve. As standard polystyrene, polystyrene with molecular weights of 3650000, 2170000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, and 550 was used. The column used a chromatographic column in which two K-805L manufactured by Showa Denko were connected in series. Chloroform was used as the solvent, the flow rate of the solvent was 1.0 mL / min, and the temperature of the column was set to 40°C for measurement. As a sample for measurement, a 1 g / L chloroform solution of PPE-1 synthesized in Synthesis Example 1 was prepared and used. The UV wavelength of the detection part is 254 nm in the case of standard polystyrene and 283 nm in the case of 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 temperature increase rate of 20°C per minute, then cooled to 50°C at a temperature increase rate of 20°C per minute, and then the glass transition temperatures were measured at a temperature increase rate of 20°C per minute.

[0223] <Determination of the number of terminal hydroxyl groups contained in resin> Weigh 5.0 mg of PPE-1 and PPE-3. Then, dissolve the weighed PPE-1 in 25 mL of dichloromethane. After adding 150 μL of 2% by mass tetraethylammonium hydroxide (TEAH) ethanol solution to 2.0 mL of the prepared solution, use a UV spectrophotometer (Hitachi: U-3210 model) to measure the absorbance (Abs) at 318 nm (using a cell with a cell length of 1 cm for absorbance measurement). Then, based on the measurement results, the simulated molecular weight obtained by the absorbance is obtained by the following mathematical formula (1). Formula (1): Simulated molecular weight obtained from absorbance (g / mol) = [((ε×5) / (25×Abs)] In formula (1), ε represents the absorption coefficient, which is 4700 L / mol·cm. In addition, the number of OH terminals per 1 g of PPE-1 or PPE-3 (μmol / g) was calculated by multiplying the reciprocal of the above-mentioned simulated molecular weight by 106.

[0224] <Determination of the Number of Terminal Methacryloyl Groups Contained in Resin> A predetermined amount of PPE-2 synthesized in Synthesis Example 2 and a 1,3,5-trimethoxybenzene standard (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight 168.19) as an internal standard sample were dissolved in deuterated chloroform to which trimethylsilane was added. 1 H-NMR measurement (manufactured by JEOL, 500 MHz).

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

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

[0227] [Table 1] (Table 1)

[0228] <Synthesis Example 4: Synthesis of Maleimide A> A MEK solution of maleimide compound A synthesized by the method described in Synthesis Example 1 of Japan Invention Association Publication No. 2020-500211 (non-volatile content 62% by mass, t" = 1.47 (mainly 1, 2 or 3), Mw / Mn = 1.81) was prepared. The maleimide compound A has a structure represented by the following formula (1). [Chemical formula 10]

[0229] <Synthesis Example 5: Synthesis of Polyimide B> Prepare a 500mL separable flask with a moisture quantitative receiver connected to a reflux condenser, a nitrogen inlet tube and a stirrer. Add 20.3g of 4,4'-oxydiphthalic anhydride (ODPA), 200g of γ-butyrolactone, 20g of toluene and 29.6g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane to the flask, stir at 45°C for 2 hours under a nitrogen stream, and react. Next, the reaction solution was heated, and the condensation water was removed azeotropically with toluene under a nitrogen stream while being maintained at about 160°C. It was confirmed that a specified amount of water was accumulated in the moisture quantitative receiver, and that water outflow was no longer observed. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. Then, the mixture was cooled to obtain a polyimide solution (non-volatile content 20% by mass) containing a polyimide resin having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin has a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). In addition, the weight average molecular weight of the above polyimide resin is 12,000. [Chemical formula 11]

[0230] <Manufacture of resin varnish> Each component was weighed according to the mass fraction described in the table, and 10 parts of MEK and 10 parts of cyclohexanone were further mixed and uniformly dispersed using a high-speed rotary mixer to obtain a resin varnish. It should be noted that the details of each component described in the table are as follows.

[0231] [Table 2] (Table 2)

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

[0233] <Determination of dielectric constant, dielectric loss tangent, and mechanical strength> (1) Preparation of Resin Sheet A Having a Resin Composition Layer Thickness of 40 μm As a support, a polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) having a release layer was prepared. On the release layer of the support, the resin varnish obtained in the examples and comparative examples was evenly applied so that the thickness of the resin composition layer after drying was 40 μm. Then, the resin composition was dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain a resin sheet A comprising a support and a resin composition layer.

[0234] (2) Preparation of Cured Material of Resin Composition Layer The resin sheets A obtained in the examples and comparative examples were 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) Determination of dielectric constant and dielectric loss tangent (dielectric properties) The cured product was cut into pieces of 80 mm in length and 2 mm in width, and the dielectric constant and dielectric loss tangent (Dk value, Df value) were measured by the resonant cavity perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. and 90° C. using "HP8362B" manufactured by Agilent Technologies. The measurement was performed on two test pieces, and the average value was calculated.

[0236] (4) Determination of maximum point stress and elongation at break (mechanical strength) The tensile strength of the cured product was measured using a tensile tester "RTC-1250A" manufactured by Orientec, and the maximum stress at 23°C and the elongation at break were measured. The measurement was carried out in accordance with JIS K7127. The measurement was performed 5 times, and the average of the top 3 values ​​from the largest to the smallest was calculated.

[0237] <Evaluation of Adhesion> (1) Base treatment of copper foil The shiny surface of the electrolytic copper foil (Mitsui Mining and Co., Ltd. "3EC-III", thickness 35 μm) was etched 1 μm with a microetchant (MEC "CZ8101") to roughen the copper surface, and then a rust-proof treatment (CL8300) was performed. The copper foil etched with the microetchant is sometimes referred to as "CZ copper foil" below. Furthermore, the copper foil was heated in an oven at 130°C for 30 minutes to obtain a copper foil I having a roughened surface.

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

[0239] (3) Lamination of resin composition layers The resin sheets prepared in the embodiments and comparative examples are laminated on both sides of the inner substrate. The lamination is performed using a batch vacuum pressurized laminator (Nikko-materials, 2-stage stacking laminator "CVP700") in such a way that the resin composition layer is in contact with the inner substrate. In addition, the lamination is performed by reducing the pressure for 30 seconds to adjust the air pressure to less than 13hPa, and then pressing at 120°C and a pressure of 0.74MPa for 30 seconds. Next, the laminated resin sheet is hot-pressed at 100°C and a pressure of 0.5MPa for 60 seconds. Then, the support is peeled off to expose the resin composition layer.

[0240] (4) Lamination of copper foil and curing of resin composition layer: Under the same conditions as in the above-mentioned "(3) Lamination of resin composition layer", the treated surface of copper foil I was laminated on the exposed resin composition layer. Then, the resin composition layer was cured under the curing conditions of 200°C and 90 minutes to form an insulating layer comprising a cured product of the resin composition. Through the above operation, an evaluation substrate C having CZ copper foil laminated on both sides of the insulating layer was obtained. The evaluation substrate C had a layer structure of copper foil I / insulating layer / inner substrate / insulating layer / copper foil I.

[0241] <Measurement of Adhesion (Peel Strength) with Copper Foil> The evaluation substrate C was cut into small pieces of 150 mm × 30 mm. In the small piece of copper foil I, a cutter was used to cut a cut that surrounded a portion with a width of 10 mm and a length of 100 mm. One end of the portion was peeled off and clamped with the clamp of a tensile testing machine (AUTOCOM universal testing machine "AC-50C-SL" manufactured by TSE). At room temperature (25°C), it was stretched in the vertical direction at a speed of 50 mm / min, and the load [kgf / cm] when peeling off 35 mm was measured as the peel strength of the copper foil. The measurement was carried out in accordance with Japanese Industrial Standard JIS C 6481. It should be noted that in Comparative Example 3, expansion occurred between the copper foil and the insulating layer, and the peel strength could not be measured.

[0242] [Table 3] (Table 3)

Claims

1. A resin composition, wherein contain: (A) polyphenylene ether resin having a terminal functional group number greater than 2, (B) Epoxy resin, (C) a curing agent, and (D) Inorganic filling materials.

2. The resin composition according to claim 1, wherein The component (A) has a structure represented by the following formula (A-1), In formula (A-1), X represents an a-valent linking group, Z each 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 the formula (A-2), or a halogen atom, However, R 22 and R 24 In the case of hydrogen atoms, R 22 and R 24 Except when one of them is a group represented by formula (A-2) and the other represents a hydrogen atom, a methyl group or an ethyl group, a and b each independently represent an integer of 2 to 6, k each independently represents an integer of 1 to 4, n each independently represents an integer from 0 to 200; 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, * indicates a bond, d and e independently represent 0 or 1; 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 hydroxyl group, a monovalent hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylamino group or a hydroxyalkyl group having 1 to 30 carbon atoms, s represents an integer of 0 to 5, * indicates a bonding 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 phenolic curing agent.

5. The resin composition according to claim 1, wherein It further contains (E) a radical polymerizable compound.

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

7. A resin sheet, wherein: Include: Support body, and A resin composition layer provided on the support and comprising the resin composition according to any one of claims 1 to 6.

8. A printed wiring board, wherein: An insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 6.

9. A semiconductor device, wherein: A printed wiring board comprising the method according to claim 8.

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